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BACKGROUND OF THE INVENTION
The present invention relates to a method of modifying a polymer surface by covalent attachment of functional compounds, also designated ligands.
1. The Technical Field
Products made of synthetic or natural polymers having modified surfaces are very important in many technical areas.
Surface modification of polymers by the introduction of various functional groups or the covalent attachment of biologically active molecules has been the subject of increased research in recent years in such different areas as the development of novel biocompatible implants, for biosensors and biomaterials, for affinity chromatography, for surface resistant materials, for biosensors, and for covalent immobilization of high or low molecular weight molecules in ELISA assays.
2. Prior Art
Thermochemical Methods
Most methods involve sequential treatment of the polymer surface with chemical reagents to introduce functional groups to function as handles for coupling of a functional compound also called ligand. However, these methods usually employ hazardous chemicals and several time-consuming steps. In addition to this, only a limited number of methods are described in which the mechanical and optical properties of the polymer can be preserved. A method of introducing primary amino groups onto polystyrene tubes using thermochemical reactions and onto microtitre plates has been described by Alexio, J. A. G.; Swaminathan, B; Minnich, S. A.; Wallshein, V. A.; J. Immunoassay 1985, 6, 391-407.
Radioanalytical Methods
EP-A-O 155 252 discloses a method of preparing an immunoreactive solid phase wherein a biologically active molecule is covalently bound to functional groups of vinyl monomers radiation grafted to a solid polymer surface. Grafting requires an adequate radiation dose under an inert atmosphere using radiation such as ultraviolet or ionizing radiation. Specific examples using 0,25 Mrad/h 60 Co irradiation source for 10-12 hours are given.
International application no. WO 91/02768 discloses radio-derivatized polymers produced by contacting non-polymerizable conjugands, such as quinones or compounds from which quinones or quinoid structures are generated during radio-derivatization, with radiolyzable polymers, such as polystyrene, in the presence of high energy gamma rays. The radio-derivatized polymers are suitable for introducing anchoring groups for covalent immobilization or for fixing of molecules on polymer surfaces with or without cross-linkers or with activators such as carbodiimides.
A disadvantage of radio-derivatization is the use of ionizing high energy gamma rays which requires costly health physical precautions in carrying out the method.
Photochemical Methods
A number of photochemical methods of modifying polymer surfaces are also known. In these methods a desired ligand (L)--often a sensitive biomolecule--is immobilized on the polymeric material surface (P) through a photochemically reactive group (Q) and a spacer (S) and optionally a thermochemical reactive group (T).
In general, the covalent attachment of the desired molecule (L) to the surface can be established in three ways:
1) The photochemically reactive group (Q) which is coupled--via a spacer (S)--to a thermochemical reactive group (Q-S-T) is bound covalently to the surface (P) by a photochemical reaction (P-Q-S-T). Subsequently, the desired molecule (L) is coupled to the surface (P-Q-S-T) by thermochemical reaction (P-Q-S-T-L).
2) The photochemically reactive group (Q) which is coupled directly--via a spacer (S)--to the desired molecule (Q-S-L) is bound to the surface (P) by a photochemical reaction (P-Q-S-L).
3) The photochemically reactive group (Q) is coupled covalently to the surface (P) by a thermochemical reaction (P-Q). Subsequently, the desired molecule (L) is coupled to the surface (P-Q) by a photochemical reaction (P-Q-L).
The first two strategies are potentially the most flexible ones and allow control of the orientation of the immobilized ligand.
EP-A2-0 319 953 discloses a photochemical method of modifying a polymer surface by immobilizing an optionally substituted two or three membered heterocyclic compound to the surface of the polymer using electromagnetic irradiation with a wavelength shorter than 700 nm. Preferred compounds are optionally substituted coumarins, benzofurans, indols, and angelicins. Particularly, optimally substituted psoralens are preferred.
A disadvantage of this method is that psoralens are multifunctional compounds which are not easy to synthesize. They are expensive and not chemically stable, e.g. spacers containing primary amines (as a functional group) can not be introduced onto the surface, because the amine will react with the psoralen.
When irradiated with UV light having a short wavelength, a secondary amine placed in the end position and coupled--via a spacer--to psoralen can be photochemically bound to a polystyrene surface. When biotin is coupled to the spacer derivative, biotin can also be photochemically bound to polystyrene surfaces and polymethyl-methacrylate particles. The method cannot be considered to be generally applicable, as only these two examples work satisfactorily. The photochemical mechanism has not been fully understood, but it is known that psoralen derivatives react with double bonds in a 2+2 cyclo addition reaction when irradiated with UV light.
A number of patent publications U.S. Pat. Nos. 4,722,906, 4,973,493, 5,002,582 and PCT/US88/04491, assigned to Biometric Systems Inc., disclose methods for photo-chemical modification of polymer surfaces. The patent publications essentially describe methods involving activating latent reactive groups selected from the group consisting of those able to generate free radicals, carbenes, nitrenes and exited states of ketones, and covalently bonding thereof to a solid surface.
The disclosed latent reactive groups responsive to ultra-violet, visible or infrared portions of the electromagnetic spectrum are: azides, acylazides, azido formates, sulfonyl azides, phosphoryl azides; diazo compounds such as diazoalkanes, diazoketones, diazoacetates, beta-ketone-alpha-diazoacetates; aliphatic azo compounds, diazirines, ketone, diphenylketone and photoactivable ketones such as benzophenone and acetophenone; and peroxy compounds such as dialkyl- and diacyl peroxides and peroxyesters.
Latent reactive groups, which upon irradiation with high energy UV light generates highly reactive radicals, carbenes or nitrenes, suffer from a number of drawbacks. Such species are extremely reactive and will either rear-range or immediately react with most organic compounds, organic solvents and water. When the irradiation takes place in a solution, this results in loss of photoreagent and ineffecient or reaction with the polymer surface. The simple precursors requires long irradiation times (typically 12 hours) which makes the application of these as photoreactive groups time consuming, inefficient and not suitable for immobilization of sensitive biomolecules.
Nothing is indicated nor suggested about photochemical coupling using quinones as the photoreactive group.
DISCLOSURE OF THE INVENTION
It is an object of the present invention to provide a photochemical method of immobilizing a desired ligand on a carbon-containing material surface which method does not suffer from the drawbacks described above.
A particular object of the invention is to provide a photochemical method which can be used generally to immobilize ligands on carbon-containing material surfaces.
Another particular object is to provide a photochemical method of immobilizing a ligand on a carbon-containing material surface which method is easier and less expensive to carry out and control, and which method is optimally faster than the known methods.
A further object of the present invention is to provide a photochemical method of immobilizing ligands on carbon-containing material surfaces, where the ligands are not subjected to damaging treatments and therefore substantially maintain their functions, even when the ligands are sensitive biomolecules.
This object is achieved by providing a method of immobilizing a ligand (L) to the surface (P) of a carbon-containing substrate material; said method comprising:
a photochemical step of linking of one or moreligand (L) via one or more photochemically reactive compounds (Q) to a carbon-containing material surface (P);
said carbon-containing material surface (P) being linked to the photochemically reactive compound (Q) either directly or via one or more spacers (S 1 ); and
said photochemically reactive compound (Q) being linked to one or more ligands (L) either directly or optionally via one or more spacers (S) and/or thermochemically reactive compounds (T);
said spacers (S 1 ) and (S) being, equal or different, thermochemically or photochemically reactive or non-reactive spacers;
wherein the photochemically reactive compound (Q) is a quinone compound selected from the group consisting of monomeric quinone compounds, dimeric quinone compounds, and symmetrical or asymmetrical oligomeric quinone compounds;
said quinone compound (Q) containing a cyclic hydrocarbon, or from 2 to 10 fused cyclic hydrocarbons, said quinone compound having at least two conjugated carbonyl groups, the number of which does not exceeding twice the number of fused cyclic hydrocarbons;
said quinone compound (Q) optionally being substituted with substituents (R) which do not result in steric hindrance to the immobilization of the ligand (L) or do not disturb the photochemistry; and
wherein the photochemical step comprises irradiation of the photochemically reactive compound (Q) with non-ionizing electromagnetic radiation having a wavelength in the range from UV to visible light, provided that said carbon-containing material does not consist of a nucleic acid probe.
The invention is based on the surprising finding that said quinone compounds as defined in claim 1 can be used as the photochemically reactive compound with very good results.
Quinone compounds are known as photochemically reactive compounds, but their use as photochemically reactive coupling compounds has never been suggested, even though there has been a rush in the development of new methods for immobilization of ligands to polymer surfaces.
Quinone Compounds
Quinone compounds are defined as compounds comprising at least 2 conjugated carbonyl groups placed in at least one cyclic hydrocarbon structure. Such compounds are well-known to a person skilled in the art.
The quinones suitable for use in the method according to the present invention are quinone, quinone dimers or oligomers of quinones, the latter having symmetrical or asymmetrical bonded quinones.
The quinone compound contains a cyclic hydrocarbon, or from 2 to 10 fused cyclic hydrocarbons, having at least two conjugated carbonyl groups. The number of carbonyl groups does not exceed twice the number of fused cyclic hydrocarbons.
The cyclic hydrocarbons may be fused in any position isomer.
The quinone compound is optionally being substituted with substituents (R) which do not result in steric hindrance to the immobilization of the ligand (L) or do not disturb the photochemistry, e.g. that the substituent has a chromophore which inhibits the activation of the quinone, e.g. by fluorescence, phosphorescence, radiation less transition, etc.
The cyclic hydrocarbons may independently of each other be of any ring size but are preferentially 5, 6, 10, 14, 18 carbon atom-membered aromatic rings which independently of each other may comprise one or several hetero atoms selected among --N--, --NH--, and --O--. The conjugated carbonyl groups may be located in any of these rings in any position provided that the quinoid structure is maintained.
Applicable Basic Quinone Compounds
Illustrations of applicable basic quinone compounds are shown in FIG. 1, wherein the compounds I-XXXVI may be substituted with one or more of the substituents R defined below.
Particularly Preferred Quinones
Particularly preferred quinones are claimed in claims 3 and 4.
In the preferred embodiment having the general formulas (XXXVII), (XXXVIII), and (XXXIX), also shown in FIG. 2, the letters m, n and o designate 0 or integers from 1-8, the sum of m, n and o being 8 or less; l indicates 0 or an integer from 1 to two times n; r and q indicate 0, 1 or 2; k indicates 0 or an integer from 1 to 2 times m; and t indicates 0 or an integer from 1 to 2 times o.
It is preferred that the sum of m, n and o is 8 or less.
R designates substituents as defined below.
The substituents are selected independently of each other. Preferably the total sum of the number of substituents (1+r+k+q+t) is less than the number of fused cyclic hydrocarbon compounds.
Specifically preferred quinones are selected from the group consisting of:
anthraquinones (V, VI, VII, X, XI, XIII, XXVIII), phenanthrenequinones (VIII, IX, XII), benzoquinones (I, II), naphthoquinones (III, IV, XXVII), and compound (XXVI, XXIX), particularly anthraquinones, phenanthrenequinones, and compound (XXVI).
Substituents R
The choice of substituents are important in controlling the solubility of the quinone and the overall affinity of the quinone towards the material surface; e.g. introduction of charged substituents will enhance the solubility in water and also increase or decrease the affinity towards charged material surfaces via attractive or repulsive ionic interactions. Thus, the substituents R may be selected in relation to the optimal hydrophobic/hydrophilic character which depends on the system and the solvent in which the photoreactive step takes place. Optimally, the quinone compound is partly soluble in the solvent.
The quinones are preferably substituted with a number of substituents which are less than three times the number of fused cyclic hydrocarbons, but they may, however, be completely saturated with substituents, provided that the quinoid structure is maintained.
Specifically the substituents (R) can themselves be quinones.
The useful substituents R may independently of each other be selected among the group consisting of:
functional groups comprising --NO 2 , --SO 3 - , --SO 2 - , --CN, --PO 3 2- , --PO 2 - , --COOH, halogen, i.e. --F, --Cl, --Br, --I, primary amines, secondary amines and tertiary amines, or derivatives thereof; and
hydrocarbyls which may be substituted with: --NO 2 , --SO 3 - , --CN, --PO 3 2- , --PO 2 - , --COOH, halogen, i.e --F, --Cl, --Br, --I, epoxide, and --H;
said hydrocarbyls comprising alkyl having from 1-30 C-atoms, alkenyl having from 1-30 C-atoms, alkynyl having from 1-30 C-atoms, aryl having from 6-50 C-atoms, preferably 6-18 C-atoms, and derivatives thereof comprising combinations of these with equal or different substituents for the functional groups defined above; and
said hydrocarbyl being straight/branched-chained, symmetric/asymmetric, chiral/achiral; containing one or more heteroatoms selected from the group consisting of --N--, --NH--, and --O--; or being fused, aromatic systems;
said fused, aromatic system containing one or more heteroatoms being heterocyclyl selected from the group consisting of pyridyl, imidazoyl, pyrimidinyl, pyridazinyl, quinolyl, acridinyl, imidazolyl, pyrrolyl, furyl, isoxazolyl, oxazolyl, which may be bound and/or fused in any position, and derivatives thereof comprising combinations of these with equal or different substituents as for the functional groups defined above.
Preferred substituents R are selected from the group consisting of: functional groups comprising --NO 2 , --SO 3 - , --SO 2 - , --CN, --PO 3 2- , --PO 2 - , --COOH, halogen, i.e. --F, --Cl, --Br, --I, primary amines, secondary amines and tertiary amines, or derivatives thereof; and hydrocarbyls which may be substituted with: --NO 2 , --SO 3 - , --CN, --PO 3 2- , --PO 2 - , --COOH, halogen, i.e --F, --Cl, --Br, --I, epoxide, and --H.
Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, undecanyl, dodecanyl, tridecanyl, tetradecanyl, pentadecanyl, hexadecanyl, heptadecanyl, octadecanyl, nonadecanyl, eicocanyl, straight or branched, with one or more double or triple bonds.
Preferred aryls are phenyl, naphtyl, biphenyl, tolyl, benzyl, cumenyl, mesityl, xylyl, pentalenyl, indenyl.
Non-ionizing Electromagnetic Irradiation
The electromagnetic radiation is chosen in order to activate the quinones. It is a non-ionizing electromagnetic radiation having a wavelength in the range from UV to visible, preferably shorter than 700 nm.
Normally the electromagnetic radiation is selected with a band of wavelengths in the range from 15 to 50 nm around a center wavelength. This band of wavelengths is chosen in order to be able to activate the quinones with electromagnetic radiation providing maximal absorption of the quinone chromophores.
The UV-light has a wavelength from UV to visible in order to minimize the interaction of the light with functional groups and sensitive ligands or biomolecules covalently linked to the quinones, such groups typically sensitive to electromagnetic radiation having wavelengths shorter than UV, whereby they are destroyed. It is thus possible to select an electromagnetic radiation having a wavelength in the wide range of wavelength where the quinones absorb electromagnetic radiation which selected radiation specifically activates the photochemically active group of interest.
Besides the above-mentioned special absorption properties of quinones, the high efficiency in the photoinduced immobilization of ligands observed in this invention, can in part be explained by the fact that the reactive state of the quinone (n¶*) is obtained in a very high yield upon excitation in the whole absorbtion range.
Normally incoherent continuous light will be chosen to activate the photoprobes. But the application of more complicated light sources such as monochromatic, polarized, pulsed or coherent light can be used.
In the examples described later on, a HPA lamp from Philips was used as light emitting source. Such HPA lamps are tubular medium-pressure metal halide lamps with iron and cobalt additives.
The lamps emit non-ionizing UV-light from 250 to 400 nm (corresponding to long-wave UV-A and UV-B, mainly 300-400 nm), and visible light from 400 to 700 nm, which makes the lamps suitable for use in the present method.
Irradiation times are selected in order to obtain a sufficient yield without degradating the immobilized ligand (L) or the carbon-containing material surface (P). The irradiation time is generally shorter than 12 hours, preferably less than 200 minutes, more preferably less than 60 minutes, most preferably less than 30 minutes.
Ligands
A ligand (L) is defined as a surface modifying compound which after immobilization to the polymer surface provides the polymer surface with a new surface characteristic.
The ligand (L) can be a functional group such as:
--COOH (carboxylic acids), sulfonic acid derivatives, --COOR (esters, including active esters), --COX (acid halides, acid fluorids and acid chlorides, acid azides or similar active carboxylic acid derivatives), --CONHNH 2 (acid hydrazides), --NHCONHNH 2 (semicarbazides), --NHCSNHNH 2 (thiosemicarbazides), --CN (nitriles), --CHO (aldehydes), RR'CO (ketons), --OH (alcohols), --SH (thioles), --SSR (disulfides), --NH 2 (amines, including primary, secondary and tertiary amines), --NHNH 2 (hydrazines), --OR (ethers), epoxides, --SR (sulfides), --X (halides: fluoride, chloride, bromide, or iodide), --NO 2 , --CH 3 . Also, the ligand can be a biologically active molecule, such as biotin, toxins, herbicides, pesticides, carbohydrates, antibiotics (e.g. penicillins and other drugs, e.g. cell poisons), steroids, peptides, nucleotides, peptide nucleic acids (PNA) and nucleic acid binding partners, proteins and haptenes, functional groups (or derivatives thereof) or non-functional groups, such as methyl, ethyl, isobutyl, tertbutyl or aromates. These non-functional groups may e.g. be used to improve the biocompatibility of contact lenses, implants, etc.
Spacer
The spacers (S 1 ) or (S) are generally chosen with respect to length, flexibility, hydrophobic/hydrophilic character for each specific new surface characteristic.
The spacer (S 1 ) or (S) is as a thermochemically or photochemically non-active distance making compound.
Optionally, the ligand is linked to the polymer surfaces via a spacer, the only function of which is to make space between the two and thereby make the immobilization easier, particularly when the ligand is a large molecule. The spacer also provides for more ligands to be immobilized on the polymer surface.
The length of the spacer is selected for the specific purpose. Generally, the length is less than or about 400 Å. In some applications, preferably less than about 100 Å. In case of longer lengths of the spacer it is preferred to link more ligands to each spacer unit.
The spacer is also selected with respect to its hydrophobic/hydrophilic character. If e.g. the spacer links the quinone to the ligand before the photoreaction to the polymer, it is very important to optimize the hydrophobic/hydrophilic character of the total Q-S-L molecule in order to obtain optimal reaction conditions also depending on the solvent in the photoreactive step.
Examples of spacers are C 1 -C 20 alkyl groups, e.g. polymethylene, optionally containing aromatic or mono/polyunsaturated hydrocarbons, polyoxyethylene such as polyethylene glycol, oligo/polyamides such as poly-β-alanine, polyglycine, polylysine, peptides in general, etc., oligosaccharides, oligo/polyphosphates such as phospho-mono/diesters, mono/diamides, etc., oligo/polysulfonic amides/esters. Moreover, the spacer may consist of combined units of the aforementioned or combined units thereof.
The importance of optimizing the spacer length and other properties are clearly illustrated in example 3 in which the photochemical grafting of primary amino groups is detected by the following thermochemical coupling of biotin and detection of the immobilized biotin with avidin. In this example a stepwise elongation of the spacer with β-alanine units was used. The oligoamide nature of the spacer allowed the easy synthesis of each compound using standard amide bond forming reactions and standard protecting group and deprotection schemes. In contrast to e.g. a simple aliphatic carbon spacer the oligoamide spacer is rather rigid due to the hindered rotation around the amide bonds and rather hydrophilic--but neutral--due to the ability of each amide bond to act both as donor and acceptor of hydrogen bonds. The optimum spacer length for this particular purpose was found to be anthraquinone amine compound 9. Increasing the spacer length with one more β-alanine unit did not increase the signal, but indicated a small decrease of signal (data not shown). This optimization of the spacer length for the biotin-avidin system is consistent with reports in the literature (see e.g. F. Kohnen et al., Complementary Immunoassays, page 62 (W. P. Collins ed.) John Wiley & Sons, New York, 1988).
Thermochemical Reactive Groups
Thermochemical reactive groups (T) are well-known in the art and are defined as functional groups, which are able to form covalent bonds to polymer surfaces (P) or ligands (L) under conditions in which the photochemically reactive group is non-reactive.
The thermochemical reactive groups may be --COOH (carboxylic acids), sulfonic acid derivatives, --COOR (esters, comprising active esters), --COX (acid halides, acid azides and similar carboxylic acid derivatives), --CONHNH 2 (acid hydrazides), --NHCONHNH 2 (semicar-bazides), --NHCSNHNH 2 (thiosemicarbazides), --CHO (aldehydes), RR'CO (ketones), --OH (alcohols), --X (halides: chloride, bromide, iodide), --SH (thioles), --SSR (disulfides), --NH 2 (amines, comprising primary, secondary and tertiary amines), --NHNH 2 (hydrazines), epoxides, maleimides.
One of the major advantages in this invention is the chemical stability of the quinone compounds. Thus, thermochemically reactive groups will not react with the quinones.
This is illustrated in synthesis of antraquinone acid hydrazide (compound 12, example 1) and antraquinone thiosemicarbazide (compound 15, example 1). Using benzophenones as the photochemically reactive group, the synthesis of such compounds would be impossible, as the acid hydrazide or thiosemicarbazide would condensate with the carbonyl group in the benzophenone, giving either cyclic compounds or oligomers.
Carbon-containing Material Surface
It is preferred that the carbon-containing material surface is a polymer surface.
The polymer may be any kind of polymer. Particularly preferred polymers are selected from the group consisting of: synthetic and natural polymers such as polystyrene, polyethylene, polyvinylacetate, polyvinylchloride, polyvinylpyrrolidone, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene, polycarbonate, poly-4-methylpentylene, polyester, polypropylene, cellulose, nitrocellulose, starch, polysaccharides, natural rubber, butyl rubber, styrene butadiene rubber, silicone rubber.
Also, the carbon-containing material can be selected from the group consisting of: premodified materials including silica, glass, control-led pore glass, silica gel, or metal which materials have been premodified to contain carbon; monolayer or multilayer films; Langmuir-Blodgett-films; micelles; biological membranes; proteins; nucleotides, peptide nucleic acids (PNA) and nucleic acid binding partners, natural or synthetic polymers coated with biological or organic material.
The polymer surfaces may e.g. be premodified by e.g. a corona treatment, a treatment of γ-lightening and silylation. Such treatment may enhance the reactiveness of the polymer and/or modify the hydrophobic or hydrophilic character of the surface.
The carbon-containing material may also be a silica, a glass, a controlled pore glass and a silica gel, or a metal which has been premodified to contain carbon, e.g. by silylation so as to make the surface able to form covalent bonds to other compounds, i.e. a quinone compound or a thermochemically reactive compound.
In the following the carbon-containing material surface is described as the "polymer surface" or "substrate". However, it is to be understood that the above-mentioned non-polymer surfaces may be treated as well.
Preferred Methods of Preparation
Preferred methods of carrying out the invention are defined in claims 11-16, wherein the respective compounds are linked to each other in a number of different ways.
A person skilled in the art will know that the method can be carried out in many other ways within the scope of the invention.
Preferred and illustrative embodiments (a)-(f) of the invention comprise the following reaction steps:
______________________________________a) Step 1: Q + L → Q-L Step 2: Q--L + P → P--Q-L (Photoreactive step)b) Step 1: Q + S → Q-S Step 2: Q-S + L → Q-S-L Step 3: Q-S-L + P → P--Q--S--L (Photoreactive step)c) Step 1: P + Q → P-Q ((Photoreactive step)) Step 2: P-Q + L → P-Q-L ↓d) Step 1: P + S.sub.1 → P-S.sub.1 Step 2: P-S.sub.1 + Q → P-S.sub.1 -Q (Photoreactive step) Step 3: P-S.sub.1 -Q + L → P-S.sub.1 -Q-L ↓e) Step 1: Q + T → Q-T Step 2: Q-T + P → P-Q-T (Photoreactive step) Step 3: P-Q-T + L → P-Q-T-Lf) Step 1: Q + S → Q-S Step 2: Q-S + T → Q-S-T Step 3: Q-S-T + P → P-Q-S-T (Photoreactive step) Step 4: P-Q-S-T + L → P-Q-S-T-L______________________________________
In embodiment (f) the reaction order of S and T may be reversed in the steps 1 and 2.
Photoreactive Step
The photoreactive step can be carried out as described under Examples, and the thermochemical reactions can be carried out using standard synthetic procedures as known to a person skilled in the art.
Quinone-ligand Linking
Q may be linked to L by any synthetic methods of linking similar compounds. The bond obtained is preferably a covalent bond such as a C--C bond, a bond through acid derivatives (e.g. ester, amide, etc.), an ether bond, an amine, a sulfide or a disulfide bond. The reaction is carried out in a suitable solvent. After completed reaction, the solvent may be removed by e.g.. evaporation, decantation or filtration, or the solvent may be replaced by another solvent which is more suitable for the following photoreaction, where Q-L is linked to P. This reaction is preferably carried out in an aqueous solvent, where Q-L is brought into contact with P. The ligand L may have to be protected with one or more protecting groups during the photoreaction. The protecting groups can be selected so as to mask the sensitive functionalities of the ligand during the photochemical step, and so that the ligand can become unmasked in a subsequent step after the photoimmobilization.
The solvent is optimally the same in all steps of coupling of the compounds.
Covalent Bonding
The reaction involved in forming the covalent bonds may be selected among the standard synthetic procedures known to a skilled person, e.g. standard organic synthesis, peptide synthesis, oligonucletide synthesis and related areas. When using intermediates having multiple functional groups suitable semipermanent and/or transient protecting groups can be chosen to mask selected functional groups, thereby allowing regioselective synthesis of the Q-L and Q-S-L molecule. For well known techniques of protecting functionalities see T. W. Greene and P. G. M. Wuts, "Protective Groups in Organic Synthesis", John Wiley & Sons, New York, 1991.
Illustrative synthesis og Q-L and Q-S-L molecules, including selection of bond forming reactions and selection of suitable protective groups are illustrated in example 1.
Solvent
The solvent used in the photochemical step is preferably an aqueous medium or an aqueous medium containing up to 10% v/v of organic solvent, preferably up to 5% v/v of organic solvent. Neat organic solvent such as tetrachlormethane and benzene may be used. However, some organic solvent may cause problems because of its reactivity with e.g. the excited quinone. Also, organic solvents are more expensive and may result in environmental problems.
The solution in contact with the polymer is then exposed to light and irradiation is performed, optionally for a period up to 200 minutes, typically for less than 60 minutes, preferably less than 30 minutes. This modification does not change the physical properties of the polymer (stability, strength, transparency, etc.). The solution, preferably an aqueous solution, in which the covalent coupling takes place, is often buffered. This is done to keep defined pH during the reaction and to secure that certain groups are ionic. The pH value is preferably in the range from 0-7 or in the range 7-12. The optimal pH value is highly dependent on the specific reaction and the compounds involved. When amines are coupled, the pH is preferably less than 8 to protonate the amino functionality. By doing this, the reagent will be readily soluble in water and together with the quinone in the other part of the compound, the reagent as a whole acts as a soap. This means that the lipophilic quinone part will stick to the polymer, and the polar amino group will point out in the solvent. When e.g. carboxy groups are to be immobilized, the pH will preferably be more than 6 to obtain the same effect. When using aqueous systems, this differential polarity of the reagent as a whole is important in the photochemical immobilization.
Further Advantages
Contrary to benzophenones, the special redox properties of quinones, enables overall reduced quinones which can be formed during photolysis and which are not covalently linked to the surface to be "recycled" as illustrated in FIG. 3.
This recycling system increases the efficiency of the overall photochemical coupling. The high efficiency of the method according to the invention and the surprising findings that quinone-ligand conjugates can be photochemically immobilized on different polymers can be partly explained by this interesting recycling and "conservation" of photoprobes (the photochemical compounds which are to be subjected to a photochemical reaction).
As mentioned above, exited quinones react in radical reactions. The initial step is in general hydrogen atom abstraction and the rate of reaction is determined by the bond energy of the covalent bond between the hydrogen and the carbon to which it is bonded. This reaction mechanism has the consequence that the exited quinones are not able to react with water which has about the strongest binding of hydrogen atoms. Therefore, by using water as the solvent it is possible to generate extremely reactive species which are not able to react with the solvent.
Preferred Uses
Preferred uses of the carbon-containing material as prepared according to the method of this invention comprise use in a detection system, use as carrier for solid phase immuno assays, particularly as well as plates, test particles such as beads and micro spheres, test tubes, test sticks, and test strips, and use as a carrier for solid phase synthesis of peptides, oligonucleotides, carbohydrates and small organic molecules.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows illustrations of applicable basic quinone compounds (I)-(XXXVI) according to the invention.
FIG. 2 shows particularly preferred quinones (XXXVII)-(XXXIX) according to the invention.
FIG. 3 shows an illustration of recycling of reduced quinones.
FIG. 4 illustrates the photochemical reaction of arylazides.
FIG. 5 illustrates the photochemical reaction of benzophenone.
FIG. 6 illustrates photochemical properties of quinones of this invention.
FIG. 7 shows quinone-ligand, quinone-spacer-ligand compounds nos. 1-22 prepared in example 1.
FIG. 8a shows a UV grafting of phenanthrene quinone amine compound no. 3 onto polystyrene surfaces (PolySorp®). Effect of photoprobe concentration and irradiation time. ⋄ No UV irradiation (control); □ 5 min. irradiation; Δ 7 min.; ∘ 10 min.
FIG. 8B shows a grafting of phenanthrene quinone amine compound no. 3 onto polystyrene surfaces (Nunclon® Delta treated). Effect of photoprobe concentration and irradiation time. ⋄ No. UV irradiation (control); □ 5 min. irradiation; Δ 7 min.; ∘ 10 min.
FIG. 9a shows a grafting of anthraquinone amine compound no. 5 onto polystyrene surfaces (PolySorp®). Effect of photoprobe concentration and irradiation time. ⋄ No. UV irradiation (control); □ 5 min. irradiation; Δ 7 min.; ∘ 10 min.
FIG. 9b shows a UV grafting of anthraquinone amine compound no. 5 onto polystyrene surfaces (Nunclon® Delta treated). Effect of photoprobe concentration and irradiation time. ⋄ No. UV irradiation (control); □ 5 min. irradiation; Δ 7 min.; ∘ 10 min.
FIG. 10 shows a UV grafting of anthraquinone amines compounds nos. 5, 7 and 9 onto polystyrene surfaces. Effect of spacer arm length on signal strength. Open symbols: results on Nunclon® Delta treated surfaces; closed symbols: results on PolySorp plates. ∘/ Amine 5, □/▪ Amine 7; Δ/▴ Amine 9.
FIG. 11 shows the storage stability of anthraquinone amine compound no. 9 UV grafted onto Nunclon® Delta treated polystyrene surfaces. Values are given relative to day zero. ∘ Storage temperature 4° C.; Δ 20° C.; □ 37° C.; ⋄ 60° C.
FIG. 12 shows the storage stability of anthraquinone amine compound no. 9 UV grafted onto PolySorp® polystyrene surfaces. Values are given relative to day zero. ∘ Storage temperature 4° C.; Δ 20° C.; □ 37° C.; ⋄ 60° C.
FIG. 13 shows the UV grafting of anthraquinone carboxylic acid derivative compound no. 13 onto polystyrene surfaces. Open symbols: results with no UV irradiation (control); closed symbols: results after 10 min. UV irradiation. ∘/ PolySorp® plates; Δ/▴ Nunclon® Delta treated plates.
FIG. 14 shows a UV grafting of peptide compound no. 19, N-terminally anthraquinone substituted, onto polystyrene surfaces: Effect of irradiation time and concentration of Hyb 161-2 anti peptide monoclonal antibody. 2 min. irradiation; 5 min.; Δ 10 min.; ▴ 15 min.; □ 30 min.; ▪ 60 min.
FIG. 15 shows a UV grafting of anthraquinone peptide compound no. 19 onto polystyrene surfaces. Effect of irradiation time with a constant concentration of Hyb 161-2 anti peptide monoclonal antibody. ∘ Non specific binding with no Hyb 161-2 added; Hyb 161-2 added (1 mg/ml).
FIG. 16 shows a UV grafting of peptide compound no. 19, N-terminally anthraquinone substituted, onto polystyrene surfaces. Effect of peptide concentration. Closed symbols: 10 min. irradiation time; open symbols: no irradiation. ∘/ Anthraquinone-peptide 9; Δ/▴ unsubstituted peptide.
FIG. 17 shows the storage stability of UV grafted peptide compound no. 19. ∘ Storage temperature 37° C.; 4° C.
FIG. 18a shows UV grafting of anthraquinone NTA derivative 20 onto polystyrene surfaces. Effect of photoprobe concentration. Open symbols: results with no UV irradiation (control); closed symbols: results after 5 min UV irradiation.
FIG. 18b shows binding of a biotinylated histidine tagged peptide onto NTA modified polystyrene surfaces. 1: no peptide added (control); 2: binding of biotinylated non-histidine tagged peptide biotin-εAhx-Leu-Lys-Leu-Lys-Trp-Lys-OH (control); 3: binding of biotinylated histidine tagged peptide biotin-εAhx-Leu-Lys-Leu-Lys-Trp-Lys-His-His-His-His-His-His-OH; 4: binding of biotinylated non-histidine tagged peptide biotin-εAhx-Arg-Thr-Gln-Asp-Glu-Asn-Pro-Val-Val-His-Phe-Lys-Asn-Ile-Val-Thr-Pro-Arg-Thr-Pro-OH (control).
FIG. 19 shows UV grafting of the anthraquinone PEG2000 derivative 22 onto polystyrene surfaces. PS063: 0.3 mM photoprobe, 5 min UV irradiation; PS064: 0.3 mM photoprobe, no UV irradiation (control); PS065: 0.3 mM PEG2000, 5 min UV irradiation (control); PS066: 0.3 mM PEG2000, no UV irradiation (control); PS067: H 2 O alone, 5 min UV irradiation (control); PS068: H 2 O alone, no UV irradiation (control).
FIG. 20 shows UV grafting of the anthraquinone PEG2000 derivative 22 onto polypropylene surfaces. PP011: 0.3 mM photoprobe, 5 min UV irradiation; PP012: 0.3 mM photoprobed no UV irradiation (control); PP013: H 2 O alone, no UV irradiation (control).
DETAILED DESCRIPTION
Prior Art--Photochemical Reaction of Arylazides
The photochemical reaction of the arylazides and derivatives thereof is illustrated in FIG. 4. Nu--H is e.g. H 2 O is R--OH, R--SH, R--NH 2 or "polymer". When irradiated with high energy UV light, i.e. as in Table 1 in example 2, a very reactive nitrene is formed and is quickly rearranged to a dehydroazepine. The latter is extremely unstable and will immediately react with the first nucleophilic compound it meets. If this is the solvent, e.g. water, the photoreagent is lost and no reaction is performed with the polymer. When using such reagents, it is therefore necessary that the surface is preincubated with the photoreagent, whereafter the redundant of the reagent is removed and the surface dried prior to the photolysis. When introducing strongly electron withdrawing groups the photochemical mechanism can be changed to nitrene photochemical reaction, but the nitrene compound will also react with the solvent, including water. Combined with long irradiation times (typically 12 hours), this makes the application of this photoreactive group time-consuming and inefficient.
Prior Art--Photochemical Reaction of Ketones
The major drawback of photochemical reactive ketones is their photchemical oxidation to the corresponding alcohol resulting in loss of the photochemical reagent. Also, they require long irradiation times of typically 12 hours which makes them unsuitable for immobilization of sensitive biomolecules.
Prior Art--Photochemical Reaction of Benzophenone
The photochemistry of benzophenones results in the formation of a C--C bonding contrary to quinones which may form an ether bonding. Both groups have the advantage of not being reactive with water. Therefore, water can be used as a solvent.
The photochemical reaction of benzophenone and derivatives thereof is illustrated in FIG. 5, wherein R designates the polymer.
Such a photoreactive group based on benzophenone forms a radical by excitation with high energy UV light followed by hydrogen atom abstraction from a substrate, which radical either combines with the formed substrate radical to the product or which radical abstracts another hydrogen atom from a substrate, which results in a photochemical reduction to the corresponding alcohol with consequent loss of the photoreagent. Substrates for these reactions are organic molecules, including synthetic polymers, but also organic solvents such as e.g. alcohols.
The photochemical coupling typically requires irradiation at 320 nm for 12 hours to obtain an effective coupling to the polymer.
Photochemical Properties of Quinones of this Invention
The excited quinone reacts in general as a free radical and results in addition to double/triple bonds, abstracts hydrogen atoms, initiates chain reactions, etc. Due to the resonance configuration of the quinone, the radical reaction can take place on both or all the carbonyl groups of the quinone as illustrated in FIG. 6.
These reaction patterns are the fundamental photochemical properties of the quinones in this invention. Due to their general behaviour most quinones will be able to perform this kind of chemistry.
EXAMPLES
In the following the invention is further described by reference to a number of specific examples.
AQ: anthraquinone
BOP: benzotriazole-1-yl-N-oxytris-(dimethylamino)-phosphonium hexafluorophosphate
But: tert-butyl
DCC: dicyclohexylcarbodiimide
DCU: dicyclohexyl urea
DIEA: diisopropylethylamine
DMF: dimethylformamide
DMSO:. dimethylsulfoxide
EI: electron ionization
ELISA: enzyme linked immunosorbent assay
FAB: fast atom bombardment
Fmoc: fluorenylmethoxycarbonyl
HPLC: high performance liquid chromatography
Mp: melting poing
MS: mass spectrometry
NMR: nuclear magnetic resonance
NTA: N-nitrilotriacetic acid
OPD: phenylene-1,2-diamine dihydrochloride
PEG: polyethylene glycol
Pmc: 2,2,5,7,8 pentamethylchroman-6-sulfonyl
TFA: trifluoroacetic acid
THF: tetrahydrofuran
TLC: thin layer chromatography
Example 1
FIG. 7 shows quinone-ligand, quinone-spacer-ligand compounds nos. 1-22 which have been synthesized as described in the following.
The mono-Boc-protected diamines were prepared as described by Krapcho and Kuell, Synthetic Communications 1990, 20, 2559-2564.
3-Carboxy-phenanthrenequinone (Compound No. 1)
3-Acetylphenanthrene (5 g, 0.23 mmol) was dissolved in warm acetic acid (100 ml, 60 ° C.) and chrom(VI)oxide (30 g, 0.6 mol) was added in small portions. During this the temperature rose to the boiling point. After addition of all chrom(VI)oxide the solution was diluted with water (500 ml) and the precipitate was filtered off, washed with acetic acid/H 2 O (1:1), cold acetic acid and finally with diethyl ether. Yield: 2.1 g (37% from 3-acetylphenanthrene); Mp: 280° C.
MS (EI): 252 (M + ).
1 H NMR (d 6 -DMSO): 8.70 ppm (s, 1H), 8.34 (d, 1H), 8.08 (m, 3H), 7.80 (t, 1H), 7.57 (t, 1H).
N-(3-Boc-aminopropyl)-phenanthrenequinone-3-carboxamide (Compound No. 2)
Compound no. 1 (250 mg, 1.0 mmol), DCC (245 mg, 1.2 mmol) and HODhbt (178 mg, 1.1 mmol) were dissolved in dioxane (50 ml), and the mixture was allowed to react overnight. The dioxane was evaporated in vacuo, and the residue was suspended in DMF (25 ml). Mono-Boc-1,3-propanediamine.HCl (333 mg, 1.2 mmol) was added to the suspension followed by excess triethylamine (1 ml). After 1 hour DCU was filtered off and water (150 ml) was added. The yellow precipitate was collected by filtration and the product recrystallized from ethyl acetate. Yield: 0.235 mg (56% from compound no. 1); Mp: 195° C. (dec.).
1 H NMR (CDCl 3 ): 8.02 ppm (t, 1H), 7.98 (s, 1H), 7.65 (d, 1H), 7.51-7.45 (m, 2H), 7.33 (d, 1H), 7.14 (t, 1H), 6.89 (t, 1H), 5.62 (b, 1H), 2.89-2.71 (m, 2H), 2.44-2.41 (m, 2H), 1.11-0.75 (m, 11H).
N-(3-Aminopropyl)-phenanthrenequinone-3-carboxamide.HCl (Compound No. 3)
Compound no. 2 (100 mg, 0.24 mmol) was dissolved in slightly warmed acetic acid (2.5 ml, 50° C.), and 1 M HCl in acetic acid was added (2.5 ml). After 5 minutes ether was added (10 ml), and the precipitate was collected by filtration and was washed several times with ether. Yield: 81 mg (95% from compound no. 2).
1 H NMR (d 6 -DMSO): 9.20 ppm (b, 1H), 8.78 (s, 1H), 8.54 (d, 1H), 8.14-7.99 (m, 6H), 7.86 (t, 1H), 7.60 (t, 1H), 3.38 (--CH 2 --N--R), 2.88 (b, 2H), 1.69 (s, 2H).
UV (ethanol/water): λ max =266 nm (ε=39000), 330 (5700), 424 (1400).
N-(3-Boc-aminopropyl)-anthraquinone-2-carboxamide (Compound No. 4)
Anthraquinone-2-carboxylic acid (2.52 g 10 mmol) was suspended in dry THF (100 ml). The suspension was cooled to 0° C., and DCC (2.06 g, 10 mmol) was added, and the mixture stirred for 5 minutes. Solid HODhbt (1.63 g, 10 mmol) was added, and the mixture stirred for 10 minutes at 0° C. and then at room temperature overnight. THF was removed in vacuo (40° C.), and the solid residue was resuspended in DMF (100 ml). Mono-Boc-1,3-propanediamine.HCl (4.21 g, 20 mmol) was added to the suspension followed by excess triethylamine (7 ml). After 2 h DCU was removed by filtration and water (200 ml) was added. The yellow precipitate was collected by filtration and the product recrystallized from ethyl acetate (200 ml). Yield: 3.53 g (87% from anthraquinone-2-carboxylic acid); Mp: 173-175° C.; TLC (ethyl acetate): R f =0.61.
MS (FAB + ): 409.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t 1H), 8.75 (s, 1H), 8.40 (dd, 1H), 8.30 (m, 3H), 8.05 (m, 2H), 6.90 (t, 1H), 3.40 (q, 2H), 3.10 (q, 2H), 1.80 (qn, 2H), 1.45 (s, 9H).
N-(3-Aminopropyl)-anthraquinone-2-carboxamide.HCl (Compound No. 5)
Compound no. 4 (5.92 g, 14.5 mmol) was suspended in methanol (200 ml). 6 M HCl in methanol (15 ml) was added, and the mixture was heated to ref lux for 1 hour. The mixture was cooled to 0° C., and diethyl ether (200 ml) was added. The precipitated product was collected by filtration and washed several times with ether. Yield: 3.98 g (80% from compound no. 4); Mp: 250° C. (dec.); TLC (1-butanol/acetic acid/water 4:1:1): R f =0.43.
MS (FAB + ): 309.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t, 1H), 8.75 (s, 1H), 8.50 (dd, 1H), 8.30 (m, 3H), 8.15 (s, 3H), 8.10 (m, 2H), 3.50 (q, 2H), 2.95 (t, 2H), 1.95 (qn, 2H).
UV (ethanol/water): λ max =256 nm (ε=49000), 332 (4700), 390 (310).
Boc-βAla-NH--(CH 2 ) 3 --NHCO--AO (Compound No. 6)
Boc-β-Ala-OH (0.605 g, 3.20 mmol) and BOP (1.283 g, 2.9 mmol) were dissolved in DMF (50 ml), and triethylamine (4 ml, 30 mmol) was added. The mixture was allowed to preactivate for 5 minutes before compound no. 5 (1.00 g, 2.90 mmol) was added in one portion. The reaction mixture was stirred at room temperature overnight, and the product was precipitated by the addition of water (50 ml). The crude product was filtered off, washed several times with water, and finally recrystallized from ethanol/water. Yield: 1.40 g (92% from compound no. 5); Mp: 178-179° C., TLC (ethyl acetate/methanol/acetic acid 85:10:5): R f =0.73. MS (FAB + ): 480.2 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t, 1H), 8.75 (s, 1H), 8.40 (dd, 1H), 8.35 (m, 3H), 8.05 (m, 2H), 7.90 (t, 1H), 6.80 (t, 1H), 3.40 (q, 2H), 3.20 (q, 4H), 2.30 (t, 2H), 1.75 (qn, 2H), 1.45 (s, 9H).
H-βAla-NH--(CH 2 ) 3 NHCO--AO.HCl (Compound No. 7)
Compound no. 6 (0.220 g 2.54 mmol) was suspended in methanol (40 ml). 6 M HCl in methanol (5 ml) was added, and the mixture was heated to reflux for 1 hour. The mixture was cooled to 0° C., and diethyl ether (40 ml) was added. The precipitated product was collected by filtration and washed several times with ether. Yield: 0.970 g (92% from compound no. 6); Mp: 219° C. (dec.); TLC (1-butanol/acetic acid/water 4:1:1): R f : 0.40.
MS (FAB + ): 380.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.10 ppm (t, 1H), 8.75 (s, 1H), 8.45 (dd, 1H), 8.35 (m, 4H), 8.15 (s, 3H), 8.10 (m, 2H), 3.45 (m, 4H), 3.25 (q, 2H), 3.10 (t, 2H), 1.80 (q, 2H).
Boc-βAla-βAla-NH--(CH 2 ) 3 --NHCO--AO (Compound No. 8)
Compound no. 7 (0.492 g, 2.60 mmol) and BOP (0.955 g, 2.16 mmol) were dissolved in DMF (80 ml), and triethylamine (1.5 ml, 10.8 mmol) was added. The mixture was allowed to preactivate for 5 minutes before compound no. 7 (0.900 g, 2.16 mmol) was added in one portion. The reaction mixture was stirred at room temperature overnight, and the product was precipitated by the addition of water (80 ml). The crude product was filtered off, washed several times with water, and finally recrystallized from ethanol/water. Yield: 0.740 g (62% from compound no. 7); Mp: 183-184° C.; TLC (ethyl acetate/methanol/acetic acid 85:10:5): R f =0.45.
MS (FAB + ): 551.3 (MH + ).
1 H NMR (d 6 -DMSO): 9.05 ppm (t, 1H), 8.75 (s, 1H), 8.30 (m, 4H), 8.10 (m, 2H), 7.90 (dt, 2H), 6.75 (t, 1H), 3.40 (q, 2H) 3.35 (q, 2H), 3.20 (dq, 4H), 2.30 (dt, 4H), 1.80 (qn, 2H), 1.45 (s, 9H).
H-βAla-βAla-NH--(CH 2 )3--NHCO--AO.HCl (Compound No. 9)
Compound no. 8 (0.740 g, 1.35 mmol) was suspended in methanol (15 ml). 6 M HCl in methanol (1 ml) was added, and the mixture was heated to reflux for 1 hour. The mixture was cooled to 0° C., and diethyl ether (15 ml) was added. The precipitated product was collected by filtration and washed several times with ether. Yield: 0.591 g (90% from compound no. 6); Mp: 216-219° C.; TLC (1-butanol/acetic acid/water 4:1:1): R f =0.26.
MS (FAB + ): 451.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t, 1 h), 8.60 (d, 1H), 8.35 (dd, 1H), 8.30 (d, 1H), 8.25 (m, 2H), 8.15 (t, 1H), 7.95 (m, 3H), 7.80 (s, 3H), 3.30 (m, 6H), 3.15 (q, 2H), 2.50 (t, 2H), 2.30 (t, 2H), 1.75 (qn, 2H).
Boc-βAla-βAla-βAla-NH--(CH 2 ) 3 --NHCO--AO (Compound No. 10)
Compound no. 9 (0.263 g, 1.39 mmol) and BOP (0.513 g, 1.16 mmol) were dissolved in DMF (50 ml), and diisopropylethyl amine (2 ml, 12 mmol) was added. The mixture was allowed to preactivate for 5 minutes before compound no. 9 (0.564 g, 1.16 mmol) was added in one portion. The reaction mixture was stirred at room temperature overnight, and the product was precipitated by the addition of water (50 ml). The crude product was filtered off, washed several times with water, and finally recrystallized from ethanol/water. Yield: 0.654 g (91% from compound no. 9); Mp: 209-213° C.; TLC (methanol): R f =0.60. MS (FAB + ): 622.2 (MH + ).
1 H NMR (d 6 -DMSO): 9.05 ppm (t, 1H), 8.75 (s, 1H), 8.30 (m, 4H), 8.10 (m, 2H), 8.00 (dt, 2H), 7.90 (t, 1H), 6.80 (t, 1H), 3.30 (dq, 6H), 3.20 (dq, 4H), 2.30 (tt, 6H), 1.80 (qn, 2H), 1.45 (s, 9H).
H-βAla-βAla-βAla-NH--(CH 2 ) 3 --NHCO--AO.HCl (Compound No. 11)
Compound no. 10 (0.500 g, 0.800 mmol) was suspended in methanol (15 ml). 6 M HCl in methanol (1 ml) was added, and the mixture was heated to reflux for 1 hour. The mixture was cooled to 0° C., and diethyl ether (15 ml) was added. The precipitated product was collected by filtration and washed several times with ether. Yield: 0.400 g (89% from compound no. 10); Mp: 235-237° C. (dec.); TLC: (1-butanol/acetic acid/water 4:1:1): R f 0.14. MS (FAB + ): 522.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t, 1H), 8.65 (d, 1H), 8.30 (d, 1H), 8.25 (m, 2H), 8.15 (t, 1H), 8.00 (m, 2H), 7.90 (s, 3H), 3.35 (t, 2H), 3.25 (q, 4H), 3.15 (q, 2H), 2.95 (q, 2H), 2.50 (t, 2H), 2.30 (dt, 4H), 1.70 (qn, 2H).
N-(5-carboxymethyl-pentyl)anthraquinone-2-carboxamide (Compound No. 12)
Anthraquinone-2-carboxylic acid (2.52 g, 10 mmol) was suspended in dry THF (100 ml) and cooled to 0° C. Then, DCC (2.26 g, 11 mmol) was added, and the mixture stirred for 5 minutes. Solid HODhbt (1.63 g, 10 mmol) and the mixture stirred at 0° C. for 10 minutes and then at room temperature overnight. THF was removed in vacuo, and the solid residue was resuspended in DMF (100 ml). 6-Aminohexanoic acid methyl ester.HCl (1.99 g, 11 mmol) followed by triethyl amine (7 ml, 50 mmol) were added, and the mixture stirred at room temperature overnight. DCU was removed by filtration, and the product was precipitated by the addition of water (200 ml). The crude product was collected by filtration and recrystallized from ethyl acetate. Yield: 3.09 g (73% from anthraquinone-2-carboxylic acid); Mp: 144-145° C.; TLC (ethyl acetate): R f =0.68. MS (FAB + ): 380.1 (MH + ).
1 H NMR (d 6 -DMSO): 9.00 ppm (t, 1H), 8.75 (s, 1H), 8.40 (dd, 1H), 8.30 (m, 3H), 8.05 (m, 2H), 3.70 (s, 3H), 3.40 (q, 2H), 2.40 (t, 2H), 1.70 (qn, 6H), 1.40 (qn, 4H).
N-(5-carboxypentyl)-anthraquinone-2-carboxamide (Compound No. 13)
Compound no. 12 (0.949 g, 2.5 mmol) was suspended in THF (15 ml). 0.5 M LiOH (15 ml) was added, and the mixture stirred at room temperature for 1 hour. THF was removed in vacuo, and the product was precipitated by the addition of 2 M HCl (6 ml). The crude product was collected by filtration, washed with water and dried in vacuo. Yield: 0.822 g (90% from compound no. 12); Mp: 198-199° C.; TLC (petroleum ether/ethyl acetate/acetic acid 5:5:1): R f =0.43. MS (FAB + ): 366.2 (MH+).
1 H NMR (d 6 -DMSO): 12.00 ppm (s, 1H), 9.00 (t, 1H), 8.75 (s, 1H), 8.40 (dd, 1H), 8.35 (m, 3H), 8.00 (m, 2H), 2.30 (t, 2H), 1.60 (qn, 6H), 1.40 (qn, 4H).
N-(6-hydrazido-hexyl)-anthraquinone-2-carboxamide (Compound No. 14)
Compound no. 12 (0.5 g, 1.32 mmol) was suspended in methanol (5 ml). Hydrazine hydrate (1 ml, 20 mmol) was added in one portion, and the reaction mixture was refluxed for 6 h and then allowed to cool to room temperature. The solvent was removed in vacuo, and the remanence was resuspended in ice cold water (20 ml). The precipitated product was collected by filtration and washed with water and dried in vacuo. Yield: 0.373 g (75% from compound no. 12); Mp: 181° C. (dec.); TLC (ethyl acetate/methanol 6:4): R f =0.48. MS (FAB + ): 380.24 (MH + ).
1-(3-(carboxamido-anthraquinone-2-yl)-propyl)-thiosemicarrbazide (Compound 15)
BOP (0.257 g, 0.58 mmol) and carbon disulfide (0.35 ml, 5.8 mmol) was dissolved in DMF. Then, triethyl amine (0.24 ml, 1.74 mmol) followed by solid compound no. 5 (0.2 g, 0.58 mmol) was added. The mixture was stirred for 1 hour at room temperature. Excess carbon disulfide was removed in vacuo, and the solution was added dropwise to a stirred ice cold solution of hydrazine hydrate (0.5 ml, 7.8 mmol) in DMF (0.5 ml). The mixture was stirred overnight at room temperature, and the product was precipitated by addition of ice cold water (25 ml). The precipitated product was collected by filtration and washed with water and dried in vacuo. Yield: 0.164 g (74% from compound no. 5); Mp: 202-205° C. (dec.); TLC (ethyl acetate/methanol 6:4): R f =0.63.
MS (FAB + ): 383.1 (MH + ).
HO 2 C--(CH 2 ) 3 --CONH--(CH 2 ) 3 --NHCO--AO (Compound No. 16)
Compound no. 12 (0.45 g, 1.31 mmol) and maleic anhydride (0.19 g, 1,9 mmol) was dissolved in DMF (30 ml). Triethylamine (1.8 ml, 13.1 mmol) was added, and the mixture was stirred at room temperature for 3 hours. The product was precipitated by the addition of ice cold 0.5 M HCl (30 ml), collected by filtration and recrystallized from ethanol/water. Yield: 0.374 g (79% from compound no. 12); TLC (ethyl acetate/methanol 6:4): R f =0.33.
MS (FAB + ): 409.1 (MH + ).
α-D-Glcp-(1-∞4)-β-D-Glcp-1-N(Ac)-(CH 2 ) 3 --NH--CO--AO (Compound No. 17)
Compound no. 5 (0.103 g, 0.300 mmol) and maltose monohydrate (0.324 mg, 0.900 mmol) were dissolved in dry methanol. DIEA (70 μl, 0.400 mmol) was added and the mixture was heated in nitrogen atmosphere overnight. The mixture was cooled to 0° C., and acetic anhydride (1 ml) was added. After standing at room temperature overnight methanol was removed in vacuo, and the residue was dissolved in water and filtered through a 0.2 μm filter and freeze dried. The resulting solid was redissolved in water and loaded onto two Sep-Pak Vac cartridges (C 18 , 100 mg sorbent).
Residual free maltose was eluted with water (2×10 ml) and the quinone-maltose conjugate eluted with 50% acetonitrile/water. The combined acetonitrile/water fractions were freeze dried to yield compound no. 17 as a slightly yellow voluminous powder. Yield: 0.203 mg (100% from compound no. 5); TLC: R f =0.32 (major spot, compound no. 17); R f =0.66 (minor spot, CH 3 --CONH--(CH 2 ) 3 --NHCO--AQ); HPLC (Delta Pak 5μ C 18 3.9×150 mm; buffer A: 0.1% TFA in H 2 O; buffer B: 0.1% TFA in acetonitrile/water 9:1; gradient: 100% A for 2 minutes, then a linear gradient from 100% A to 100% B over 20 minutes, then 100% B for 5 minutes): Rt=12.07 minutes (77%, 332 nm), 12.29 (5%), 12.67 (14%), 13.35 (4%, CH 3 --CONH--(CH 2 ) 3 --NHCO--AQ).
MS (FAB + ): 675.25 (MH + ); 717.48 (MH + +CH 3 --CO); 759.58 (MH + +2CH3CO); 351.16 (CH 3 --CONH--(CH 2 ) 3 --NHCO--AQ.H + ).
AO--CO--(CH 2 )3--NH-6-ketoestradiol-6-(O-carboxymethyl)-oxime (Compound No. 18)
Compound no. 5 (48 mg, 0.139 mmol), 6-ketoestradiol-6-(O-carboxymethyl)-oxime (50 mg, 0.139 mmol) and BOP (65 mg, 0.139 mmol) were suspended in DMF. Diisopropylethyl amine (49 μl, 0.278 mmol) was added and the mixture stirred at room temperature for 3 hours. Water (3 ml) was added, and the precipitated product was filtered off, washed with 10% Na 2 CO 3 (three times), 10% KHSO 4 (three times), several times with water and finally dried in vacuo. Yield: 90 mg (100%); TLC (ethyl acetate/acetic acid 95:5): R f =0.27. MS (FAB + ): 650.26 (MH + ); 672.28 (M+Na + ).
AO--CO-εAhx-Gln-Glu-Ser-Gly-Val-Ser-Gly-Arg-OH (Compound No. 19)
H-Gln-Glu(OBu t )-Ser(bu + )-Gly-Val-Ser(bu t )-Gly-Arg(Pmc)-PepSyn-KA was synthesized using a standard Fmoc-protocol on a custom-made fully automatic continuous flow peptide synthesizer with solid phase online monitoring of coupling reactions. Fmoc-Arg(Pmc)-PepSyn-KA resin (750 mg, 0.09 mmol/g) was loaded onto a column and each individual coupling was performed with the corresponding Fmoc-amino-acid-OPfp-esters (3 equivalents) and HODhbt (1 equivalent) added as catalyst/indicator except serine which was coupled as the Dhbt-ester. At the end of the synthesis the peptidyl resin was transferred to a bubbler apparatus and N-(5-carboxypentyl)-anthraquinone-2-carboxamide (compound no. 13) (3 equivalents) and BOP (3 equivalents) followed by DIEA (9 equivalents) added to the resin. The coupling was allowed to proceed overnight. The N-terminally quinone substituted peptide was cleaved from the resin with Reagent K (TFA/H 2 O/thioanisole/phenol/ethane diethiol 82.5:5:5:2.5). The resin was filtered off on a sintered glass filter, washed several times with TFA, and the cleavage mixture concentrated in a stream of nitrogen. The peptide was precipitated with ice cold diethyl ether, and the peptide pellet was redissolved in 2% acetic acid/water, filtered through a 0.2 μm filter and finally freeze dried. HPLC (Delta Pak 5μ C 18 3.9×150 mm; buffer A: 0.1% TFA in H 2 O; buffer B: 0.1% TFA in acetonitrile/water 9:1; gradient: 100% A for 2 minutes, then a linear gradient from 100% A to 100% B over 20 minutes, then 100% B for 5 minutes): Rt=13.64 minutes; purity ≧90% (220 nm). MS (FAB + ): 1166.35 (MH + ).
NTA-βAla-βAla-NH--(CH 2 )3--NHCO--AO (Compound No. 20)
Glycerine tert.butyl ester Hcl (3.34 g, 20 mmol) was dissolved in aqueous sodium carbonate. The free tert.butyl ester was extracted into dichloro methane (3×100 ml) and dried above sodium carbonate. The solvent was removed in vacuo giving 2.44 g (92%) of the free tert.butyl ester. DIEA (20 ml) was added followed by benzyl-2-bromoacetate (8 ml). The mixture was heated to reflux for 45 min, then cooled to room temperature, diluted with ethyl acetate and washed with aqueous sodium carbonate followed by water. The solvent was removed in vacuo and the NTA-tert-butyl-dibenzyl ester purified on a silicagel column using a gradient of 10-30% ethyl acetate in hexane as eluent. Yield 7.1 g (83%). The tert.butyl ester was cleaved by refluxing for two hours with a 1:1 mixture of TFA and dichloro methane giving NTA-dibenzyl ester as the trifluoro acetate.
Compound no. 9 (0.394 g, 0.809 mmol), NTA-dibenzyl ester (0.383 g, 1.03 mmol) and BOP (0.456 g, 1.03 mmol) was suspended in DMF (20 ml). DIEA (0.87 ml, 5 mmol) was added, and the mixture was left overnight. Water was added (20 ml), and the precipitated product was collected by filtration and washed several times with water. The crude product was dissolved in hot ethanol (75 ml), and the solution was decolorised with activated carbon. Water was added (50 ml), and the solution was concentrated to approx. 60 ml. The mixture was left overnight at room temperature, and the precipitated product was filtered off. The solid was suspended in THF (10 ml) and 0.5 M LiOH (5 ml) was added. The solution was stirred at room temperature for 2.5 hour, then THF was removed in vacuo and 10% phosphoric acid added. The product was collected by filtration, washed with water and dried in vacuo. Yield: 0.214 g (42% from compound no. 9); Mp: 158-163° C.; TLC (methanol/pyridine/acetic acid 80:20:6): R f =0.42.
MS (FAB + ): 624.23 (MH + ); 646.20 (M+Na + ).
Anthraquinone-2-carboxylic acid chloride (Compound No. 21)
Anthraquinone-2-carboxylic acid (2.52 g, 10 mmol) was suspended in dichloro methane (100 ml). Thionyl chloride (50 ml) was added and the mixture heated to reflux in a nitrogen atmosphere for several hours giving a clear yellow solution. Dichloro methane and excess thionyl chloride was removed in vacuo giving a yellow solid. The solid was filtered off, washed several times with petroleum ether and dried in vacuo. Yield 2.69 g (99% from anthraquinone-2-carboxylic acid); MP: 143-144.5° C.; TLC (analyzed as the methyl ester: a small sample of the acid chloride was dissolved in dry methanol and analyzed immediately using ethyl acetate as eluent); R f =0.68. MS (FAB + ): 307.1 (MH + ).
AO--CO-PEG2000 (Compound No. 22)
PEG2000 (2.00 g, 1 mmol) was dissolved in toluene (100 ml). 50 ml of the toluene was distilled off and the solution cooled to r.t.. Anthraquinone-2-carboxylic acid chloride (0.271 g, 1 mmol) followed by pyridine (1.6 ml, 20 mmol) was added and the mixture heated to reflux in a nitrogen atmosphere for one hour. Toluene and excess pyridine was removed by distillation, then water (100 ml) was added and residual toluene removed by azeotrope distillation. The target compound was isolated by freeze drying from water. Yield 2.28 g (102%). HPLC (Delta Pak 5μ C 18 3.9×150 mm; buffer A: 0.1% TFA in water; buffer B: 0.1% TFA in acetonitrile/water 9:1; gradient: 25% A+75% B for 2 minutes, then a linear gradient from 25%+75% B to 100% B over 10 minutes, then 100% B for 10 minutes; R t =2.4 min (anthraquinone-2-carboxylic acid: 2.6% (330 nm)); R t =3.69 min (AQ--CO-PEG2000: 78.9% (330 nm)); R t =7.08 min (AQ--CO-PEG2000-CO--AQ: 18.5% (330 nm)).
Example 2
Compound no. 5 in Example 1 substituted antraquinone (VII) (in this experiment designated Q1) and compound no. 3 in Example 1 substituted phenanthrenequinone (VIII) (in this experiment designated Q2) and a selected number of other photoprobes were studied for absorbance in the wavelength range from 190-820 nanometers. Compound XXVI correspond to the structure shown in FIG. 1.
The following absorption maxima and extinction coefficient (ε) was found (see Table 1).
TABLE 1______________________________________UV/data of photoprobes (n.a. = no absorption) ε.sub.max ε.sub.max ε.sub.max .sub.max (M.sup.-1 .sub.max (M.sup.-1 .sub.max (M.sup.-1Compound (nm) cm.sup.-1) (nm) cm.sup.-1) (nm) cm.sup.-1)______________________________________Azidobenzene 247 7900 315 80 (n.a.) --Benzophenone 260 14000 333 110 (n.a.) --Anthracenequinone 252 39000 325 4700 390 110Phenanthrenequinone 266 29000 328 4300 425 1400Q1 256 49000 332 4700 390 310Q2 266 39000 330 5700 424 1400XXVI 253 2500 263 2350 398 69000______________________________________
Example 3
Introduction of Primary Amino Groups onto Polystyrene Surfaces by UV Grafting
The effect of quinone type as well as the effect of photoprobe concentration and irradiation time on the introduction of primary amino groups were tested with phenanthrene quinone amine compound no. 3 and anthraquinone amine compound no. 5 on two types of polystyrene: 1) Nunc-Immuno® Module F16 PolySorp (untreated polystyrene, Nunc cat. no. 467679); 2) non-sterile Nunc F96 Nunclon® Delta treated plates). The quinone amines compound no. 3 and compound no. 5 were dissolved in distilled water, and 100 μl was added to each well of the ELISA plates in a five-fold dilution series with a start concentration of 0.58 μM of the photoprobes. The plates were placed 14 cm under the UV lamp (Philips HPA 400: the lamp emits low energy UV-A and UV-B light mainly between 300 and 400 nm), and they were irradiated for 5, 7 and 10 minutes, respectively. The wells were rinsed three times with demineralized water and dried for 50 minutes at 60° C. Plates containing the photoprobes were kept in the dark during photolysis as controls. Biotin-succinimide ester (Sigma cat. no. H 1759) in PBS buffer (phosphate buffered saline: 0.15 M Na + , 4.2 mM K + , 7.9 mM phosphate, pH 7.2) was added (100 μl/well), and the wells were allowed to incubate overnight at room temperature. The wells were washed three times with CovaBuffer (PBS buffer pH 7.2+2 M NaCl+4.1 mM MgSO 4 +0.5% (v/v) Tween 20 R ) leaving CovaBuffer (PBS buffer pH 7.2+2 M NaCl+4.1 mM MgSO 4 +0.5% (v/v) Tween 20 R ) leaving CovaBuffer in the wells for 10 minutes after the last wash. The wells were aspirated and avidin mix (4 μg/ml avidin (Sigma cat. no. A 9390) and 0.13 μg/ml Horse Radish Peroxidase conjugated avidin (DAKO cat. no. P 347) in PBS buffer pH 7.2) was added to each well (100 μl/well). The wells were incubated for 2 hours at room temperature and washed twice with CovaBuffer as described above. The amount of bound protein was quantified by measuring the peroxidase activity in citrate buffer (0.1 M, pH 5.0) containing 0.015% (v/v) H 2 O 2 and 0.6 mg/ml OPD (Sigma cat. no. P 8412) as chromogenic substrate. The enzymatic reaction was terminated after 6 minutes by addition of H 2 SO 4 (2M, 100 μl/well), and the color reaction quantified by measuring the absorption at 490 nm on the ELISA reader (InterMed Immuno reader NJ 2000). The results for phenanthrene quinone amine compound no. 3 are shown in FIGS. 8a and 8b. On PolySorp® surfaces (FIG. 8a) no significant higher signal was observed than the control level, while on Nunclon® Delta treated surfaces higher signals were observed for all irradiation times with a maximum with 0.116 mM photoprobe concentration and 5 minutes irradiation time. Results for anthraquinone amine compound no. 5 are shown in FIGS. 9a and 9b. On PolySorp® surfaces (FIG. 9a) a significant higher signal than the background (control) was clearly seen. Maximum was obtained with a photoprobe concentration between 0.116 mM and 0.0232 mM and 10 minutes irradiation time. On Nunclon® Delta treated surfaces significant higher signals than the background (control) were observed at all irradiation times with concentrations of the photoprobe higher than 3.72·10 -5 mM.
The effect of varying spacer arms was tested on anthraquinone amines compounds nos. 5, 7 and 9. The anthraquinone amines were dissolved in distilled water to a concentration of 0.1 mM photoprobe, and 100 μl was added to each well of a Nunc-Immuno® Module F16 PolySorp 35 and a non-sterile Nunc F96 (Nunclon® Delta treated) plate. The plates were placed 10 cm below the UV lamp and irradiated for 10 minutes. The wells were rinsed three times with demineralized water and dried for 50 minutes at 60° C.. A two-fold dilution series of biotin-succinimide ester in PBS buffer was added (100 μl/well), and the wells were allowed to incubate overnight at room temperature. The wells were washed three times with CovaBuffer, avidin mix was added, and the amount of bound protein quantified as described earlier. The results are shown in FIG. 10 and clearly indicate the effect of the linker length. Compound no. 9, with two β-alanine units, showed the overall highest signal when grafted on PolySorp®. Lower signals were seen, when compound no. 9 was grafted on Nunclon® Delta treated plates. However, the signal was still higher than for compound no. 5 and compound no. 7, indicating the advantage of having an optimal spacer length between the photoprobe and the primary amino group.
The uniformity of photochemically grafted amino groups on polystyrene surfaces was tested with anthraquinone amine compound no. 9. Compound no. 5 was dissolved in distilled water to a concentration of 0.1 mM photoprobe. 100 μl of the solution was added to each well in four non-sterile Nunc F95 (Nunclon® Delta treated) plates, placed 10 cm below the UV lamp and irradiated for 10 minutes. Each well was washed three times with demineralized water and dried for 50 minutes at 60° C. Biotin-succinimide ester in PBS buffer was added (125 μg/ml, 100 μl/well), and the wells allowed to incubate overnight at room temperature. After washing three times with CovaBuffer avidin mix was added to each well, and the amount of bound protein was quantified as described earlier. The results are shown in Table 2.
TABLE 2______________________________________Uniformity of primary amino groups polystyrene surfacesby UV grafting. Mean of four plates.Mean (Abs. 490 nm) St. dev. % CV______________________________________1.959 0.063 3.2______________________________________
The storage stability of photochemically grafted amino groups on polystyrene surfaces was tested with anthraquinone amine compound no. 9. Compound no. 5 was dissolved in distilled water to a concentration of 0.1 mM photoprobe. 100 μl of the solution was added to each well in non-sterile Nunc F96 (Nunclon® Delta treated) plates and Nunc-Immuno® Module F8 PolySorp plates (Nunc. cat. no. 469078), placed 10 cm below the UV lamp and irradiated for 10 minutes. Each well was washed three times with demineralized water and dried for 50 minutes at 60° C. One plate of each type was packed in sealed plastic bags and stored for up to 30 days at 4° C., 20° C., 37° C., and 60° C. Plates were taken out for testing at intervals of 1, 2, 6, 13, 20, and 30 days of storage. One plate of each type was used for stability testing. The plates were incubated with biotin-succinimide ester followed by avidin mix, and the amount of bound protein was quantified as described earlier. Results are shown in FIGS. 11 and 12. All date have been normalized relative to day zero (no storage). The results show that no significant reduction in activity is seen at a store temperature of 37° C. or below, while plates stored at 60° C. showed a slight decrease in signal.
Introduction of Carboxylic Acids onto Polystyrene Surfaces by UV Grafting
The anthraquinone carboxlylic acid derivative compound no. 13 was dissolved in 0.1 M LiOH and diluted with distilled water to a concentration of 5 mM. A two-fold dilution series of the photoprobe (100 μl/well) was made in non-sterile Nunc F96 (Nunclon® Delta treated) plates and in Nunc-ImmunoR Module F8 PolySorp plates. The plates were placed on a shaker for one hour at 50° C. before UV irradiation. the wells were aspirated and placed 14 cm from the UV lamp and irradiated for 10 minutes. Non-irradiated plates were used as control. The wells were rinsed three times with demineralized water and crytal violet (Merck cat. no. 1408, 15 mg in 100 ml of distilled water) added to each well (100 μl/well). The plates were incubated for 30 minutes at room temperature, washed three times with demineralized water and dried for 30 minutes at 60° C. Dissolution of bound crystal violet was done by adding a solution of 1 M HCl in 96% ethanol to each well. The results were read on an InterMed Immuno reader NJ 2000 at 590 nm and are shown in FIG. 13. As crystal violet binds as an ion pair to carboxylic acids, an increase in signal will indicate the presence of immobilized carboxylic acid groups on the surface. No signal was obtained on plates that had not been UV irradiated, while a significant increasing signal with increasing concentration of the photoprobe was seen on PolySorp® surfaces.
Example 4
Covalent Coupling of a Peptide onto Polystyrene Surfaces by UV Grafting
Peptide compound no. 19, N-terminally anthraquinone substituted, was dissolved in distilled water (0.1 mg/ml).
100 μl was added to each well of two Nunc-Immuno® Module F16 PolySorp®--except for row A--which was used as blank control. One strip (2×8 wells) at a time was irradiated 2, 5, 10, 15, 30, and 60 minutes, respectively (14 cm under the UV lamp). After UV irradiation the plates were rinsed three times with 0.4 M NaOH containing 0.25% Tween 20 R , and three times with PBS buffer. Immobilized peptide was detected with a monoclonal anti-peptide antibody (culture supernatant Hyb 161-2 from Statens Seruminstitut, Copenhagen, Denmark). A two-fold dilution series of the antibody in PBS-Tween® buffer was made in the Immuno Modules from row C and onwards (100 μl/well). In row A (peptide blank) undiluted culture supernatant was added, while row B was used as control without Hyb.161-2. The Immuno Modules were incubated for two hours at room temperature, and then washed three times with PBS buffer containing 0.05% Triton X-100 R . A mixture of rabbit anti-mouse (2 μg/ml DAKO code Z 259) and horse radish peroxidase conjugated goat anti-mouse (1:500, DAKO code P 447) was added to each well (100 μl), incubated for one hour at room temperature and washed three times as described above. OPD substrate (100 μl) was added to each well, and the substrate reaction was stopped after four minutes with 2 M H 2 SO 4 (100 μl/well). The results are shown in FIG. 14 and clearly show that 30 the optimum irradiation time was between 2 and 15 minutes. Optimal dilutaion factor of Hyb 161-2 culture supernatant was approx. 10 and was used in the subsequent experiments.
The effect of irradiation time was further investigated. the experiment was done as described above, except that a constant concentration of Hyb 161-2 (culture supernatant diluted 10 times) was used. The results are shown in FIG. 15 and clearly show that 10 minutes irradiation time was the optimum, but even after two minutes more than 80% of the maximum response was obtained. The background (non-specific reaction) in wells without peptide as well as wells without Hyb 161-2 was low. The decrease in signal at longer irradiation times is most likely due to increasing photochemical crosslinking of peptide backbone and the anthraquinone photoprobes leading to destruction of epitope recognition.
The effect of peptide concentration was tested. The N-terminally anthraquinone substituted peptide compound no. 19 and peptide without the anthraquinone moiety (free N-terminus) were dissolved in water (2 mg/ml), and a two-fold dilution series made for each peptide solution in Nunc F16 PolySorb® Immuno Modules. The modules were irradiated for 10 minutes (14 cm under the UV lamp) and washed as described earlier. Immuno modules with anthraquinone-peptide and free peptide were kept in the dark during photolysis as controls. The amount of immobilized peptide was measured as described above, using a constant concentration of Hyb 161-2 (culture supernatant diluted 10 times). The results are shown in FIG. 16. Only irradiated wells containing the anthraquinone-peptide showed any detectable signal. Optimum concentration of the anthraquinone-peptide was approx. 4 μg/ml. The decrease in signal in higher concentrations can, as described earlier, be atributed to photochemical crosslinking of peptide backbone of the immobilized peptides, leading to destruction of epitope recognition. In addition to this, higher concentration of anthraquinone peptide in the solution, favours solution-phase photochemistry to the reaction with the polymer, leading to soluble photochemical crosslinked peptide aggregates, which is later removed in the washing steps.
The storage stability of the photochemically grafted peptide was investigated. The anthraquinone peptide number 19 was dissolved in distilled water (0.1 mM), and the solution was added to each well of a Nunc-Immuno® Module F16 PolySorp . The wells were irradiated for 10 minutes (14 cm under the UV lamp) and finally washed as described earlier. the wells were coated with 1% sucrose in PBS buffer (300 μl/well), incubated for one hour at room temperature, then aspirated and dried with compressed air. The plates were packed in sealed plastic bags and stored at 4° C. and 37° C. The plates were taken out for testing at intervals from 1 to 32 days. ELISA was performed as earlier described, and the data are presented in FIG. 17. All data are normalized relative to day zero. No drop in signal was detected during the storage period, but a storage temperature of 37° C. consistently gave a slightly lower signal than at 4° C..
Example 5
UV Grafting of Anthraquinone Nitrolotriacetic Acid (NTA) Derivative 20 onto Polystyrene Surfaces
The anthraquinone NTA derivative 20 was dissolved in phosphate buffer (pH 5.5) to a start concentration of 1 mM. A two fold dilution series of the solution was made 30 in two Nunc-Immuno™ Module F16 PolySorp plates (100 μl/well) and incubated for 1 hour at 50° C. The wells were aspirated and one plate was placed 14 cm below the UV-lamp (Philips HPA 400) and irradiated with UV-light for 5 minutes while the other plate was kept in the dark as control. All wells were washed with demineralized water followed by the addition of crystal violet solution (15 mg in 100 ml demineralized water; 100 μl/well) and incubated at r.t. for 30 minutes. The plates were washed with water and dried at 60° C. for 1 hour. Dissolution of bound crystal violet was done by adding a solution of 1M Hcl in ethanol to each well. The results were read on an InterMed Immuno reader NJ 200 at 590 nm. The results are shown in FIG. 11 and shows a significant increase in signal with increasing concentration of the photoprobe. No signal was obtained in the wells that had not been UV-irradiated.
Metal chelates, especially nickel chelates, hare been reported to have specific binding properties for histidine tagged peptides and proteins (Hochuli et al., J. Chromat. 411, 177-184 (1987). To test the ability of the new NTA-derivatized microtitre plates to selectively bind histidine tagged peptides three biotinylated peptides, with and without a hexahistidine tag, were synthesized by standard Fmoc solid phase peptide synthesis (the three peptides were prepared similarly to the anthraquinone substituted peptide (compound 19) in example 1).
Peptide 1: Biotin-εAhx-Leu-Lys-Leu-Lys-Trp-Lys-OH
Peptide 2: Biotin-εAhx-Leu-Lys-Leu-Lys-Trp-Lys-His-His-His-His-His-His-OH
Peptide 3: Biotin-εAhx-Arg-Thr-Gln-Asp-Glu-Asn-Pro-Val-Val-His-Phe-Phe-Lys-Asn-Ile-Val-Thr-Pro-Arg-Thr-Pro-OH
Photocoupling of the anthraquinone substituted NTA derivative was done as described above except that the plate was irradiated with UV-light for 10 min without prior aspiration of the solution. The plate was washed three times with PBS buffer (pH 7.2) and then charged with nickel by adding NiSO 4 (50 mM in Milli Q water, 100 μl/well). After incubation for 30 min at room temperature the wells were washed three times with Milli Q water. Solutions of each peptide (23 μM, 100 μl/well) in the assay buffer (PBS buffer (pH 7.2) containing 0.05% Tween 20® and 500 mM NaCl) were added to separate rows of the plate. Water was added to the rest of the rows as control. The peptides were allowed to incubate overnight at room temperature, then the wells were washed three times with the assay buffer, and avidin mix (100 μl/well, for details see example 3) in the assay buffer added to the wells. After two hours at room temperature the wells were emptied, washed three times with assay buffer, and the amount of immobilized avidin quantified by measuring the peroxidase activity (for details see example 3). The results are shown in FIG. 18a and clearly show that only the histidine tagged peptide gave any significant binding in the nickel chelate plate.
Example 6
UV-grafting of Anthraquinone Substituted Polyethylene Glycol 2000 (AO--CO-PEG2000) Derivative 22 onto Polystyrene Surfaces
The anthraquinone PEG2000 derivative 22 was dissolved in Milli Q water to a concentration of 0.3 mM. Polystyrene slides (from Nunc, Denmark) were rinsed with 96% ethanol (1×5 minutes with ultrasonication) and Milli Q water (2×5 minutes with ultrasonication) and dried in a non-evacuated desiccator above CaCl 2 (residual water in the atmosphere above the CaCl 2 : 0.14-1.4 mg/l). Before photoimmobilization the slides were brought into equilibrium with the natural water content in the atmosphere. Two slides were placed in a small metal container and the photoprobe solution added to cover the surface of the slide with approx. 2.5 mm of the solution above the surface. One of the slides was placed 10 cm below the UV-lamp (Philips HPA 400) and irradiated for 5 minutes, while the other slide was kept in the dark as control. Both slides were rinsed thoroughly with Milli Q water from a bottle and then three times with Milli Q water with ultrasonication (3×5 minutes). The slides were dried in a non-evacuated desiccator above CaCl 2 . As further controls two slides were treated as described above with a solution of PEG2000 (0.3 mM) and another two slides with Milli Q water alone. The effect of the photografting were tested by measuring the advancing contact angles using a VCA-2000 instrument (AST Products, Inc.). Five drops (1.5-2.5 μl) of Milli Q water were placed on each slide and the advancing contact angle measured (two contact angles per drop giving 10 contact angles per slide) using the manufacturers software. Prior to each series of measurements, the slides were brought into equilibrium with the natural water content in the atmosphere. The results are shown in FIG. 12 and clearly show a decrease of the advancing contact angle on the anthraquinone substituted PEG2000 photografted polystyrene slide relative to the controls.
Example 7
UV-grafting of Anthraquinone Substituted Polyethylene Glycol 2000 (AO--CO-PEG2000) Derivative 22 onto Polypropylene Surfaces
The anthraquinone PEG2000 derivative 22 was dissolved in Milli Q water to a concentration of 0.3 mM. Polypropylene slides (from Nunc, Denmark) rinsed and dried as described for the polystyrene slides (Example 6). Two slides were placed in a small metal container and the photoprobe solution added to cover the surface of the slide with approx. 2.5 mm of the solution above the surface. One of the slides was placed 10 cm below the UV-lamp (Philips HPA 400) and irradiated for 5 minutes, while the other slide was kept in the dark as control. Both slides were rinsed thoroughly with Milli Q water from a bottle and then ten times with Milli Q water with ultrasonication (10×5 minutes). The slides were dried in a non-evacuated desiccator above CaCl 2 . As a further control one slide was washed and dried as described above. Advancing contact angle measurements were performed as described for the polystyrene slides. The results are shown in FIG. 13 and clearly show a decrease in the advancing contact angle on the anthraquinone substituted PEG2000 photografted polypropylene slide relative to the controls. | A method of immobilizing a ligand (L) to the surface (P) of a carbon-containing substrate material; said method comprising: a photochemical step of linking of one or more photochemically reactive compounds (Q) to a carbon-containing material surface (P); wherein the photochemically reactive compound (Q) is a quinone compound containing a cyclic hydrocarbon, or from 2 to 10 fused cyclic hydrocarbons, with at least two conjugated carbonyl groups; and wherein the photochemical step comprises irradiation of the photochemically reactive compound (Q) with non-ionizing electromagnetic radiation having a wavelength in the range from UV to visible light. | 8 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of high density data storage and imaging and more specifically to a data storage and image medium, a data storage and imaging system, and a data storage and imaging method.
BACKGROUND OF THE INVENTION
[0002] Current data storage and imaging methodologies operate in the micron regime. In an effort to store ever more information in ever smaller spaces, data storage density has been increasing. In an effort to reduce power consumption and increase the speed of operation of integrated circuits, the lithography used to fabricate integrated circuits is pressed toward smaller dimensions and more dense imaging. As data storage size increases and density increases and integrated circuit densities increase, there is a developing need for data storage and imaging methodologies that operate in the nanometer regime.
SUMMARY OF THE INVENTION
[0003] A first aspect of the present invention is a method, comprising: pushing a probe, heated to at least 100° C., into a cross-linked resin layer formed by curing a layer of polyimide oligomers; and removing the probe from the resin layer, resulting in formation of a deformed region in the resin layer.
[0004] A second aspect of the present invention is the first aspect wherein the polyimide oligomers have the structure:
wherein R′ is selected from the group consisting of
wherein R″ is selected from the group consisting of
[0005] A third aspect of the present invention is the second aspect, wherein the layer of polyimide oligomers includes a reactive diluent, the reactive diluent selected from the group consisting of:
where R 1 , R 2 and R 3 are each independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, alkylamino groups, arylamino groups, alkylarylamino groups, arylthio, alkylthio groups and
[0006] wherein the polyimide oligomers are cross-linked by reactive diluent groups derived from the reactive diluent during the curing.
[0007] A fourth aspect of the present invention is the third aspect wherein a glass transition temperature of the resin layer with the reactive diluent groups is within about 50° C. of a glass transition temperature of an otherwise identical resin layer formed without the reactive diluent groups.
[0008] A fifth aspect of the present invention is the first aspect wherein the polyimide oligomers have the structure:
wherein R′ is selected from the group consisting of
where R″ is selected from the group consisting of
[0009] A sixth aspect of the present invention is the first aspect wherein after the curing, the resin layer is cross-linked by reactive endgroups of the polyimide oligomers.
[0010] A seventh aspect of the present invention is the first aspect wherein after the curing, the resin layer is cross-linked by reactive pendent groups attached to a backbone of the polyimide oligomers.
[0011] An eighth aspect of the present invention is the first aspect wherein a glass transition temperature of the resin layer is less than about 250° C.
[0012] A ninth aspect of the present invention is the first aspect wherein a modulus of the resin layer above a glass transition temperature of the resin layer is between about 1.5 and about 3.0 decades lower than a modulus of the resin layer below the glass transition temperature of the resin layer.
[0013] A tenth aspect of the present invention is the first aspect wherein the resin layer is thermally and oxidatively stable to at least 400° C.
[0014] An eleventh aspect of the present invention is the first aspect further including: removing the resin layer in the deformed region to form an exposed region of a substrate and a region of substrate protected by the resin layer; and modifying at least a portion of the exposed region of substrate.
[0015] A twelfth aspect of the present invention is the first aspect further including: dragging the probe in a direction parallel to a top surface of the resin layer while heating and pushing the probe, resulting in formation of a trough in the resin layer.
[0016] A thirteenth aspect of the present invention is the first aspect wherein the cross-linked resin layer has a thickness between about 10 nm and about 500 nm and a thickness variation of less than about 1.0 nm across the cross-linked resin layer.
[0017] A fourteenth aspect of the present invention is a method, comprising: bringing a thermal-mechanical probe into proximity with a resin layer multiple times to induce deformed regions at points in the resin layer, the resin layer comprising cross-linked polyimide oligomers, the thermal mechanical probe heating the points in the resin layer above about 100° C. and thereby writing information in the resin layer.
[0018] A fifteenth aspect of the present invention is a data storage device, comprising: a recording medium comprising a resin layer overlying a substrate, in which topographical states of the resin layer represent data, the resin layer comprising cross-linked polyimide oligomers; and a read-write head having one or more thermo-mechanical probes, each of the thermo-mechanical probes including a resistive region locally exerting heat at a tip of the thermo-mechanical probe in response to electrical current being applied to the one or more thermo-mechanical probe; and a scanning system for scanning the read-write head across a surface of the recording medium.
BRIEF DESCRIPTION OF DRAWINGS
[0019] The features of the invention are set forth in the appended claims. The invention itself, however, will be best understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
[0020] FIGS. 1A through 1C illustrate the structure and operation of a tip assembly for a data storage device including the data storage medium according to the embodiments of the present invention;
[0021] FIG. 2 is an isometric view of a local probe storage array including data storage medium according to the embodiments of the present invention;
[0022] FIGS. 3A through 3D are cross-section views illustrating formation of a pattern in a substrate according to one embodiment of the present invention;
[0023] FIGS. 4A through 4E are cross-section views illustrating formation of a pattern in a substrate according to another embodiment of the present invention;
[0024] FIGS. 5A through 5E are cross-section views illustrating formation of a pattern in a layer on a substrate according to an embodiment of the present invention;
[0025] FIG. 6 is a diagram illustrating cross-linking of a polyimide resin with a reactive diluent according to embodiments of the present invention;
[0026] FIG. 7 is thermo-gravimetric analysis plotting percentage of weight remaining and temperature versus time of a polyimide resin according to an embodiment of the present invention compared to polystyrene resins;
[0027] FIG. 8 is a plot of modulus versus temperature of polyimide resins according to embodiments of the present invention;
[0028] FIGS. 9A through 9D are SEM photomicrographs of tips of various tip assemblies; and
[0029] FIG. 10 is an AFM scan-line cross-section showing data bits written in a storage medium according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0030] For the purposes of describing the present invention, on a scale of 0-100 units, a decade is 10 units. On a scale of 0-1000, a decade is 100 units. Therefore a decade of a range is defined as one-tenth of a range of units from 0 units to 10 n units, wherein n is a whole positive integer equal to or greater than 0.
[0031] FIGS. 1A through 1C illustrate the structure and operation of a tip assembly 100 for a data storage device including the data storage medium according to the embodiments of the present invention. In FIG. 1A , probe tip assembly 100 includes a U-shaped cantilever 105 having flexible members 105 A and 105 B connected to a support structure 110 . Flexing of members 105 A and 105 B provides for substantial pivotal motion of cantilever 105 about a pivot axis 115 . Cantilever 105 includes a tip 120 fixed to a heater 125 connected between flexing members 105 A and 105 B. Flexing members 105 A and 105 B and heater 125 are electrically conductive and connected to wires (not shown) in support structure 110 . In one example, flexing members 105 A and 105 B and tip 120 are formed of highly-doped silicon and have a low electrical resistance, and heater 125 is formed of lightly doped silicon having a high electrical resistance sufficient to heat tip 120 , in one example, between about 100° C. and about 400° C. when current is passed through heater 125 . The electrical resistance of heater 125 is a function of temperature.
[0032] Also illustrated in FIG. 1A is a storage medium (or a recording medium) 130 comprising a substrate 130 A, and a cured polyimide resin layer 130 B. In one example, substrate 130 A comprises silicon. Cured polyimide resin layer 130 B may be formed by solution coating, spin coating, dip coating or meniscus coating uncured polyimide resin formulations and performing a curing operation on the resultant coating. In one example, cured polyimide resin layer 130 B has a thickness between about 10 nm and about 500 nm and a variation in thickness of less than about 1.0 nm across the cured polyimide resin layer. The composition of cured polyimide resin layer 130 B is described infra. An optional penetration stop layer 130 C is shown between cured polyimide resin layer 130 B and substrate 130 A. Penetration stop layer 130 C limits the depth of penetration of tip 120 into cured polyimide resin layer 130 B.
[0033] Turning to the operation of tip assembly 100 , in FIG. 1A , an indentation 135 is formed in cured polyimide resin layer 130 B by heating tip 120 to a writing temperature T W by passing a current through cantilever 105 and pressing tip 120 into cured polyimide resin layer 130 B. Heating tip 120 allows the tip to penetrate the cured polyimide resin layer 130 B forming indentation 135 , which remains after the tip is removed. In one example, the cured polyimide resin layer 130 B is heated to above 200° C. by heated tip 120 to form indentation 135 . As indentations 135 are formed, a ring 135 A of cured polyimide polymer is formed around the indentation. Indentation 135 represents a data bit value of “1”, a data bit value of “0” being represented by an absence of an indentation.
[0034] FIGS. 1B and 1C illustrate reading the bit value. In FIGS. 1 B and 1C , tip assembly 100 is scanned across a portion of cured polyimide resin layer 130 B. When tip 120 is over a region of cured polyimide resin layer 130 B not containing an indentation, heater 125 is a distance D 1 from the surface of the cured polyimide resin layer (see FIG. 1B ). When tip 120 is over a region of cured polyimide resin layer 130 B containing an indentation, heater 125 is a distance D 2 from the surface of the cured polyimide resin layer (see FIG. 1C ) because the tip “falls” into the indentation. D 1 is greater than D 2 . If heater 125 is at a temperature T R (read temperature), which is lower than T W (write temperature), there is more heat loss to substrate 130 A when tip 120 is in an indentation than when the tip is not. This can be measured as a change in resistance of the heater at constant current, thus “reading” the data bit value. It is advantageous to use a separate heater for reading which is mechanically coupled to the tip but thermally isolated from the tip. A typical embodiment is disclosed in Patent Application EP 05405018.2, 13 Jan. 2005.
[0035] “Erasing” (not shown) is accomplished by positioning tip 120 in close proximity to indentation 135 , heating the tip to a temperature T E (erase temperature), and applying a loading force similar to writing, which causes the previously written indent to relax to a flat state whereas a new indent is written slightly displaced with respect to the erased indent. The cycle is repeated as needed for erasing a stream of bits whereby an indent always remains at the end of the erase track. T E is typically greater than T W . The erase pitch is typically on the order of the rim radius. In one example, the cured polyimide resin layer 130 B is heated to above about 200° C. by heated tip 120 , and the erase pitch is 10 nm to eliminate indentation 135 .
[0036] FIG. 2 is an isometric view of a local probe storage array 140 including data storage medium according to the embodiments of the present invention. In FIG. 2 , local probe storage array 140 includes substrate 145 having a cured polyimide resin layer 150 (similar to cured polyimide resin layer 130 B of FIGS. 1A, 1B and 1 C), which acts as the data-recording layer. An optional tip penetration stop layer may be formed between cured polyimide resin layer 150 and substrate 145 . In one example, substrate 145 comprises silicon. Cured polyimide resin layer 150 may be formed by solution coating, spin coating, dip coating or meniscus coating uncured polyimide resin formulations and performing a curing operation on the resultant coating. In one example, cured polyimide resin layer 150 has a thickness between about 10 nm and about 500 nm and a variation in thickness across a writeable region of cured polyimide resin layer 150 of less than about 1.0 nm across the cured polyimide resin layer. The composition of cured polyimide resin layer 150 is described infra. Positioned over cured polyimide resin layer 150 is a probe assembly 155 including an array of probe tip assemblies 100 (described supra). Probe assembly 155 may be moved in the X, Y and Z directions relative to substrate 145 and cured polyimide resin layer 150 by any number of devices as is known in the art. Switching arrays 160 A and 160 B are connected to respective rows (X-direction) and columns (Y-direction) of probe tip assemblies 100 in order to allow addressing of individual probe tip assemblies. Switching arrays 160 A and 160 B are connected to a controller 165 which includes a write control circuit for independently writing data bits with each probe tip assembly 100 , a read control circuit for independently reading data bits with each probe tip assembly 100 , an erase control circuit for independently erasing data bits with each probe tip assembly 100 , a heat control circuit for independently controlling each heater of each of the probe tip assembles 100 , and X, Y and Z control circuits for controlling the X, Y and Z movement of probe assembly 155 . The Z control circuit controls a contact mechanism (not shown) for contacting the cured polyimide resin layer 150 with the tips of the array of probe tip assemblies 100 .
[0037] During a write operation, probe assembly 155 is brought into proximity to cured polyimide resin layer 150 and probe tip assemblies 100 are scanned relative to the cured polyimide resin layer. Local indentations 135 are formed as described supra. Each of the probe tip assemblies 100 writes only in a corresponding region 170 of cured polyimide resin layer 150 . This reduces the amount of travel and thus time required for writing data.
[0038] During a read operation, probe assembly 155 is brought into proximity to cured polyimide resin layer 150 and probe tip assemblies 100 are scanned relative to the cured polyimide resin layer. Local indentations 135 are detected as described supra. Each of the probe tip assemblies 100 reads only in a corresponding region 170 of cured polyimide resin layer 150 . This reduces the amount of travel and thus the time required for reading data.
[0039] During an erase operation, probe assembly 155 is brought into proximity to cured polyimide resin layer 150 , and probe tip assemblies 100 are scanned relative to the cured polyimide resin layer. Local indentations 135 are erased as described supra. Each of the probe tip assemblies 100 reads only in a corresponding region 170 of cured polyimide resin layer 150 . This reduces the amount of travel and thus time required for erasing data.
[0040] Additional details relating to data storage devices described supra may be found in the articles “ The Millipede—More than one thousand tips forfuture AFM data storage ,” P. Vettiger et al., IBM Journal of Research and Development . Vol. 44 No. 3, May 2000 and “ The Millipede—Nanotechnology Entering Data Storage ,” P. Vettiger et al., IEEE Transaction on Nanotechnology , Vol. 1, No, 1, March 2002. See also United States Patent Publication 2005/0047307, Published Mar. 3, 2005 to Frommer et al. and United States Patent Publication 2005/0050258, Published Mar. 3, 2005 to Frommer et al., both of which are hereby included by reference in there entireties.
[0041] FIGS. 3A through 3D are cross-section views illustrating formation of a pattern in a substrate according to one embodiment of the present invention. In FIG. 3A , formed on a substrate 200 is a cured polyimide resin layer 205 (similar to cured polyimide resin layer 130 B of FIGS. 1A, 1B and IC and cured polyimide resin layer 150 of FIG. 2 ) which will be an imaging layer. Cured polyimide resin layer 205 may be formed by applying (by solution coating, spin coating, dip coating or meniscus coating) a layer of uncured polyimide oligomers (including reactive end capping agents and optional reactive diluents or reactive backbone linking agents as described infra) and then heating the substrate and uncured polyimide oligomers to a curing temperature causing cross-linking of the polyimide oligomers into a polyimide resin.
[0042] In FIG. 3B , a heated probe tip 210 is pushed down (perpendicular to a top surface 215 of substrate 200 ) into cured polyimide resin layer 205 and then dragged parallel to top surface 215 of substrate 200 thus exposing a region of substrate 200 .
[0043] In FIG. 3C , a trench 220 is etched into substrate 200 wherever the substrate is not protected by cured polyimide resin layer 205 . In FIG. 3D , cured polyimide resin layer 205 (see FIG. 3C ) is removed.
[0044] FIGS. 4A through 4E are cross-section views illustrating formation of a pattern in a substrate according to another embodiment of the present invention. FIGS. 4A are 4 B are similar to FIGS. 3A and 3B except in FIG. 4B , heated probe 210 is not pressed completely through cured polyimide resin layer 205 forming a cured polyimide resin thinned region 225 in cured polyimide resin layer 205 . In FIG. 4C , cured polyimide resin thinned region 225 (see FIG. 4B ) is removed exposing top surface 215 of substrate 200 and also producing a thinned cured polyimide resin layer 205 A. In one example, the removal of cured polyimide resin thinned region 225 is done by reactive plasma. In one example, the removal of cured polyimide resin thinned region 225 is done by controlled exposure to a liquid or a vapor.
[0045] In FIG. 4D , trench 220 is etched into substrate 200 wherever the substrate is not protected by thinned cured polyimide resin layer 205 A. In FIG. 4E , thinned cured polyimide resin layer 205 A (see FIG. 4D ) is removed.
[0046] FIGS. 5A through 5E are cross-section views illustrating formation of a pattern in a layer on a substrate according to an embodiment of the present invention. FIGS. 5A and 5B are similar to FIGS. 4A and 4B except a hard mask layer 230 is formed between substrate 200 and cured polyimide resin layer 205 . In FIG. 5C , cured polyimide resin thinned region 225 (see FIG. 5B ) is removed exposing a top surface 235 of hard mask layer 225 and also producing a thinned cured polyimide resin layer 205 A.
[0047] In FIG. 5D , trench 240 is etched into hardmask layer 225 wherever the substrate is not protected by thinned cured polyimide resin layer 205 A. In FIG. 5E , thinned cured polyimide resin layer 205 A (see FIG. 5D ) is removed. Hardmask layer 230 may be used to etch substrate 200 or to block diffusion and ion implantation or as a mandrel for deposition of other coatings including conformal coatings.
[0048] The methodologies illustrated in FIGS. 3A through 3D , 4 A through 4 E and 5 A through 5 E may advantageously be applied to fabrication of integrated circuits and other semiconductor devices. Using these methods, features having a minimum dimension of less than about 40 nm may be formed.
[0049] Turning to the composition of cured polyimide resin layer 130 B of FIGS. 1A through 1C , cured polyimide resin layer 150 of FIG. 2 and cured polyimide resin layer 205 of FIGS. 3A through 3C , FIGS. 4A and 4B and FIGS. 5A and 5B , there are three general formulations of uncured polyimide resins. It should be understood that for the purposes of the present invention curing an oligomer implies cross-linking the oligomer to form a polymer or cross-linked polymer or resin.
[0050] The polyimide medium or imaging layer of the embodiments of the present invention advantageously meets certain criteria. These criteria include high thermal stability to withstand millions of write and erase events, low wear properties (low pickup of material by tips), low abrasion (tips do not wear out), low viscosity for writing, glassy character with no secondary relaxations for long data bit lifetime, and shape memory for erasability.
[0051] Thermal and oxidative stability was imparted to cured polyimide resins by incorporating a large aromatic content in the polymer backbone and by ladder type linkages such as imide functionalities. Cured polyimide resins according to embodiments of the present invention have high temperature stability while maintaining a low glass transition temperature (T g ), which is contrary to current teaching that high temperature stability results in a high T g and vice versa. In one example, cured polyimide resins according to embodiments of the present invention are thermally and oxidatively stable to at least 400° C.
[0052] Wear and erasability of the media were improved by cross-linking the polyimide oligomers without increasing the T g which was unexpected. By placing the cross-linking sites at the chain ends, the molecular weight of polyimide oligomers is predefined and therefore cross-linking was found to have a lesser effect upon the glass transition temperature than is currently thought. The width of the transition from the rubbery to glassy state of the cured polyimide resin was found not to increase significantly over that of the polyimide oligomer. The sharp and practically temperature-invariant transition from the glassy to rubbery state as seen in polyimide oligomers was maintained in the cross-linked resin. Again, this is contrary to what is currently tought. The molecular weights of the polyimide oligomers themselves are controlled by the ratio of anhydride, amine and reactive end group precursor used in the polyimide oligomer synthesis.
[0053] Further control over the cross-link density was achieved by adding controlled amounts of reactant diluents described infra that enhance cross-linking. These reactive diluents formed a high density of cross-links that enhanced the wear properties of the polyimide medium without greatly increasing the T g or width of the glass transition.
[0054] The glass transition temperature was adjusted for good write performance. To optimize the efficiency of the write process there should be a sharp transition from the glassy state to the rubbery state. A sharp transition allows the cured resin to flow easily when a hot tip is brought into contact and quickly return to the glassy state once the hot tip is removed. However, too high a T g leads to high write currents and damage to the probe tip assemblies described supra. Incorporation of flexible aryl ether and thioether linkages resulted in polyimide resins of lower than expected T g . In one example, cured polyimide resins of the embodiments of the present invention have T g s of less than about 250° C., preferably between about 120° C. and about 250° C., more preferably between about 120° C. and 150° C.
[0055] Long data bit lifetime of the polyimide resin medium was obtained by the incorporation of hetero-atoms such as oxygen and sulfur in the polyimide resin backbone and varying the catenation of aromatic rings from para to meta linkages.
[0056] A first formulation of uncured polyimide resin comprises polyimide oligomers having the structure:
wherein R′ is selected from the group consisting of
and wherein R″ is selected from the group consisting of
[0057] The endgroups, having the structure:
provide the cross-linking of the polyimide oligomers into a polyimide resin. The reactive end group is the phenylethynyl group of structure (XI). In one example, curing is performed at about 300° C. to about 350° C.
[0058] In a second formulation of uncured polyimide resin, one or more of the following reactive diluents (including combinations of different structures (XII)) is added to the first formulation:
where R 1 , R 2 and R 3 are each independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, alkylamino groups, arylamino groups, alkylarylamino groups, arylthio, alkylthio groups and
[0059] It should be noted that reactive diluents XII and XIII contain three substituted phenylethynyl groups. The phenylethynyl groups of the polyimide oligomers and the phenylethynyl groups reactive diluents provide the cross-linking of the polyimide oligomers into a polyimide resin. In one example, curing is performed at about 300° C. to about 350° C.
[0060] In one example, a Tg of a cured polyimide resin layer formed using the second formulation of the present invention with a reactive diluent is within about 50° C. of a Tg of an otherwise identical cured polyimide resin layer formed without the reactive diluent.
[0061] FIG. 6 is a diagram illustrating cross-linking of a polyimide resin with a reactive diluent according to embodiments of the present invention. In FIG. 6 , a mixture of straight chain polyimide oligomer 250 of repeating units n and having two reactive endgroups 255 (which represents structure (I)) a reactive diluent 260 having three reactive functionalities 265 (representing structures (XII and XIII) is heat cured to produce a cross-linked polyimide resin 270 . In resin 270 , polyimide oligomers 250 are linked to each other through respective reactive endgroups; polyimide oligomers 250 are linked to reactive diluents 260 through respective reactive endgroups and reactive diluents 260 and linked to each other through respective reactive endgroups. Although Tg is usually a function of molecular weight and cross-link density, in this case it is largely independent of the percentage by weight of reactive diluent in the polyimide oligomer/reactive diluent mixture.
[0062] A third formulation of uncured polyimide resin comprises polyimide oligomers having the structure:
wherein R′ is selected from the group consisting of
and wherein R″ is selected from the group consisting of
Experimental
[0063] All materials were purchased from Aldrich and used without further purification unless otherwise noted.
[0000] Preparation of Thioether Dianhydride Oligomers (mTEDA and pTEDA)
[0064] Either 1,3-benzenedithiol or 1,4-benzenedithiol was dissolved in DMSO (20% solids) with triethylamine and 4-fluorophthalic anhydride. The mixture was heated to 60° C. for 4 hours and then either the mTEDA or pTEDA were precipitated on ice, filtered, and re-crystallized twice from DMSO/acetic anhydride.
[0000] Preparation of Phenylene Ether Dianhydride Oligomers
[0065] A bisphenol (e.g. 4-hydroxyphenyl ether) was dissolved in dry DMF with 4-nitrophthalonitrile and potassium carbonate. The solution was heated to 120° C. and the water generated was removed by azeotropic distillation with toluene. After 24 hours, the solids were precipitated on ice. The resulting solid was collected by vacuum filtration. The solid was then refluxed in toluene, ethanol, and hydrochloric acid to hydrolyze the nitrile groups to carboxylic acids. The mixture was again poured over ice and the resulting solid collected by vacuum filtration. The tetraacid was then dissolved in toluene and acetic anhydride, and heated to reflux for 8 hours. The resulting precipitate was collected by vacuum filtration and re-crystallized from acetic anhydride.
[0000] Preparation of Diamines
[0066] A bisphenol was dissolved in dry DMF with 4-fluoronitrobenzene, and potassium carbonate. The same procedure was followed as above for the nucleophilic aromatic substitution. The resulting solid was dissolved in THF and NaBH 4 was added slowly. The reaction was allowed to stir overnight and the product was collected by removal of the solvent under vacuum, and then extracted with CH 2 Cl 2 and water. The organic phase was collected and the solvent removed under vacuum. The resulting solid was purified by vacuum sublimation.
[0000] Preparation of Bishydroxyphenylethers
[0067] The reagent 3-bromophenol was reacted with benzylbromide in the presence of potassium carbonate and 18-crown-6 in THF for 24 h. The reaction mixture was filtered to remove excess potassium carbonate and resultant potassium bromide, and the solvent was removed under vacuum. The remaining liquid was filtered through silica to give 3-bromophenylbenzylether in 92% yield. This product was then dissolved in dry NMP together with resorcinol, copper iodide, cesium carbonate, and tetramethylheptanedione. The mixture was stirred vigorously and heated at 120° C. for 72 hours. The solution was then precipitated by pouring over ice and extracted with methylene chloride. The organic phase was collected and the solvent removed. The resulting oil was dissolved in toluene and concentrated hydrochloric acid and heated to reflux.
[0000] Polyimide Oligomer Synthesis from Amic Acid
[0068] In a dry atmosphere, the oligomers, a diamine, and acetic anhydride were dissolved in dry cyclohexanone (20% solids) and allowed to stir for 24 hours. The poly(amic acid) formed was used to cast films from cyclohexanone. NMR spectra of the amic acids were acquired by removal of the solvent under vacuum and the addition of dry DMSO-d 8 .
[0000] Polyimde Oligomer Synthesis by Chemical Imidization
[0069] Under an inert atmosphere, a bisanhydride and a diamine (purified by vacuum sublimation) were dissolved in dry NMP and allowed to stir for 24 hours. Acetic anhydride and triethylamine were then added and the reaction was allowed to stir under inert atmosphere for 48 hours. Finally the mixture was heated to 60° C. for 2 hours and then precipitated by pouring into stirring methanol. The resulting solid was washed on the frit with water, and methanol, and re-precipitated twice from cyclohexanone (or NMP).
[0000] Film Preparation from Polyimide
[0070] The polymer was dissolved in cyclohexanone (5% by weight) and filtered through a 0.2-micrometer filter onto UV/ozone cleaned silicone wafers. The wafer was then spun at 2500 rpm for 30 seconds yielding an approximately 100 nm thick film. The films were cross-linked on a hotplate under an inert atmosphere with a heating program of a 1-hour ramp from 50° C. to 350° C. and held an additional hour at 350° C. Bulk films and samples containing reactive diluent structure (XIII) were prepared in a similar fashion except for bulk films where a 20 weight % solution was used.
[0000] Film Preparation from Amic Acid
[0071] Under dry atmosphere, the polyamic acid precursors were diluted with cyclohexanone to the appropriate concentration (5% solids). Minimizing the exposure to ambient air, films of the precursor were spun at 2500 rpm for 30 seconds and then cured with a heating program of a 1-hour ramp from 50° C. to 350° C. and held an additional hour at 350° C.
[0072] In a first synthesis example, polyimide resins of varying molecular weights were synthesized by varying the ratios of the two oligomers 1,3-bis(4-aminophenoxy)benzene (XXVI) and 4,4′(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (XXV) and the end capping agent 4-phenylethynylpthalic anhydride (XXVII). Bulk samples and thin films of these materials were prepared and then cured at 350° C. for one hour to yield highly cross-linked films.
[0073] One preparation (Sample A) of structure (XXVIII) was extensively studied. Cured sample A had a <Mn> 14,400 g/mol, Mw/Mn=1.9 and when cured at 350° C. had a Tg of about 175° C.
[0074] In a second synthesis example:
Other Syntheses
[0075] In order to reduce the glass transition temperature, the rigidity of the polymer backbone must be decreased. To that end, polyimide oligomers with an increased number of flexible aryl ether linkages as well as thioether linkages were synthesized.
[0076] Dianhydride phenylene ether containing oligomers were synthesized from the reaction of 4-nitrophthalonitrile with the requisite bisphenol precursor followed by hydrolysis of the cyano groups and dehydration to form the cyclic anhydride. The thioether variants were synthesized directly in one step from the reaction of a bisthiophenol with 4-fluorophthalic anhydride. This synthetic scheme allowed a series of ether- and thioether-containing oligomers with two or more ether or thioether linkages and all possible combinations of meta and para catenation. Furthermore the scheme was easily adapted to synthesize a number of phenylene ethers containing diamines with the same variation on number of ether linkages and catenation schemes by reaction of a bisphenol derivative with 4-fluoronitrobenzene and subsequent reduction of the nitro group to an amine.
[0077] The thioether dianhydrides were reacted with a series of diamines and 4-phenylethynylphthalic anhydride in specific ratios to yield polyimide oligomers with molecular weights ranging from 4×10 3 g/mol to 10×10 3 g/mol. The first step in the polymerization mechanism is the reaction of one diamine with one anhydride to form an amic acid. One of two steps can be taken at this point. For polymers where the fully imidized form exhibited good solubility and good film forming properties with cyclohexanone as the solvent, the polymer was imidized by a chemical dehydration with triethyl amine and acetic anhydride, and then isolated and characterized. With certain polymer compositions, the fully imidized material was difficult to process. To circumvent these issues with solubility and film forming properties, these polymers were processed into thin films from the amic acid. The polymers were then imidized thermally as thin films concurrently with the final cross-linking reaction. The amic acid precursors were analyzed by removal of the solvent under vacuum and transfered to dry sample containers with dried and distilled solvents for analysis by GPC and 1 H-NMR. The thermal and mechanical properties of cured films were studied by TGA, DSC, and DMA.
[0078] Example of synthesis and structures of thioether containing dianhydride oligomers:
TABLE I Properties of thioether based polyimides T g before T g Dianhydride Diamine <M n > × 10 −3 g/mol cure ° C. cured ° C. pTEDA APTE 4.0 T m 261(a) 162 mTEDA APTE 4.0 163 178 mTEDA mAPB 7.0 (b) (b) mTEDA mAPB 7.0 (c) 209 Processed from amic acid mTEDA mAPB 14.0 (c) 151 Processed from amic acid where
(a) T m indicates the temperature at which the sample melted.
(b) Semicrystalline, Tg not available.
(c) In processing from amic acid, cross-linking occurs concurrently with the conversion of the acid to the polyimide. Therefore there's no opportunity to measure Tg previous to cross-linking.
[0079] Example synthesis of bis-4,4′-isophthaloyloxyphenylene ether.
[0080] The phenylene ether materials exhibited similar solubility limitations as the thioether based materials. However, when all linkages in the diamine and the dianhydride were meta catenated, materials showed much improved solubility in solvents such as THF and cyclohexanone. These materials could be processed either from the amic acid or fully imidized states. Exclusively para catenated materials also exhibited semi-crystalline properties. However, once cured, the films were no longer crystalline due to the cross-links preventing crystallization of the chains. Working from the amic acid precursors avoided all solubility issues associated with the para-arylene ether polymers.
TABLE 2 Phenylene ether based polyimides, imidized chemically % II % III <M n > × 10 −3 g/mol T g before cure ° C. T g cured ° C. 100 0 10.0 T m 261 162 50 50 10.0 163 178 where
[0081] FIG. 7 is thermo-gravimetric analysis (TGA) plotting percentage of weight remaining and temperature versus time of a polyimide resin according to an embodiment of the present invention compared to polystyrene resins. The primary limiting factor in the use of polystyrene (PS) or of polystyrene-co-vinylbenzocyclobutene (PSBCB) for a storage medium was poor thermal stability. The results of a TGA study showed that polyimides resins outperformed PS and PSBCB resins. The styrenic material began to decompose rapidly once the furnace reached 250° C. while the polyimide resin showed no appreciable degradation until above 350° C. in scanning TGA and no weight loss over hours at 250° C. in isothermal TGA. The polyimide resin used in this TGA study was XXVIII.
[0082] FIG. 8 is a plot of modulus versus temperature polyimide resins according to embodiments of the present invention. FIG. 8 plots the storage modulus versus temperature for cured sample A and for a polyimide resin made by curing sample A with 30% by weight reactive diluent structure (XIII). Cured sample A exhibited a change in modulus of about 3 decades transitioning from the glassy state to the rubbery state. Cured sample A and 30% by weight reactive diluent structure (XIII) exhibited a drop in modulus of about 2 decades transitioning from the glassy state to the rubbery state. The Tg range for both samples was about the same with a Tg of about 175° C. In general a polyimide resin layer according to embodiments of the present invention had a modulus above a glass transition temperature between about 1.5 and about 3.0 decades lower than a modulus of the polyimide resin layer below the glass transition temperature of the polyimide resin layer.
[0083] FIGS. 9A through 9D are SEM photomicrographs of tips of various tip assemblies. FIG. 9A is an SEM photomicrograph of an unused tip 120 (see FIG. 1A ). FIG. 9B is an SEM photomicrograph of a worn tip 120 after use on a polystyrene layer. FIG. 9C is an SEM photomicrograph of an worn tip 120 after use on a PSBCB layer showing pickup of the storage medium. FIG. 9D is an SEM photomicrograph of tip 120 after about 2.4E6 write/erase and about 2.3E8 read cycles of a polyimide resin medium according to embodiments of the present invention. As can be seen there is virtually no tip wear.
[0084] FIG. 10 is an AFM scan-line cross-section showing data bits written in a storage medium according to an embodiment of the present invention. In FIG. 10 a pattern of data bits (indentation for a “1”, no indentation for a “0”) were written and the definition of the data determined using an AFM. Each “1” bit generated a very sharp and distinct signal, while the noise generated by “0” bits was very low. The write pitch was 34 nm which is greater than 500 Gb/inch 2 .
[0085] Thus, the embodiments of the present invention provide data storage and imaging methodologies that operate in the nanometer regime.
[0086] The description of the embodiments of the present invention is given above for the understanding of the present invention. It will be understood that the invention is not limited to the particular embodiments described herein, but is capable of various modifications, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, it is intended that the following claims cover all such modifications and changes as fall within the true spirit and scope of the invention. | An approach is presented for designing a polymeric layer for nanometer scale thermo-mechanical storage devices. Cross-linked polyimide oligomers are used as the recording layers in atomic force data storage device, giving significantly improved performance when compared to previously reported cross-linked and linear polymers. The cross-linking of the polyimide oligomers may be tuned to match thermal and force parameters required in read-write-erase cycles. Additionally, the cross-linked polyimide oligomers are suitable for use in nano-scale imaging. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a portable floor system and in particular to an improved locking assembly and mounting system for the locking assembly.
2. Description of the Prior Art
Portable floors generally have a number of interlocking, rectangular sections or panels and are used for providing an extended hard surface that may be set up over carpeting or other surfaces on a temporary basis, by joining the floor sections together in an edge-to-edge relationship. Locks or other connectors are provided along the edges of the panels to secure the adjacent panels together to form the extended floor surface.
Portable floors are used for a variety of purposes and are particularly useful in the hospitality and entertainment industry. It is often desired to provide a temporary smooth hard surface for dancing or other activities that can be removed so the space may be used for other activities. Floors are usually connected together in an edge-to-edge fashion with releasable locks along their edges. A portable floor of this general type is disclosed in U.S. Pat. No. 3,310,919, which discloses floor panels with each floor panel having an extruded tongue section along certain edges and a complementary extended groove section along certain other edges. The adjoining sections can be fitted together in an edge-to-edge relationship by a tongue and groove arrangement and held in place by threaded locking screws mounted above the grooves to engage notches in the tongue members. Although the portable floor disclosed in that patent has been successful in providing a convenient and efficient portable floor, further improvements are possible.
Another patent showing portable floors is U.S. Pat. No. 6,128,881. Cam-type rotary locks having complementary male and female members on the edge of the panels are used to engage and lock the panels together in proper alignment. Although the cam-type rotary locks are an improvement, there are challenges with mounting such locks. As weight is a concern in the portable floor panels, it is often desired to utilize a panel construction having a light weight core panel to reduce overall weight. Although using core materials such as foam, honeycomb or balsa wood aids in reducing weight, these materials are not suitable as a mounting structure. Prior methods of mounting the rotary locks to the floor panel with a core that provides little support is difficult. Moreover, such systems are difficult to replace when failure occurs. Typically, a portion of the core is removed and a wood block is inserted for mounting by joint connector nuts and bolts or mounting using standard wood screws. Such a system requires a precise alignment for a joint connector bolt inserting into a complementary joint connector nut having a complementary orifice. Great precision is required for aligning the nuts and bolts. Moreover, such systems using either wood screws or joint connector require drilling of a pilot hole. Improper positioning of such pilot holes may ruin the panel during the manufacturing process.
In addition, such systems are difficult to repair should failure occur. Although the rotary locks are generally held by at least two screws or joint connector bolts, they typically have four mounting holes. However, due to the proximity between the holes, if failure occurs, the adjacent hole is typically too close to the position of the failure to allow for repair and mounting of a separate joint connector nut and bolt.
A further problem is the precise alignment that is required and the special manufacturing methods needed to align all of the various elements. The anchoring block and the rotary lock member are also spaced apart with light weight core material or alternate fill material between the elements when mounted so that when force is applied, the material between the wood block and the lock member can collapse, which can lead to failure and/or misalignment.
Another problem with portable floors is alignment of wood grain surfaces to provide continuity. Due to imprecise manufacturing, floors that have aligned wood grains have been difficult to achieve. It can be appreciated that a method that provides for properly aligning and orienting the wood grain so that the pattern on the top surface is consistently placed so that each panel has an identical appearance and aligns with any other panel improves overall appearance of the floor system.
It can be seen that a new portable floor system using new and improved portable floor panels is needed that overcomes the problems related to locking assemblies and their mounting. Such a system should provide for simple and easy insertion and manufacture of the floor panel and the locking devices. Such a system should also eliminate soft core material between the locking member and the anchoring element. Such a system should also improve alignment and provide a light weight anchor that is easily replaced should failure occur. The present invention addresses these, as well as other problems associated with portable floor systems.
SUMMARY OF THE INVENTION
The present invention is directed to a portable floor system and in particular to a floor system wherein the individual floor panels have an improved mounting assembly for mounting the arrangement for the locking assemblies.
The portable floor system of the present invention provides a temporary floor surface that is suitable for dancing or other activities while providing multi-use capability for the space where the floor is removed. The present invention provides a portable floor having substantially rectangular floor panels connecting and locking along their edges to form a continuous extended floor surface. Along the edges of the floor are edge trim panels that provide a transition from the portable floor surface to the underlying surface.
Each of the floor panels includes a planar floor portion with an extruded edge section. These edges form complementary tongues and grooves for aligning the panels together. The panels are locked together by a cam-type rotary lock having complementary male and female members on the edges of adjacent panels. As the cam locks engage, the camming action tends to slide the panels relative to one another along the edges, thereby locking the panels together and ensuring a proper fit with no gaps between the panels. The present invention provides for a lightweight and easy to manufacture mounting arrangement for the locking assemblies. The lock members attach directly to an anchor element mounted into a slot formed in the floor panel. The anchor element is a light weight plastic element having holes receiving mounting screws that attach through the locking member directly to the anchor element. The direct mounting eliminates the need for making precise pilot holes as was needed with the prior art lock mounting systems. In addition, the direct abutment of the locking devices to the anchor element provides a stronger rigid mount that eliminates the sagging and compression that may occur if the soft core material between the lock and the mounting blocks of the prior art has pressure applied.
In addition to a sturdier mounting arrangement, the mounting system of the present invention is also easy to manufacture. A first slot for the anchor element is formed in the bottom of the panel and a second slot for receiving the lock is formed in the edge of the panel to intersect the first slot and form a continuous opening. This provides for mounting the lock member directly against the anchor element for additional support. Moreover, the pattern on the upper surface may be continuous panel to panel and the lock and anchoring elements are aligned off a particular indexing feature of the surface panels so that the various panels are precisely aligned and therefore, can form a continuous wood grain pattern from panel to panel over the entire floor.
The mounting arrangement also provides for easy replacement as damaged screws may simply be replaced by removing the anchor element and the lock and replacing the damaged pieces. It can also be appreciated that if a mounting screw or hole is stripped, an adjacent hole may be utilized for mounting, thus eliminating the need for replacement of the anchor element. Moreover, the present invention does not require any type of adhesive or special steps for mounting. The anchor element is a rigid light weight plastic material such as nylon, with much of the slot into which it inserts remaining empty so that the mounting system achieves weight savings over the prior art systems.
These features of novelty and various other advantages that characterize the invention are pointed out with particularity in the claims annexed hereto and forming a part hereof. However, for a better understanding of the invention, its advantages, and the objects obtained by its use, reference should be made to the drawings that form a further part hereof, and to the accompanying descriptive matter, in which there is illustrated and described a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a portable floor system according to the principles of the present invention;
FIG. 2 is a bottom exploded perspective view of a floor panel for the portable floor system shown in FIG. 1 ;
FIG. 3 is a top view of the floor panel shown in FIG. 2 with portions removed to show the locking assembly;
FIG. 4 is a bottom perspective view with portions removed of two panels for the floor system shown in FIG. 1 joined together;
FIG. 5 is a side sectional view of a portion of the panel shown in FIG. 2 ;
FIG. 6 is top detail view of the floor panel shown in FIG. 2 showing the locking assembly;
FIG. 7 is a bottom perspective view of two locking assemblies shown in FIG. 6 and their mounting to the panels with the locking assemblies connected;
FIG. 8 is a top plan view of a portion of the panel shown in FIG. 2 showing slots for installation of the locking assembly;
FIG. 9 is a perspective view of the anchor element for the locking assembly shown in FIG. 6 ; and
FIG. 10 is a side elevational view of an anchor element shown in FIG. 9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, and in particular to FIG. 1 , there is shown a portable floor system, generally designated 10 . The floor system 10 includes a plurality of generally rectangular floor panels 12 joined in an edge-to-edge relationship to form an extended, continuous floor surface. Such panels generally include a lightweight planar portion 14 with an extruded edge elements including tongues 16 along two edges and grooves 18 along the other two edges. With this arrangement, the tongues 16 insert to the corresponding grooves 18 and provide engagement of the edges of adjacent panels.
Referring now to FIG. 5 , the planar portion 14 typically includes a light weight center core layer 20 , a hard bottom exterior layer 22 and a bottom inner support layer 24 . A top support layer 28 extends over the core layer 20 and a top exterior layer 26 covers the top support layer 28 . The top exterior layer 26 may have a pattern and in one embodiment, includes a wood grain pattern to give the impression of a hardwood floor. It can be appreciated that fewer or more layers may be utilized, depending upon the use, but should include a lightweight core layer 20 . Referring again to FIG. 1 , the wood grain layer 70 is a continuous repeating pattern and includes a designated indexing feature 72 that it utilized for positioning the necessary cuts and for positioning the edges of the panel and the so that the pattern is continuous from one panel 12 to the next.
Referring again to FIG. 1 , the floor system 10 also includes edge trim pieces 30 and 32 . The edge trim pieces 30 and 32 form a safe transition from the upper surface of the floor system 10 to the underlying ground or floor. The edge trim pieces 30 and 32 have either tongues or grooves (not shown) similar to the tongues and grooves of the extruded edge 16 and 18 and mate in a similar manner. As explained hereinafter, the edge trim pieces 30 and 32 have corresponding locking devices that also engage complementary locking devices of the floor system 10 .
Referring now to FIGS. 2 , 3 and 4 , the floor panels 12 are shown with the planar portions 14 and the extruded edge members including tongues 16 and grooves 18 . The tongues 16 are along two adjacent sides while the grooves 18 are along the two adjacent opposite sides. The tongues 16 engage the complementary grooves 18 of adjacent panels 12 so that the edges of the floor panels 12 abut and the floor panels 12 form an extended continuous floor surface.
The floor panels 12 are connected to one another with lock assemblies 40 , as shown more clearly in FIG. 7 . Referring again to FIGS. 2-4 , the lock assemblies include female locks 42 and complementary male locks 44 . The complementary rotary locks 42 and 44 provide for pulling the edges together to ensure a tight fit. The female rotating cam lock devices 42 have a rotatable circular cam and mount at the center of the two edges having grooves 18 . The complementary male cam lock members 44 mount at the center of the edges having tongues 16 and receive and retain the rotary cam member when the lock is actuated and the cam member extends into the male lock member 44 . The female cam members 42 are actuated by rotating the cam with an Allen-type tool inserted into an orifice 64 in the upper surface of the floor panels 12 . When actuated, the cam pulls the cam lock devices 42 and 44 and therefore the floor panels 12 together to ensure that no gaps are formed in the floor 10 and a tight edge-to-edge connection is maintained between adjacent panels 12 .
Referring now to FIGS. 5-7 , the improved mounting arrangement of the lock assemblies 40 of the present invention is shown. The lock assemblies 40 include the bodies of the female and male lock members 42 and 44 that mount directly into slots 66 formed through the tongues 16 and grooves 18 of the edges and slots 62 formed in the planar panel portion 14 . The female lock devices 42 and the male lock devices 44 mount directly to an anchoring element 48 . The slots 62 are formed in the edges of the center core of the planar portion 14 . The anchoring element fits into a slot 60 , shown most clearly in FIGS. 2 and 8 . Mounting screws 46 extend through the back of the female and male locks 42 and 44 and into receiving portions 52 of the anchoring element 48 , shown most clearly in FIG. 9 . It can be appreciated that with this arrangement, the lock devices 42 and 44 mount directly to the anchoring element 48 and abut the anchoring element, thereby eliminating the less dense and poorly supporting material of the lightweight center layer 20 of the prior art. The anchoring element 48 provides added support for the lock members 42 and 44 . Moreover, installation is straight forward and requires no special tools or application of adhesive.
Should damage occur, repair is simple so that the panel 12 is not ruined. If a mounting screw 46 or orifice 52 is stripped, a new screw may simply be inserted into the adjacent unused receiving orifice 52 and no replacement parts are needed. It can be appreciated that if the anchoring element 48 or other elements do need to replacement, they are simply removed with a screwdriver and new lock devices 42 or 44 or anchoring elements 48 may be remounted without any adverse effect to the floor panel 12 .
The anchoring element 48 provides further advantages over the prior art wood mounting blocks. The anchoring elements 48 are preferably made of a sturdy but light weight plastic material such as nylon 6/6 or other suitable material well known in the art. The plastic material includes an upper flange 50 that extends slightly around the slot 60 and over a portion of the bottom of the floor panel 12 . Horizontal ribs 56 and vertical ribs 54 provide a sturdy support structure for the mounting portions 52 . As the anchoring element 48 provides much empty space, it provides weight savings over solid wood block mounting systems.
Forming of the slots 62 and 60 is accomplished quite simply with a router and is positioned to ensure a proper placement from an indexing feature 72 of the surface pattern 70 . The edges of planar portion 14 are formed at the same time as the slots 60 and 62 so that the slots 60 and 62 are precisely located to ensure proper alignment of the lock devices 42 and 44 . This also provides sufficiently precise alignment to ensure that the patterns that are configured for being continuous are consistently aligned and oriented to give an improved overall continuous natural wood grain or other floor appearance.
It is to be understood, however, that even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and function of the invention, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. | A portable floor system having a plurality of floor panels configured for connection along abutting edges to form an extended floor surface. Each panel has a planar portion including a top surface, a core, and a bottom surface. Extruded edge portions include tongues along two edges and complementary tongues along the other two edges. Each edge also includes a panel connecting assembly along each edge, having a lock device extending from an edge into the core. The lock device mounts directly against an anchor element. The anchor element extends through the bottom surface and having a connector receiving portion. | 4 |
BACKGROUND OF THE INVENTION
When excavating long trenches with a digging or trenching machine, the geological formation through which the trench extends often changes from highly frangible dirt, to other unconsolidated formations, and then to rock. There are digging implements made especially for penetrating dirt-like formations, and there are other radically different digging teeth especially adapted for forming a trench through rock. For this reason, it would be advantageous to be able to readily substitute a rock-type digging tooth for a dirt-type digging tooth, and vice versa, depending upon the characteristics of the geological formation through which the trench extends.
Swisher U.S. Pat. No. 4,335,921 teaches a cutting head which can be placed within a box wherein the box is designed to receive a cylindrical shank of a digging tooth. Means are provided by which the digging tooth is rendered non-rotatable. College, et al U.S. Pat. No. 4,346,934 also provides means by which the digging teeth are rendered non-rotatable.
The present invention constitutes an improvement over the prior art by the provision of a combination digging tooth and support box wherein the support box and digging tooth cooperate to proclude rotation of the digging tooth, yet the support box bore can also receive rock-type bits of the rotatable type when it is deemed desirable to do so.
SUMMARY OF THE INVENTION
A non-rotatable digging tooth in combination with a support box therefor, wherein the box has a bore adapted to receive a rotatable rock-type bit therein. A shoulder formed at a medial part of the tooth engages a forwardly projecting relief formed on the box, with the tooth shoulder and box shoulder confronting one another when the tooth shank is removably mounted in the bore formed within the box. The box bore is cylindrical and is made complimentary respective to the tooth shank. A keeper of prior art design prevents significant longitudinal movement between the tooth and the box. The confronting shoulders prevent rotational motion of the tooth respective to the box. The box shoulder is a relief which forms a face. The face is spaced from and lies parallel to the longitudinal axial centerline of the box bore. This construction allows the combination to be used on various different excavating apparatus, so that dirt, for example, can be excavated, and when the geology of the ground changes into a hard formation, a rock-type rotatable bit can be rotatably captured within the same box, thereby enabling the rock-type formation to be penetrated by the rock bit, and thereafter, the dirt type digging tooth of the combination can be replaced within the box.
Accordingly, a primary object of the present invention is the provision of an improved combination box and tooth assembly, wherein a dirt type digging tooth is held non-rotatable respective to the box, with the box bore being of a configuration to admit the use of a rotatable type rock bit therewith.
Another object of the present invention is the provision of a dirt type digging tooth in combination with a box having a circular bore, with the box bore being of a design which admits the use of a rotatable type tooth therewith.
A still further object of the present invention is the provision of an improved dirt type digging tooth which is non-rotatably affixed to a support box, with the support box having a forwardly projecting shoulder against which there is received a shoulder formed on a medial part of the digging tooth, so that the digging tooth is non-rotatably captured in a removable manner within the box.
Another and still further object of the present invention is the provision of improvements in non-rotatable type digging teeth for use on digging machines, comprising a tooth and box combination wherein the box has a circular bore formed therein for receiving both a non-rotatable dirt-type digging tooth as well as a rotatable type rock bit, with the non-rotatable type tooth having a shoulder formed thereon which abuttingly engages a shoulder on the box, with there being an interface between the shoulders of the box and tooth which lie in spaced relationship and parallel to the longitudinal axial centerline of the box bore.
An additional object of the present invention is the provision of an improved non-rotatable digging tooth for use in a support box of the type which is designed to receive a rotatable type rock bit therein, wherein the non-rotatable digging tooth has means located thereon which abuttingly engages means located outside of the box bore so that part of the tooth abuttingly engages part of the box and thereby prevents relative rotational motion therebetween.
A further object of the present invention is the provision of an improved non-rotatable digging tooth having a flat ground engaging end of sinusodial wave pattern in cross-section which increases in thickness towards a cylindrical shank, with the shank being received within a cylindrical bore of a support box, and with there additionally being confronting shoulders formed on the digging tooth and the support box which confront one another and thereby prevents relative rotation of the tooth respective to the box.
These and various other objects and advantages of the invention will become readily apparent to those skilled in the art upon reading the following detailed description and claims and by referring to the accompanying drawings.
The above objects are attained in accordance with the present invention by the provision of a combination of elements which are fabricated in a manner substantially as described in the above abstract and summary.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a part diagrammatical, part schematical, part cross-sectional side view representative of a prior art digging machine having digging teeth and support boxes associated therewith in accordance with the present invention;
FIG. 2 is a broken, enlarged, detail of part of the digging machine disclosed in FIG. 1;
FIG. 3 is a further enlarged, part cross-sectional, side elevational view of a support box and non-rotatable digging tooth made in accordance with the present invention;
FIG. 4 is a perspective view of part of the apparatus disclosed in FIG. 3;
FIG. 5 is a front view of the apparatus disclosed in FIG. 4;
FIG. 6 is a cross-sectional view taken along line 6--6 of FIG. 5;
FIG. 7 is a top, plan view of the digging tooth disclosed in FIG. 3;
FIG. 8 is an oblique top view of the digging tooth disclosed in FIG. 7, with some parts being broken away therefrom;
FIG. 9 is a side elevational view of the tooth disclosed in FIG. 7;
FIG. 10 is a rear view of the tooth disclosed in FIG. 7;
FIG. 11 sets forth a top plan view of a second embodiment of the present invention;
FIG. 12 is a side view of the tooth disclosed in FIG. 7, with some parts being broken away therefrom and the remaining parts being shown in cross-section;
FIG. 13 is a cross-sectional view taken along line 13--13 of FIG. 12;
FIG. 14 is an end view of the tooth disclosed in FIG. 11;
FIG. 15 is a plan view of another embodiment of the present invention;
FIG. 16 is a side view of the tooth disclosed in FIG. 15; with some parts being broken away therefrom, and some of the remaining parts shown in cross-section;
FIG. 17 is a cross-sectional view taken along line 17--17 of FIG. 16; and,
FIG. 18 is an end view of the tooth disclosed in FIG. 15.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, an excavating machine 10, as for example, a trenching machine such as a John Deer or I.H. Corporation, is provided with a digging wheel 12 having buckets 14 circumferentially spaced about the periphery thereof. As seen in FIG. 2, each bucket 14 has a plurality of digging teeth removably attached to a plurality of support boxes, as indicated by the numeral 16.
In FIG. 3, together with other figures of the drawings, the combination digging tooth and support box 16 comprises a support box 18 to which there is removably attached, in a non-rotatable manner, an improved digging tooth 20. The support box has downwardly converging lower sloped surfaces 19 and 21 by which the box is rigidly attached to a bucket lip in the manner of FIG. 2. The box can be welded to the bucket lip in any number of different manners, and the surfaces 19 and 21 can be arranged at various different angles to achieve the proper alignment of the tooth 20 respective to the bucket lip.
As seen in FIGS. 3-6, together with other figures of the drawings, the support box includes an outer face 22 which is perpendicularly disposed respective to the longitudinal axial centerline of a cylindrical bore 24. The bore 24 has a large i.d. length 26 at the entrance thereof which opens into the before mentioned face 22. The rear marginal length of the bore reduces in diameter as indicated by numeral 28. In FIGS. 4 and 5, the arrow at numeral 30 indicates a tang or forwardly projecting lip which forms a shoulder 32. The shoulder 32 is relieved or slightly recessed so that it is spaced slightly below and forwardly of the nearest peripheral wall surface of large i.d. 26. Sidewalls 34 and 36 are opposed to one another and define the lateral dimension of the projection. Numeral 38 indicates the forwardmost wall surface of the support box, which also defines the forward terminal end of the shoulder 32.
Looking now again to FIG. 3, together with FIGS. 7-10, the digging tooth 20 has a forward marginal length in the form of a ground engaging end 40 of substantially flat or blade-like configuration, and a rear marginal length in the form of a shank 42 made integrally therewith, with the shank and blade being diametrically opposed to one another. The blade, in the embodiment of FIGS. 7-10, has a flat portion 44 defined by opposed sides 46 and 48, and a pointed terminal end 50. The sides 46 and 48 each curve outwardly away from one another in the indicated manner of numeral 52, and terminate at its widest portion 54, which is also the medial portion of the digging tooth. The termination at 54 preferably is in the form of an oblated boss having a more or less vertical sidewall as indicated by the numeral 54 in FIGS. 9 and 10. The medial portion of the digging tooth then curves back inwardly as noted by numeral 56, in a direction towards the shank 42. The shank is comprised of large o.d. part 58 and small o.d. part 60. A groove 62 is formed circumferentially about the marginal end of the reduced diameter portion 60 of the shank 42. Numeral 64 indicates the inner terminal end of the digging tooth.
One surface or side of the medial portion 66 of the digging tooth is provided with an outwardly projecting tang which terminates in a shoulder 68. The shoulder 68 lies in a plane which is more or less parallel to the longitudinal axial centerline of the shank 42. Moreover, the shoulder 68 is spaced from the shank axis an amount substantially equal to the distance from shoulder 32 to the axial centerline of the bore 24 of the support box, with there being a slight spacing between shoulders 32 and 68; although, where the criticality of manufacture will permit, it is advantageous for the juxtapositioned shoulders 32 and 68 to slidably engage one another in an abutting manner, with the latter expedient being the most desirable arrangement.
In FIGS. 7-10, numeral 70 indicates a rear wall which forms the rear edge of shoulder 68. The wall 70 preferably is made parallel respective to the wall 22 of the box, so that the wall surface 70 and 22 abuttingly engage one another when the tooth is mated to the support box. Numeral 72 indicates the curvature from shoulder 68 to the oblated surface 54. The outward projection 54 found on either side of the medial part 66 of the tooth enables a tool to be placed between surface 56 and 38 or 22, and the tooth pried in a forcibly manner so that it is removed from bore 24.
In the embodiment of the digging tooth set forth in FIGS. 11-14, wherein like or similar numerals found therein refer to like or similar numerals used throughout the other figures of the drawings, the earth engaging end of the tooth is seen to be in the form of a sinusoidal wave pattern. The wave pattern preferably is formed by a centrally located teardrop shaped depression 145 having the illustrated large concave portion located closely adjacent to the shoulder 168, with the small concave portion of the teardrop depression being located adjacent to the marginal terminal end of the blade in spaced relation respective to the forward end 150, which preferably terminates in the form of a chisel. The opposed surface of the blade is provided with two spaced depressions 147 made slightly smaller than the opposed depression 145, with the two depressions 147 located on one side of the blade straddling the opposed depression 145 located on the other side of the blade. The depressions 146 and 147 enhance the digging action of the blade part of the digging tooth, as well as conserving material of construction.
In the embodiment of the digging tooth disclosed in FIGS. 15-18, the shank is made into a configuration slightly different from the shank found in the first two embodiments of the invention. The shank 242 has a reduced diameter part 262 for receiving a keeper therewithin which is significantly larger than the keeper of the second embodiment. Moreover, the rear wall 270 of the third embodiment is much larger in area as compared to the rear wall surface of the first and second embodiments, because of the difference in the physical dimensions of the blade width.
In each embodiment of the invention, the medial length 66, 166, and 266, which is formed at the juncture of the blade and shank, is provided with a tang which extends laterally from the longitudinal central axis of the shank and terminates in a shoulder 68, 168, or 268. The shoulder lies in a plane which is parallel to a plane passing through the longitudinal axis of the shank. The longitudinal axis of the shank also coincides with the longitudinal axis of the bore 24 formed into the support box. The spacing or shoulders 68, 168, 268 is such that when the shank is slidably received within the bore 24 of the support box, the shoulders 32 and 68 slidably engage one another, or almost slidably engage one another, in a manner whereby any rotational force imparted into the digging tooth is arrested as the two confronting surfaces 32, 68 abut one another as a consequence of the rotational forces, thereby rendering the digging tooth non-rotatable respective to the support box.
The combination of the digging tooth and support box disclosed herein provides a new and unobvious box and tooth assembly which enables most any trencher to dig through different types of geological formations, where a non-rotatable type digging tooth must occasionally be substituted for a rotatable type rock bit. When an extremely hard formation is encountered, and it is found that the progress of the ditch has diminished, the digging teeth of this invention are readily removed from the illustrated support box and a rock-type bit such as is readily substituted therefor, whereupon the digging operation proceeds in an efficient manner until the ditch has been cut through the hard formation, and the dirt-type teeth can then be replaced into the support box of this invention.
There are several unexpected advantages achieved with the present invention of a digging tooth and box combination. As seen illustrated in the figures of the drawings, the profile presented by the forward end of the combination avoids the deleterious clogging effect of debris which must flow about the medial part 66 of the tooth, passed the support box, and into the bucket without clogging the area where the tooth and box mate. The drawbacks of the debris lodging in an area of the combination which makes subsequent disassembly of the tooth from the box unduly difficult has been overcome with this invention. The intervening area between shoulders 32 and 68 is so small that lodgment of debris therein does not affect the digging operation, nor the subsequent disassembly of the tooth from the box. The configuration of the tooth blade and the medial part thereof progressively increases the structural integrity of the tooth in a direction towards the shank, and accordingly, the transfer of digging loads from the blade into the bucket lip occurs in a progressive manner such that there is no isolated forces present to damage or break either the blade or box.
An important and unexpected advantage achieved with the present invention is that the resisting force presented by the blade is transferred by the circumferentially extending wall 70 into the wall 22 of the box, rather than between the confronting shoulders 32 and 68 and accordingly, the forces imposed by the digging action of the apparatus have little tendency to rotate the tooth about its longitudinal axis. Hence, the digging action imparts forces into the confronting walls 70 and 22 in a direction which tends to move the tooth shank rearwardly rather than generating a rotational force about the axial centerline of the shank. | A non-rotatable digging tooth has a forward working portion designed to excavate dirt, with a rearward cylindrical shank portion of a configuration to be removably received within the circular bore of a support block. The block includes a forward projection which forms a shoulder having a face positioned substantially parallel to the axial centerline of the bore. The juncture between the shank and digging part of the tooth is provided with a shoulder made complementary respective to the shoulder on the support block so that the two shoulders confront one another. The confronting shoulders abuttingly engage one another and provide a resisting force which prevents rotation of the tooth respective to the block. The block can be attached to various different trenching and digging apparatus. | 4 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This application is based upon and claims the benefit of priority from prior German Patent Application No. 10 2010 036 826.1, filed Aug. 3, 2010, the entire contents of which are incorporated herein by reference in their entirety.
BACKGROUND
An equalizing unit of a drive train of a motor vehicle with a housing and with drive members comprises an input shaft and at least one first output shaft. The first output shaft can be coupled to a second output shaft or to the input shaft or to an intermediate shaft driven by the input shaft via a clutch device, which is to be supplied with oil via a delivery device directly or indirectly driven via the drive members.
The construction of an equalizing unit described above is known from German publication DE 10 2008 002 844 A1. There, a drive train for a motor vehicle is shown, including a transverse equalizing unit without differential wherein the output shafts for driving the drive wheels are driven via two individually activatable side shaft clutches. The side shaft clutches are formed by disc packages which for cooling and lubrication have to be oiled. The outer discs of the disc package are connected in a rotationally fixed manner to an intermediate shaft driven by the input shaft—in DE 10 2008 002 844 A1 this is the crown wheel carrier shaft—and through their special configuration deliver the oil to the outside into an oil collection pocket provided in the housing, from where the oil via housing bores flows back to the interior of the disc package where it is again collected by the discs so that—based on a disc package of a side shaft clutch—an internal oil circuit is formed.
Because of this internal oil circuit a large part of the oil volume expended for the cooling and lubrication remains in the described internal oil circuit for a long time without the oil volume being sufficiently mixed with “fresh” oil or replaced with such. Oil volume, which has only just absorbed heat between the clutch discs, is directly returned to the discs again. The clutch temperature therefore rises disproportionally to the cooling output that could be achieved with the oil quantity present in the equalizing unit. The disproportionate heating of the clutch brings disadvantages with regard to wear characteristics and thus the lifespan, and also is problematic with regard to response and control behavior.
A further disadvantage of the equalizing unit shown in DE 10 2008 002 844 A1 is that the clutch packages of the side shaft clutches stand in the oil in order to collect it and deliver it to the oil collection pocket. The concomitant splashing losses increase the dissipation of the drive train.
In addition to undesirable dissipation, even in the case described in DE 10 2008 002 844 A1 where the secondary part of the drive train is decoupled from the drive wheels and the side shaft clutches are fully opened, the secondary drive wheels roll on the street in driving mode and drag the inner disc carrier and the inner discs connected with the latter in a rotationally fixed manner. The inner discs, however, are in permanent contact with the oil since they are immersed in it. Not only the region of the extremely narrow air gap (gap width approximately 0.1 mm) between inner and outer discs which is directly located in the oil is filled with oil, but the oil is additionally delivered through the rotating inner discs into the intermediate space between inner and outer discs of the disc clutch which do not stand in the oil. The fluid friction or hydrodynamic friction created as a consequence in turn transmits drag torque, acting from the secondary drive wheels, to the inner discs, and then to the outer discs, and because of this the friction drives the outer discs. However, as soon as these start to rotate these in turn deliver oil into the previously described internal oil circuit and on their part thus again increase the delivered oil volume and thus the friction loss or dissipation. The undesirable effect amplifies itself.
Tests have shown that because of this effect the secondary drive train, contrary to the assumptions made in DE 10 2008 002 844 A1, does not come to a halt even when it is decoupled from the primary part of the drive train. Through the low-friction configuration of the surfaces of the inner discs proposed in DE 10 2008 002 844 A1, the negative consequences of this effect can only be reduced to a very minor degree. In addition, the low-friction surfaces of the inner discs result in a significantly poorer response and control behavior of the clutch package.
SUMMARY OF PREFERRED EMBODIMENTS
As disclosed herein, the oiling concept described in DE 10 2008 002 844 A1 may be optimized with regard to the dissipation caused upon a secondary part decoupled from the primary part of the drive train without having to accept compromises with the response and control behavior of the clutch packages.
For example a delivery device may be formed by an oil delivery wheel arranged distant from the clutch device.
The arrangement of the oil delivery wheel distant from the clutch device results in the oil following a passage through the clutch device to be oiled always flowing back into the oil sump of the equalizing unit before it is again fed into the oil circuit. Thus, adequate mixing-through of the entire oil volume, and consequently the utilization of the maximum cooling output of the total oil quantity, is guaranteed at all times, which in turn reduces thermal loading of the clutch devices.
The equalizing gear can be both a transverse as well as a longitudinal equalizing unit. For example, a transverse equalizing unit may act in a purely frictionally connected manner without a differential, wherein the side shafts of the drive wheels are coupled into the drive power flow via side shaft clutches, as is already shown in DE 10 2008 002 844. In principle, conventional longitudinal and transverse differentials may be employed acting in a positively connected manner in order to oil clutch packages of the differential locks, be it in shaft-shaft arrangement or in shaft-cage arrangement. The intermediate shaft with a conventional differential is formed by the differential cage.
The mentioned configuration additionally makes possible designing the oil delivery wheel in such a manner that it is able to deliver the cooling and lubricating oil from an oil sump with an oil level located below the clutch device. The clutch device for example, dragged clutch components, can thus be permanently located above the oil level. Even the outer disc carrier located radially outside, and the outer discs, do not cause any splashing losses either under load, that is, for example, with a connected secondary part of the drive train, nor in the opened mode, that is with a disconnected secondary part.
The oil delivery wheel may be formed by a crown wheel arranged on the intermediate shaft, via which, as part of the angular gear, the drive power introduced by the input shaft is transmitted to the intermediate shaft. If, because of the dimensioning of the crown wheel, the crown wheel itself does not have an adequate diameter for immersing itself in an oil sump even located below the clutch device, the oil delivery wheel can comprise the crown wheel arranged on the intermediate shaft, wherein the crown wheel is radially expanded to the outside by an oil delivery ring. The oil delivery ring can be designed as integral material-unitary part of the crown wheel. For weight and cost reasons, and in order to keep masses to be accelerated and decelerated low, the oil delivery ring may be produced as a separate component from a lighter material and may be joined, e.g., screwed, to the crown wheel.
Realizing the oil delivery wheel with the help of a gear wheel of the equalizing gear standing in the power flow is not absolutely essential. An oil delivery wheel that is separate from the crown wheel can also be provided on the input shaft or the intermediate shaft.
In order to increase the oil flow, at least part-circumferential bulkheads can be provided which minimize the lateral outflow of the oil taken along by the oil delivery wheel.
In addition to the improvement measures described above, it has been shown that the oiling concept can be optimized further still. The self-amplifying effect of an undesirable clutch oiling caused through drag torques of wheels that are not driven but are rolling on the road, despite a decoupled secondary part of the drive train, was observed during tests despite the remedial measures described above.
At a torque at which the clutch device is opened for decoupling the secondary part from the primary part of the drive train, oil continues to be delivered by the rotating oil delivery wheel, because of a running-down due to mass inertia, among other reasons. In addition, oil is remains present between the two clutch sides despite opened clutches, so that the clutch, although it is in the open state, transmits a drag power from the one clutch side to the other clutch side. The latter clutch side as drive member of the secondary part of the drive train in turn drives the oil delivery wheel, which consequently does not completely cease the oil delivery as actually desired, but continues to deliver oil to the clutch device. As a consequence of the non-interrupted oil flow, and supported by the drag power introduced via the drag torque, a state of equilibrium is established which prevents a complete stoppage of the drive members of the secondary part of the drive train. The secondary part continuously co-rotates and causes dissipation although it is not integrated in the drive power flow.
In order to interrupt this equilibrium, a braking or decoupling device is provided, by which the oil delivery wheel can be stopped when there is no oiling need for the clutch device. With such a braking or decoupling device, the state of equilibrium which would otherwise materialize can be effectively prevented. Depending on where and how the braking or decoupling device intervenes, the drag power can no longer be transmitted from a first clutch side to a second clutch side because the first clutch side is already braked, and/or because, through the decoupling of the oil delivery wheel from its drive member, the drag power is not transmitted to the oil delivery wheel. However, as soon as the oil delivery wheel is stationary, the oil flow is interrupted and the undesired oiling in the drag state is terminated. The clutch device briskly runs dry and the two clutch sides rotate with significantly lower loss.
Because the braking torque, which the braking device has to provide for stopping the oil delivery wheel, is small, the braking device can also be realized with the help of smaller drive train components of the secondary part. For example, the braking device can comprise the sliding sleeve of a synchronizing device that interacts with a fixed part of the motor vehicle via a friction surface, and that is capable of generating a braking torque for braking the drive members of the secondary part to be stopped. Here, the sliding sleeve for generating the frictional torque can support itself, for example against a bearing block or another component that is capable of supporting the braking torque. Alternatively or additionally, the sliding sleeve for creating the frictional torque can comprise a friction surface facing a shifting fork of the synchronizing device.
Stopping the oil delivery device through a braking or decoupling device be realized not only with oil delivery devices which are formed by an oil delivery wheel. Other oil delivery devices can be employed delivering oil to the clutch device by other mechanisms.
Accordingly, the drive train can comprise an equalizing gear with drive members comprising an input shaft and at least one first output shaft, wherein the first output shaft can be coupled to a second output shaft or to the input shaft, or to an intermediate member driven by the input shaft, via a clutch device to be oiled. The clutch device can be supplied with oil via a delivery device directly or indirectly driven via the drive members. In the drive train a braking or decoupling device is provided, by which the delivery device can be stopped if there is no oiling need for the clutch device.
The previously described braking device can act not only on drive members of the equalizing unit. For example, a drive train can have a permanently driven primary part for the permanent driving of primary drive wheels as well as a secondary part for the driving of secondary drive wheels. The secondary part if required can be decoupled from the primary part and the secondary drive wheels or connected to these; the braking device can act on any parts of the secondary part of the drive train.
The braking device thus need not necessarily be part of the equalizing unit, it merely needs to generate an adequate frictional torque somewhere in the secondary part of the drive train to be effective for the secondary part to be deactivated.
Accordingly, the drive train can comprise a permanently driven primary part for the permanent driving of primary drive wheels and a secondary part for the driving of secondary drive wheels, wherein the secondary part if required can be decoupled from the primary part and the secondary drive wheels. However, the secondary part may be connected to these. Further, in the secondary part at least one clutch device may be provided. At least one clutch side of the clutch device is dragged via the secondary axle drive wheels which roll during operation of the vehicle even with the secondary part decoupled and to be supplied with oil via a delivery device directly or indirectly driven via drive members of the secondary part, wherein a braking device is provided by which the secondary part can be braked in the state decoupled from the primary part.
In summary a revised oiling concept of an equalizing unit of a drive train of a motor vehicle with a clutch device to be oiled in driving mode and measures connected with this is disclosed. In order to stop drag torques which act on the clutch device from the outside and lead to increased dissipation when said clutch device is not required due to the operating state, measures are provided which promote the dry-running of the clutch device. The measures include the spatial-functional separation of the oil delivery device from the clutch device and the provision of a braking or decoupling device, by which the oil delivery device can be deactivated when no oil is required.
DESCRIPTION OF THE DRAWINGS
Further features and advantages are obtained from the subclaims and from the following description of exemplary embodiments by means of the drawings.
In the drawings:
FIG. 1 is a drive train construction known from the prior art with a permanently driven primary part and a secondary part that can be connected when required with a equalizing unit without differential for driving the secondary drive wheels,
FIG. 2 is an equalizing unit without a differential during operation with an oil delivery wheel formed by a crown wheel for clutch oiling,
FIG. 3 is an alternative embodiment of the equalizing unit without differential in the stationary state with a schematically represented oil delivery ring fastened to the crown wheel, and
FIG. 4 is a power takeoff unit (PTU) provided for a drive train according to FIG. 1 with an additional braking device for braking the secondary part of the drive train.
FIG. 5 is a detailed view of a braking device and a synchronizing device.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a drive train construction known from the prior art with a permanently driven primary part and a secondary part only driven when required with an equalizing unit 1 without a differential for driving the secondary drive wheels 2 . The secondary part of the drive train, whose drive members can be decoupled from or connected to the primary part depending on requirement, is shown obliquely hatched, while those drive members, which interact with the secondary part in driving mode for power transmission and rotate permanently are marked black throughout.
The equalizing unit 1 is an equalizing unit without a differential, wherein power flow is transmitted to the secondary drive wheels 2 via two individually activatable clutch devices formed through side shaft clutches 3 , and via the half shafts 4 . Here, the side shaft clutches 3 , which are formed by disc clutches acting in a frictionally connected manner not only compensate for the different rolling paths of the secondary axle drive wheels 2 when driving through curves but are also utilized for actively influencing the dynamic driving behavior. In operation, the clutches have to be oiled with cooling and lubricating oil.
Tests with the system shown in FIG. 1 have shown that even when the secondary part of the drive train is decoupled from the primary part, particularly when said secondary part is decoupled while driving at a speed at or greater than approximately 50 km/h, the drive members of the secondary part do not stand still as desired, but continue to rotate through the drag power introduced into the side shaft clutches 3 by the secondary drive wheels 2 , and thus cause dissipation. The reason for this is particularly the oiling concept selected in the prior art as described at the outset.
FIG. 2 shows an equalizing unit 1 without a differential during the operation with an oil delivery wheel for clutch oiling formed by the crown wheel 5 . The crown wheel 5 because of its rotation scoops the oil along the housing inner wall to an oil collection pocket 6 provided in the housing. From there it reaches the side shaft clutches 3 via oil feed channels 7 . The crown wheel 5 is arranged on the intermediate shaft 19 and is driven via an input shaft (not shown).
By utilizing the crown wheel 5 as oil delivery wheel or bucket wheel it is ensured, compared with a solution where the discs of the side shaft clutches predominantly deliver the oil, that the oil flowing back from the clutches—before it is again fed to the oil circuit—collects in the oil sump and is mixed with the entire oil volume. It is prevented that an inner oil circuit forms, because of which the oil after it has flowed through the clutches is directly fed back to the clutches again so that the oil in consequence would be heated up disproportionately.
FIG. 3 shows the equalizing unit from FIG. 2 , wherein in the example of FIG. 3 the equalizing unit is stationary. The diameter of the crown wheel 5 is not adequate to immerse itself in the oil. For this reason, an only schematically represented oil delivery ring is provided on the crown wheel 5 , which radially expands the active diameter of the crown wheel 5 with respect to the oil delivery capability. The oil delivery ring 8 need not necessarily be a ring-shaped component but individual non-continuous blades can also be arranged on the crown wheel 5 which are distributed over its circumference.
Likewise only schematically shown is a part-circumferential oil bulkhead 9 , which prevents the oil during the delivery process from laterally flowing out of the oil sump to the oil collection pocket located above due to centrifugal force. The application of a bulkhead 9 can be used not only with an oil delivery ring, but also in a configuration according to FIG. 2 or for other arrangements of oil delivery wheels on the intermediate shaft. The bulkhead 9 may be provided on both sides of the oil delivery wheel and can either be formed by a part to be separately inserted or directly by a projection protruding to the inside or a rib of the housing, wherein installation space and installation aspects obviously have to be taken into account.
In addition as can be seen in FIG. 2 and FIG. 3 , the oil level in the oil sump both in the operating state as well as when stationary is located below the side shaft clutches 3 . This also contributes to minimizing the dissipation since the clutch members dragged by the half shafts 4 do not stand in the oil and can thus not deliver any oil between the clutch discs. When the secondary part of the drive train is decoupled from the primary part the clutches 3 can thus run in a completely dry and thus low-friction manner.
Despite the spatial-functional separation of clutch device and oil delivery device it can happen, as described at the outset, that the secondary part of the drive train, after separation from the primary part particularly as a consequence of the continuing running down of oil in the clutch device, continues to rotate and causes dissipation. In order to stop this, and, to make it possible that the oil flow can be completely stopped, a braking device is provided which in the following is explained exemplarily by means of a special configuration of the power takeoff unit 10 (PTU) shown in FIG. 1 .
So as to make it possible that the secondary part of the drive train shown in FIG. 1 can also be connected to or decoupled from the drive train even while driving, the PTU 10 has a synchronizing device 11 . FIG. 4 shows a PTU 10 that can be employed in a drive train according to FIG. 1 with an additional braking device 12 for braking the secondary part of the drive train, wherein the braking device 12 is provided on the synchronizing device 11 . FIG. 5 provides a detailed view of the devices 11 , 12 .
The synchronizing device 11 comprises a sliding sleeve 13 which is slid onto a guide sleeve 14 in a rotationally fixed but axially displaceable manner. A shifting fork 15 , by which the sliding sleeve 13 can be actuated, rests in the sliding sleeve 13 . In FIG. 4 the sliding sleeve 13 is shown in a position in which the secondary part of the drive train is decoupled from the primary part. In order to connect the secondary part of the drive train to the primary part, the sliding sleeve in FIG. 4 therefore would have to be shifted to the left in order to come into engagement with the driver ring 16 .
Laterally, next to the sliding sleeve 13 , a schematically shown additional friction surface 17 ′ is provided, which interacts with a fixed component capable of supporting a braking torque (for example a bearing block 18 ). The friction surface is preferably arranged on the sliding sleeve 13 but can just as well be additionally or alternatively provided on the fixed component.
A further friction surface 17 ″ can act between sliding sleeve 13 and shifting fork 15 additionally or alternatively to the friction surface 17 ′. Here, too, the friction surface 17 ″ can be provided on one of the two or on both components.
If the secondary part of the drive train is now decoupled from the primary part by sliding the synchronizing device into the position shown in FIGS. 4 and 5 , a frictional torque can be created in that the sliding sleeve 13 and the shifting fork 15 respectively are specifically set against the friction surfaces 17 ′ and 17 ″ respectively, through which the drive members of the secondary part of the drive train are braked. This interrupts the oil flow in the equalizing unit shown in FIGS. 2 and 3 so that the clutches can run dry and the transmission of the drag torque from the secondary drive wheels via the half shafts into the secondary part-sided clutch device is significantly minimized. The clutch discs subsequently run in an extremely low-friction manner, the secondary part of the drive train stands still.
The synchronizing device 11 shown in FIGS. 4 and 5 is additionally particularly low in friction because of its special arrangement. While usually the guide sleeve 14 is positioned on the permanently rotating drive members of the primary part of the drive train, and the driver ring 16 is located on the drive members of the secondary part of the drive train to be accelerated during the synchronizing process, this is exactly the opposite in the example of FIG. 4 . When the secondary part of the drive train is decoupled and stationary, the guide sleeve 14 and the sliding sleeve 13 also stand still so that between shifting fork 15 and sliding sleeve no friction, and thus no dissipation, can occur. In addition, only this configuration makes possible braking the secondary part of the drive train via the synchronizing device, since no braking torque acting on the drive members of the secondary part of the drive train could otherwise be generated via the sliding sleeve 13 or the shifting fork 15 . This arrangement of the components of the synchronizing device is an additional conceptive independent of the oiling concept and the remaining construction of the drive train. | An equalizing unit of a drive train of a motor vehicle includes a clutch device to be oiled in driving mode. In order to stop drag torques which act on the clutch device from the outside, and result in increased dissipation when said clutch device is not required due to an operating state, measures are provided which promote the dry running of the clutch device. The measures include the spatial-functional separation of the oil delivery device from the clutch device and the provision of a braking or decoupling device by which the oil delivery device can be deactivated if there is no oil requirement. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of U.S. patent application Ser. No. 10/217,179, filed Aug. 12, 2002 now U.S. Pat. No. 6,779,707, Which is a continuation of Ser. No. 09/571,789, filed May 16, 2000, now abandoned each of which is hereby incorporated herein by reference.
Priority of U.S. Provisional Patent Application Ser. No. 60/152,770, filed Sep. 3, 1999, incorporated herein by reference, is hereby claimed.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
The inventions described herein were made in the performance of work under Lockheed Martin Michoud Space Systems IRAD (Internal Research and Development).
REFERENCE TO A “MICROFICHE APPENDIX”
Not applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the manufacture of aircraft, space vehicles and the like wherein panels are connected using friction stir welding. More particularly, the present invention relates to the construction of aircraft, space vehicles and the like wherein an improved method enables stringer stiffened panels to be joined with friction stir lap welds, in replacement of the traditional riveting practice.
2. General Background of the Invention
Friction stir welding (FSW) is a solid state joining process developed by The Welding Institute (TWI), Cambridge, England and described in U.S. Pat. No. 5,460,317, incorporated herein by reference. Compared with traditional fusion welding processes, it offers simplified processing, improved mechanical properties, diminished weld defect formation, equivalent corrosion resistance, and reduced distortion, shrinkage, and residual stresses. Using conventional milling equipment with a backside anvil support, a non-consumable, cylindrical pin tool is rotated and plunged into the butt or lap joint of the material to be welded. Pin tools are specifically designed for a given alloy and gauge. Also incorporated herein by reference are U.S. Pat. No. 5,718,366 and all references disclosed therein. The following additional references of possible interest are incorporated herein by reference: U.S. Pat. Nos. 3,853,258, 3,495,321, 3,234,643, 4,087,038, 3,973,715, 3,848,389; British Patent Specification No. 575,556; SU Patent No. 660,801; and German Patent No. 447,084. Publications that discuss friction stir welding include “New Process to Cut Underwater Repair Costs”, TWI Connect, No. 29 , January 1992; “Innovator's Notebook”, Eureka Transfer Technology, October 1991, p. 13; “Repairing Welds With Friction-Bonded Plugs”, NASA Tech. Briefs, September 1996, p. 95; “Repairing Welds With Friction-Bonded Plugs”, Technical Support Package, NASA Tech. Briefs, MFS-30102; “2195 Aluminum-Copper-Lithium Friction Plug Welding Development”, AeroMat '97 Abstract; “Welding, Brazing and Soldering”, Friction welding section: “Joint Design”, “Conical Joints”, Metals Handbook: Ninth Edition, Vol. 6, p. 726. A publication authored by applicants is entitled “Friction Stir Welding as a Rivet Replacement Technology”; Brian Dracup and William Arbegast; SAE Aerofast Conference, Oct. 5, 1999.
BRIEF SUMMARY OF THE INVENTION
The present invention provides an improved method of constructing structures such as aircraft using friction stir welding, to thereby replace the traditional riveting practice of previously unweldable aluminum alloys. Possible applications include the intertank of the External Tank of the Space Shuttle and airplane manufacturing.
Friction Stir Welding is a Solid State joining process that now allows the welding of previously unweldable aluminum alloys. Traditionally, these aluminum alloys have found use only in mechanically joined structures such as in aircraft and space vehicles. The present invention provides a method of joining overlapped panels using friction stir welding, replacing the traditional riveting practice. The method of the present invention is a viable, and cost reducing alternative to aluminum riveted structures.
The present invention features a non-consumable friction stir weld pin tool (see FIGS. 1–4 ) that is preferably constructed of H13 tool steel. The tool is rotated, plunged, and traversed along the stringer flanges of a stringer-skin panel to produce a friction stir lap weld. The tool is preferably tilted at an angle of about 2½ degrees.
As the pin tool initially plunges into the weld jointline, the material is frictionally heated and plasticized at a temperature below that of the alloy's melting temperature and typically within the material's forging temperature range. When the metal becomes sufficiently soft and plastic, and the appropriate penetration depth has been reached, the tool is traversed along the weld line. As the tool is traversing, metal flows to the back of the pin tool where it is extruded/forged behind the tool. It then consolidates and cools under hydrostatic pressure conditions [2–8].
Unlike fusion welding processes in which there are numerous inputs to the welding schedule, friction stir welding requires only three: spindle speed (RPM), travel speed (IPM), and the penetration depth of the tool in the material (heel plunge or penetration ligament). Penetration depth can be monitored either through load control or displacement [9].
The present invention thus discloses a method and apparatus that uses a friction stir welding tool that fully penetrates through the top sheet and partially penetrates into the bottom sheet. The material around the pin tool is frictionally heated, plasticized, and extruded/forged to the back of the pin where it consolidates and cools under hydrostatic pressure conditions.
Friction stir lap welding stringer-skin panels will eliminate the inter-rivet buckling commonly seen on mechanically joined structures and consequently, increase the buckling strength of the vehicle. In addition, the present invention enables simpler processing as compared with the traditional riveting practice by replacing any touch labor required with an automated process. Eliminating the rivets and other associated parts will also reduce quality control and material handling issues. Consequently, friction stir welding will increase production build rates and reduce production costs. Overall vehicle weight will also be decreased by eliminating the rivets and their associated parts.
BRIEF DESCRIPTION OF THE DRAWINGS
For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
FIG. 1 is a side view of the pin tool portion of the preferred embodiment of the apparatus of the present invention that is used in the method of the present invention;
FIG. 2 is an end view of the pin tool of FIG. 1 , taken along lines 2 — 2 of FIG. 1 ;
FIG. 3 is a side, partial section view of the pin tool of FIG. 1 , taken along lines 3 — 3 of FIG. 1 ;
FIG. 4 is a fragmentary, enlarged section view of the pin tool of FIG. 1 ;
FIG. 5 is a perspective view of the preferred embodiment of the apparatus of the present invention;
FIG. 6 is a sectional view taken along lines 6 — 6 of FIG. 5 ;
FIG. 7 is a sectional view taken along lines 7 — 7 of FIG. 5 ;
FIG. 8 is a perspective view of the preferred embodiment of the apparatus of the present invention;
FIG. 9 is a schematic top view illustrating the method of the present invention;
FIG. 10 is a schematic view showing typical microstructure of a full penetration friction stir weld in 0320″ 2195-T8 alloy;
FIG. 11 is an illustration of typical microstructure of a partial penetration friction stir lap weld with no faying surface intermixing in 0.160″ 2024-T83 alloy;
FIG. 12 is a graphical representation of mechanical properties of friction stir welding vs. fusion welds;
FIG. 13 is an illustration of a friction stir weld with tunnel defect;
FIG. 14 is an illustration of a friction stir weld with a lack of penetration defect;
FIG. 15 is an illustration of a friction stir lap weld with cold lap defect in 2024-T83 alloy;
FIG. 16 is a graphical illustration showing shear strength in relation to processing parameters for 2090-T83 alloy friction stir lap welds;
FIG. 17 is a schematic view showing scalloped fracture surface in 2090-T83 alloy friction stir weld;
FIG. 18 is a schematic view showing sheared fracture surface in 2090-T83 alloy friction stir weld;
FIG. 19 is a schematic illustration showing the metallurgy of stringer-stiffened friction stir welded 2090-T83 alloy panels;
FIG. 20 is a graphical illustration showing compression buckling results for each strain gauge showing initial buckling and ultimate failure load (shown are results obtained from friction stir weld panel and riveted panel);
FIG. 21 is a schematic view showing initial buckling on a riveted panel;
FIG. 22 is a schematic illustration showing compression failure of a riveted panel;
FIG. 23 is a schematic view showing initial buckling of a friction stir welded panel;
FIG. 24 is a schematic view showing a compression failure of a friction stir welded panel;
FIG. 25 is a schematic elevation, exploded view of an additional embodiment of the apparatus of the present invention;
FIG. 26 is a sectional, elevation view of the additional embodiment of the apparatus of the present invention;
FIGS. 27 and 28 are a schematic sectional, elevation views showing the additional embodiment of the apparatus of the present invention and illustrating the method of the present invention showing movement of the pin tool from one side of the weld site to the other;
FIG. 29 is a fragmentary enlarged sectional view of the additional embodiment of the apparatus of the present invention; and
FIG. 30 is an elevation view of a completed, welded tee-shaped panel.
DETAILED DESCRIPTION OF THE INVENTION
In FIGS. 1–4 , the pin tool that is used as part of the method of the present invention is shown in detail, and designated generally by the numeral 10 in FIG. 1 . Pin tool 10 provides a first end portion 11 , a second end portion 12 , and a middle section. The middle section includes frustoconical shaped section 14 and cylindrical larger diameter section 13 . Tool 10 has a central longitudinal axis 24 . End portion 12 provides a smaller diameter cylindrical section 20 and a frustoconical section 21 . The lower smaller diameter cylindrical portion 20 can include a plurality of angular grooves 15 as shown in FIG. 3 . During use, the pin tool 10 is rotated, plunged, and traversed along the stringer flanges of a stringer-skin panel to produce a friction stir lap weld. The tool 10 is preferably tilted at an angle of about 2½ degrees. The tool 10 fully penetrates through the stringer and partially penetrates into the skin. The material around the pin tool 10 is frictionally heated, plasticized, and extruded/forged to the back of the pin where it consolidates and cools under hydrostatic pressure conditions.
End portion 12 provides a tip 16 that actually penetrates the portions of the materials that are to be stir welded together. The tip 16 can be a generally cylindrical shaped portion 17 and dished end 18 having convex surface 19 (see FIG. 4 ). An annular shoulder 22 can surround tip 16 extending radially between the cylindrical section 17 and frustoconical section 21 as shown in FIGS. 3 and 4 . The annular shoulder 22 can form an angle 23 of about 8 degrees with a line that is perpendicular to the central longitudinal axis 24 of the pin tool 10 . Thus, the annular shoulder 22 defines an annular cavity 25 .
The generally cylindrically shaped portion 17 can have an external thread 26 as shown in FIGS. 1 , 3 and 4 . This external thread 26 helps produce a uniform stir weld. The concavity 25 enables some material to flow from the parts being welded into cavity 25 rather than laterally away from the weld site.
The threads 26 act to push the material down against the backside anvil. The cavity acts as a temporary reservoir that holds plastic metal that has been displaced by the volume of the pin ( 16 ).
FIGS. 5–9 show the method and apparatus of the present invention during the lap welding of two stringer panels 28 , 29 . It should be understood that the method and apparatus of the present invention can be used with any type of lap weld wherein there is full penetration through a top sheet and partial penetration through a bottom sheet. That top sheet can be of any geometry, including flat. In the example drawing of FIGS. 5 and 6 , the top sheet has a “hat stringer” shape. The bottom sheet can be of any geometry, including flat. In the drawings shown such as in FIGS. 5 , 6 , 7 and 8 , the bottom sheet is a flat sheet and can be called a “skin”. In the embodiment shown in FIGS. 5–9 , the method and apparatus of the present invention illustrates a “hat stringer” being joined to a “skin”. The resulting panel can be referred to as a “stringer-stiffened panel”. In airplane manufacturing for example, the method and apparatus of the present invention would almost solely deal with two flat panels as opposed to the hat stringer and skin illustrations of FIGS. 5–9 . In FIG. 5 , a welding machine or welding head 27 is shown gripping pin tool 10 at end portion 11 . The opposing end portion 12 of pin tool 11 engages each of the stringer panels 28 , 29 as shown in FIGS. 5 and 6 . The stringer 29 can be generally flat. The stringer 28 can include one or more inclined portions 30 and flat flange portions 31 as shown in FIG. 6 .
The stir welding machine 27 rotates the pin tool 10 as shown in FIG. 9 , indicated generally by the arrow 35 . The numeral 34 shows the position of the pin tool 10 in hard lines. In FIG. 6 , curved arrow 35 shows rotational motion that is transmitted from the stir welding machine 27 to the pin tool 10 . In addition to rotation that is imparted to the pin tool 10 from the stir welding machine 27 , linear motion is also transferred from the stir welding machine 27 to the pin tool 10 . In FIGS. 5 , 8 and 9 , this linear motion is indicated schematically by the numeral 32 . In FIG. 7 , a weld 30 is shown penetrating an upper stringer panel 28 and part of a lower stringer panel 29 . In FIG. 7 , the weld 33 penetrates the flange 31 portion of stringer panel 28 and a majority of the thickness of the skin panel 29 .
As the pin tool initially plunges into the weld 33 jointline, the material is frictionally heated and plasticized at a temperature below that of the alloy's melting temperature and typically within the material's forging temperature range. When the metal becomes sufficiently soft and plastic, and the appropriate penetration depth has been reached, the tool is traversed along the weld line. As the tool is traversing, metal flows to the back of the pin tool where it is extruded/forged behind the tool. It then consolidates and cools under hydrostatic pressure conditions.
Unlike fusion welding processes in which there are numerous inputs to the welding schedule, friction stir welding requires only three: spindle speed (RPM), travel speed (e.g., inches per minute or IPM), and the penetration depth of the tool in the material (heel plunge or penetration ligament). Penetration depth can be monitored either through load control or displacement.
As shown in FIG. 10 , several distinct metallurgical zones have been identified for both full penetration butt welds and partial penetration lap welds. Within the weld nugget, there exists a dynamically recrystallized microstructure consisting of fine, equiaxed grains on the order of 3–6 microns in size. Closer to the surface is a re-heated dynamically recrystallized zone (flow arm) where the trailing edge of the pin tool's shoulder drags parent material from the retreating side toward the advancing side after the pin tip has passed through. Further away from the weld jointline, there is insufficient heating and strain energy to cause complete recrystallization of the grains. This thermal-mechanical zone (TMZ) shows some degree of plastic deformation and grain boundary coarsening. The heat affected zone (HAZ) separates the TMZ from the parent metal.
The basic metallurgy in friction stir lap welds is similar to full penetration butt welds. A dynamically recrystallized zone, a thermal mechanical zone, a re-heated surface zone (flow arm), and a heat affected zone are all apparent in lap welds (see FIGS. 10–11 ). Of particular interest is the path of the interlayer's faying surface through the weld nugget.
Friction Stir Welding offers several mechanical benefits over its fusion counterparts ( FIG. 12 ). Both ultimate tensile strengths and yield strengths are significantly higher over a broad range of temperatures and thicknesses. In addition, friction stir welds show improved fatigue and fracture properties over VPPA/SPA welded plate. Like wrought aluminum products, friction stir welds experience an increase in elasticity and strength with decreasing testing temperature. There is also a marked increase in ductility as compared with fusion welding.
Weld preparation and cleanliness are much less stringent than that required for fusion welding. A simple Scotchbrite® rub of the area to be welded, coupled with an alcohol wipe and deburring of the root side is sufficient to produce quality welds. In addition, friction stir welding is a very robust process with a large operating parameter box.
There are two types of defects that may occur in butt joints when welds are processed far from normal operating conditions. The first characteristic is a “wormhole” or “tunnel” that runs in the longitudinal direction through the length of the weld ( FIG. 13 ). This defect occurs when there is insufficient forging pressure under the tool shoulder, preventing the material from consolidating. This is normally caused by too quick a welding speed. This defect is readily detectable through radiographic inspection. The second type of defect is a “root lack of penetration” or “root lack of fusion” that occurs when the dynamically recrystallized zone fails to penetrate fully to the bottom surface of the joint ( FIG. 14 ). It can be caused by inadequate tool penetration, insufficient heat and pressure, or improper pin tool geometry. This defect can have an effect on mechanical properties and may be difficult to detect through conventional non-destructive examination techniques. Root lack of penetration is not a concern with partial penetration lap welds.
A third type of defect that has been identified specifically for friction stir lap welds can exist when the faying surface between the two sheets becomes stirred into the weld, producing a cold lap defect ( FIG. 15 ). Hot parameters, produced by a relatively fast spindle speed and low travel speed, are required to break up this faying surface and prevent a reduction in the weld's effective thickness. However, one must take caution in not producing too hot a weld, characterized by excessive flash and a powdery surface finish (galling). Alternative pin tool designs are being investigated in an attempt to break up the faying surface within the nugget while operating under colder parameters.
Successful butt and lap friction stir welds have been made at Lockheed Martin Michoud Space Systems (LMMSS) in multiple aluminum alloys including: 2014, 2024, 2219, AFC-458, 2090, 2195, 5083, 6061, 7050, 7075, and 7475. Table 1 shows the average strengths of the welds for some of these alloys. Large grain size extrusion, metal matrix composites (Al—SiC, Al—Al2O3), and dissimilar metal (2219 to 2195) friction stir welds have also been produced that exhibit good strength and quality. Various thicknesses have been joined ranging from 0.063″ 2024-T3 sheet to 2″ thick 6082-T6 plate welded in a single pass and 3″ thick 6082-T6 plate welded in a double pass. Welds up to 43 feet long have been successfully joined with no weld defects and no tool wear.
TABLE 1
Friction stir butt weld joint efficiencies for various aluminum alloys
Parent Metal
Alloy
UTS
Friction Stir Weld UTS
Joint Efficiency
AFC458-T8
79.0 [18]
52.5
66%
2014-T651
70.0 [19]
49.0
70%
2024-T351
70.0 [18]
63.0
90%
2219-T87
69.0 [19]
45.0
65%
2195-T8
86.0 [18]
59.0
69%
5083-O
42.0 [19]
43.0
102%
6061-T6
47.0 [18]
31.5
67%
7050-T7451
79.0 [18]
64.0
81%
7075-T7351
68.5 [18]
66.0
96%
Prior shear testing was performed at LMMSS on 2090 lap shear joints mechanically joined with 3/16″ diameter 2017 solid “icebox” rivets. Test specimens were manufactured and tested in accordance with MIL-STD-1312-4. Two different sheet thicknesses were tested (t=0.063″ and 0.083″) at room temperature.
TABLE 2
Lap shear strengths for 2090-T83 sheet joined with
a 2017 “icebox” aluminum rivet
2090 Sheet
Avg. Strength
St. Dev.
0.063″ to 0.063″
1083
46.3
0.080″ to 0.080″
1056
8.1
Lap shear results on 2090-T83 sheet mechanically joined with 3/16″ diameter 2017 aluminum rivets showed little variation between the 0.063″ and 0.080″ sheet thicknesses (Table 2). Consequently, it can be presumed that the test was appropriately determining the shear strength of only the rivet. Failure occurred by shear through the rivet.
EXAMPLE 1
2090-T83 is an Al—Cu—Li alloy that has been solution heat treated, cold worked and artificially aged. The specified chemical composition and general mechanical properties are given in Tables 3 and 4.
TABLE 3
Chemical composition for 2090-T83 aluminum alloy (wt %) [20]
Alloy
Cu
Fe
Li
Mg
Mn
Si
Ti
Zn
Zr
Others
Al
2090-T83
2.4–3.0
.12
1.9–2.6
.25
.05
.10
.15
.10
.08–.15
.20
Rem
TABLE 4
As tested parent metal properties for 2090-T83
Sheet Thickness (in.)
Grain Direction
UTS (ksi)
YS (ksi)
% EL (2″)
0.060
Longitudinal
86.5
78.9
6.0
0.082
Longitudinal
85.8
78.0
6.0
Friction stir lap welds were produced on flat panels of 2090-T83 with the top and bottom sheets having thicknesses of 0.063″ and 0.083″, respectively. The welds fully penetrated through the top sheet and partially penetrated the bottom sheet. They were done at various spindle and travel speeds in an attempt to achieve the highest weld quality as determined through lap shear strength, metallurgy and non-destructive evaluation. Welds were examined for internal defects using radiography to Grade 1 requirements for manned flight. Of particular interest was the path of the panels' interlayer faying surface.
Lap welded panels were cut for metallographic examination and mechanical shear testing. Shear samples were tested at room temperature on a 20 kip MTS testing machine at a constant cross head deflection of 0.05 in/min. In contrast to the riveted lap shear specimens, the sheet thicknesses of the friction stir welded lap joint varied. Consequently, although the specimens were pin loaded, they were additionally held by offset friction grips to account for the difference in top and bottom sheet thicknesses to ensure loading through the specimen interlayer.
Once desirable friction stir weld parameters had been set, a 21″ long, 0.063″ thick 2090-T83 stringer 28 having a cross-section shown in FIGS. 5–6 , was lap welded to a 0.083″ 2090-T83 skin sheet 29 . Welds were performed on a conventional mill with a steel backing anvil and traditional finger clamps. A specially designed pin tool 10 (see FIGS. 1–4 ) was contoured to accommodate the specific geometry of the stringer 28 . A duplicate test set was created by mechanically joining the stringer 28 to the skin 29 with 3/16″ diameter 2017 solid “icebox” rivets spaced 1″ apart.
Two friction stir welded and two riveted compression buckling samples (L/p=11.4) were produced, all identical except for their joining method. Both friction stir welded panels were non-destructively examined using ultrasonic inspection and radiography. These four panels were prepared for compression testing by potting their ends with Hysol Epoxy EA9394. The compression tests were performed at room temperature on a 200 kip MTS testing machine at a constant cross head deflection rate of 0.05 inches per minute.
Larger scale panels having 5 stringers across their width and having dimensions of 60.05″×33.2″ are being fabricated. One riveted and one friction stir welded panel will be compression tested at NASA Langley Research Center (LaRC) for comparison.
Lap Shear Results
Friction stir lap welds on 2090-T83 were done at various spindle speeds, travel speeds, and heel plunges. Metallurgical examination of the weld revealed remnant interlayer faying surface across the width of the nugget in all welds. The extent at which the faying surface remained across the weld nugget varied from weld to weld, and is currently being quantified to compare its effect on shear strength results.
In general, higher strengths were found on welds produced at faster spindle speeds (Table 5). An increase in pin tool rotation enhances the break up of the interlayer surface within the weld nugget. Furthermore, as shown in FIG. 16 , for a given rotation speed, the faster travel speed also produced the stronger weld. Lengthening the time at temperature experienced by the panel, resulting from a slower travel speed, increases the heat input into the weld. This additional heat input may cause a softening of the weld zone and consequently, lower shear strengths. Within this experiment, the weld that produced the highest shear strength was that which was processed at the highest spindle speed and the highest travel speed of all those fabricated (970 RPM and 9 inches per minute). Although the friction stir lap welds possessed cold lap defects, they still had shear strengths approximately 50%–100% higher on average than that of the mechanically joined specimens (Table 2). Future work will include testing friction stir welds processed at even higher spindle and travel speeds to produce defect free welds and determine the upper limit of shear strength.
TABLE 5
Processing parameters and strengths for 2090-T83 friction stir lap welds
Weld
Weld Pitch
Heel Plunge
Peak Load Avg.
St. Dev.
Typical Fracture
No.
RPM
IPM
(RPM/IPM)
(in)
(lbs/in)
(lbs/in)
Location
3
440
4.5
98
0.010
1277
37.1
Interface Shear
10
645
5.25
123
0.007
1441
7.0
0.080” Sheet
6
542
6.5
83
0.006
1517
27.5
Interface Shear
5
542
6.5
83
0.010
1524
59.5
Interface Shear
8
815
7.5
109
0.007
1529
41.4
0.080” Sheet
4
542
5.25
103
0.010
1581
30.7
0.080” Sheet
2
542
4.5
120
0.010
1610
108.3
0.080” Sheet
1
542
3.75
145
0.010
1619
20.7
0.080” Sheet
7
645
6.5
99
0.007
1624
131.0
0.080” Sheet
11
970
7.5
129
0.007
1668
15.2
0.080” Sheet
9
815
9
91
0.007
1909
38.2
0.080” Sheet
12
970
9
108
0.007
2175
89.2
0.080” Sheet
Two types of fracture surfaces were seen in the shear specimens. In the first type of failure, the friction stir weld shears at the interlayer between the 2090 sheets, with neither of the sheets ultimately failing. The interlayer is strongly present within the weld nugget, and consequently, the weld is of poor quality with only a weak diffusion bond occurring between the two sheets. The fracture surface reveals a scalloped pattern and the resultant shear strengths are low ( FIG. 17 ).
In the second type of failure, fracture initiation occurs within the thicker, bottom sheet where the weld nugget, TMZ, and faying surface all intersect. The fracture traverses along this faying surface and up to the interlayer. The true minimum thickness of the specimen is now the distance from the faying surface to the bottom edge of the 0.083″ sheet. Consequently, fracture also moves down from the initiation point and through the thickness of this sheet, where the specimen ultimately fails ( FIG. 18 ).
Compression Buckling Results
Stringer stiffened panels of 2090-T83 were successfully fabricated using friction stir lap welding in place of traditional riveting methods. Visual inspection of the weld showed good bonding, limited flash, and a smooth rippled surface with no galling or excess heat. All welds passed both ultrasonic and radiographic inspection. Metallurgic examination showed that the majority of the interlayer's faying surface was consumed by the fast rotation action of the pin tool at the weld nugget ( FIG. 19 ).
Prior to testing, predicted crippling compression loads for both the riveted and friction stir welded panels were obtained using two different techniques that were based upon specimen geometry (Table 6). It was calculated that ultimate failure for both types of panels would occur at similar loads.
From the data for each strain gauge, a straight line was drawn along the elastic region of the compression test. Initial buckling was determined to occur at the tangential point of this line with the data, i.e. when inelastic deformation began ( FIG. 20 ).
TABLE 6
Predicted failure loads for compression buckling tests
Ultimate Compression Load (Pc) =
32.3 kips
(Johnson-Euler method)
Ultimate Compression Load (Pc) =
32.7 kips
(Gerard Crippling
Panel Deflection (d @ Pc) =
0.078 in.
method)
Although the riveted specimens ultimately failed at a slightly higher load on average then the friction stir welded panels, initial buckling first occurred in the riveted specimens at approximately 16% (3700 lbs.) lower than the welded panels as determined for each strain gauge. Results are shown in Tables 7 and 8.
TABLE 7
Initial buckling loads for FSW Panel 1 and Riveted Panel 1
Strain Gauge
FSW (kips)
Riveted (kips)
1
26.1
24.3
2
26.8
22.7
3
25.1
19.8
4
26.6
23.1
Average
26.2
22.5
TABLE 8
Failure loads and deflections for FSW and Riveted Panels
Ultimate Compression Load
Panel Deflection
Panel
(Pc) - kips
(d @ Pc) - in.
Friction Stir Weld 1
30.2
0.092
Friction Stir Weld 2
29.5
0.084
FSW Avg.
29.9
0.088
Riveted 1
32.1
0.110
Riveted 2
32.7
0.095
Riveted Avg.
32.4
0.103
Both riveted panels failed in the same manner. Initial buckling occurred in the skin panel ( FIG. 21 ) and as the buckling continued, the energy was transferred directly into the riveted flanges. As shown in FIG. 22 , failure ultimately occurred along the stringer flange, near the row of rivets. Both friction stir welded panels also failed in a similar manner but unlike the riveted panels. Here, the specimen is a more isotropic configuration by virtue of the continuous weld, and consequently the panel acted more as a single “cross-section”. As the skin underwent initial buckling ( FIG. 23 ), the load was transmitted to the overall cross-section causing the outer part of the stringer to fail in a combined bending and axial compression mode ( FIG. 24 ).
The welded panel was less stiff at the flange/weld location than the riveted specimen. Since loads seek the stiffest path, more load was transmitted to the riveted flange at a faster rate than the welded specimen. The stringer wall on the riveted panel was not strong enough to distribute the load any further and ultimately failed at the row of rivets in the bend radius of the stringer flange. The welded panel attracted a somewhat lesser load at a slower rate allowing the stringer wall to transfer the stress to the location furthest from the neutral axis. Consequently, once initial buckling of the skin plate and stringer flanges occurred, the overall specimen performed as a column in axial compression and bending, induced by lateral deflection. Results of the large scale panel compression tests are to be reported at a later date.
In Summary 2090-T83 sheet can be successfully joined using friction stir welding in place of traditional mechanical joining processes. High spindle speeds aid in the break up of the interlaying faying surface within the weld nugget. Low travel speeds appear to have a detrimental effect on weld shear strength. Favorable friction stir lap welded shear specimens of 2090-T83 thin sheet had maximum peak loads approximately 100% higher than mechanically joined 2090-T83 using a 3/16″ diameter 2017 solid rivet. Calculated predictions of failure load and associated deflections for compression buckling tests were nearly identical to the actual test values obtained. Small scale compression buckling tests performed on friction stir welded stringer-stiffened panels had initial buckling loads approximately 16% higher than identical panels mechanically joined with 2017 solid rivets spaced 1″ apart. The failure mechanism for these two types of panels varied.
In FIGS. 25–30 , an additional embodiment of the apparatus of the present invention is shown, designated generally by the numeral 50 . Friction stir welded joint 50 provides a T-joint design (or tee-shaped structure) that joins three plates 51 , 52 , 53 . The plates 51 , 52 and 53 include two plates 51 , 52 that are positioned end to end at a plate 53 that forms an angle of about 90 degrees with each of the plates 51 and 52 .
Before friction stir welding is to begin, the plates 51 , 52 , 53 were oriented as shown in FIGS. 25–29 wherein the plate 53 is positioned in between edge portions 54 , 55 of the respective plates 51 , 52 as shown. Additionally, a projecting part 59 of plate 53 extends above the respective upper surfaces 61 , 62 of plates 51 , 52 . This projecting portion 59 can be seen in FIGS. 26–29 . The projecting or protruding portion 59 of the vertically oriented plate 53 in FIGS. 25–29 provides material that can be used for filling the void at contoured corners 81 , 82 of respective anvil supports 63 , 64 .
The vertical plate 53 provides an upper edge 56 that is the upper most part of the plate 53 . The vertically oriented plate 53 provides opposed generally parallel planar surfaces 57 , 58 that are engaged by anvils 63 , 64 . The anvil 63 provides a surface 65 that engages surface 57 of plate 53 . The anvil 64 provides a surface 66 that engages the surface 58 of plate 53 .
Each of the anvils 63 , 64 provides a generally flat, planar upper surface. The anvil 63 has an upper surface 67 that is engaged by the lower surface 69 of plate 51 . Similarly, the anvil 64 provides a flat, planar upper surface 68 that engages the flat, lower surface 70 of plate 52 . Each of the plates 51 and 52 provides a flat, planar upper surface. The plate 51 provides an upper surface 61 that is engaged by the flat, lower surface 73 of clamp 71 . Similarly, the plate 52 has an upper surface 62 that is engaged by the flat, planar undersurface 74 of clamp 72 .
In the drawings, the numeral 75 refers to the plate centerline for plate 53 that is the vertical plate. In FIGS. 26–29 , a pin tool 60 is shown that has a lower end portion 76 with a pin tool tip 79 that engages the upper end portion of plate 53 (including the protruding part 59 ) and the edges 54 , 55 of plates 51 , 52 respectively and material of those plates 51 , 52 that is next to the edges 54 , 55 as seen in FIGS. 25–29 . FIG. 26 illustrates the pin tool 60 when centered, aligning its pin tool centerline with the centerline 75 of plate 53 . In FIG. 27 , the pin tool 60 is shown at a left position at one side of the friction stir weld joint while FIG. 28 shows the pin tool 60 at a position to the right side of the friction stir weld joint. Generally speaking, the friction stir weld tool 60 will travel in between the position shown in FIGS. 27 and 28 .
The position of the clamps 71 , 72 relative to the anvils 63 , 64 and plates 51 , 52 , 53 is shown in FIGS. 26–29 . FIG. 29 shows an enlarged view of the lower end portion 76 of pin tool 60 and more particularly, the pin tip 79 , pin tip contoured sections 80 , and cylindrically shaped part 78 . The cylindrically shaped part 78 is a smaller diameter cylindrical portion when compared to the larger diameter cylindrically shaped portion 77 that defines the largest diameter of the pin tool 60 . Tip 79 communicates with smoothly curved, contoured portions 80 as shown in FIG. 29 . The contoured portions 80 communicate with smaller diameter cylindrically shaped part 78 of pin tool 60 .
Each of the anvil supports 63 and 64 has a contoured corner. This contoured corner is illustrated as reference numeral 81 for anvil support 63 in FIG. 29 . The contoured corner 82 is shown for the anvil support 64 in FIG. 29 . The protruding portion of the vertical plate 53 is used for filling the void at contoured corners 81 , 82 . Those void spaces are indicated by the numerals 83 , 84 in FIG. 29 .
A larger pin diameter is preferred to ensure that the amount of off centerline is preferably less than about 25 percent of the pin radius 85 (see FIG. 29 ) The contoured corner 81 , 82 of the anvil supports 63 , 64 will enable material to conform to the same contour that reduces and/or eliminates stress concentration.
A contour 80 is provided at the pin tip 79 as shown in FIG. 29 . This contour 89 at pin tip 79 will have a deeper penetration during friction stir welding in order to completely break the faying surface. In FIG. 30 , the completed tee-shaped structure is shown after the welding of FIGS. 25–29 . Reference numerals 86 – 87 designate material that has “filled” the void spaces 83 – 84 of FIG. 29 . That fill material 86 – 87 is a volume of material that is generally equal to the volume of material that comprised projecting portion 59 (above surfaces 61 , 62 ) in FIG. 29 . The fill material 86 is below surface 69 and to the left of plate 53 as shown by dotted lines in FIG. 30 . Similarly, fill material 87 is the material below surface 70 and to the right of plate 53 as shown by dotted lines in FIG. 30 .
The following is a list of parts and materials suitable for use in the present invention:
PARTS LIST
Part Number
Description
10
pin tool
11
end portion
12
end portion
13
large cylindrical section
14
large frustoconical section
15
groove
16
tip
17
cylindrical section
18
dished end
19
convex surface
20
small cylindrical section
21
small frustoconical section
22
annular shoulder
23
angle
24
central longitudinal axis
25
annular cavity
26
external thread
27
welding machine
28
stinger panel
29
stringer panel
30
inclined portion
31
flange
32
arrow
33
weld
34
pin tool position
35
arrow
50
stir welded joint
51
plate
52
plate
53
plate
54
edge
55
edge
56
edge
57
surface
58
surface
59
protruding part
60
pin tool
61
surface
62
surface
63
anvil support
64
anvil support
65
side surface
66
side surface
67
upper surface
68
upper surface
69
lower surface
70
lower surface
71
clamp
72
clamp
73
lower surface
74
lower surface
75
plate centerline
76
lower end pin tool
77
cylindrically shaped part
78
cylindrically shaped part
79
pin tip
80
contoured section pin tool
81
contoured corner
82
contoured corner
83
void space
84
void space
85
pin radius
86
fill material
87
fill material
All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used or intended to be used in a human being are biocompatible, unless indicated otherwise.
The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. | The present invention provides an improved method and apparatus for joining aluminum allow panels (eg. 2090-T83 aluminum lithium alloy). The method preliminarily positions two panels and skin panels next to each other so that a stringer panel overlaps a skin panel. A friction stir weld pin tool penetrates through one panel and at least partially into another panel. The panel material around the pin tool is frictionally heated, plasticized and joined until the faying surface is substantially consumed. In another embodiment, a tee-shaped structure is formed using friction stir welding to join three panels together. A projecting part of one panel (center, vertical) provides material that becomes a contoured corner panel below two side, horizontal panels after friction stir welding is completed (FIGS. 29, 30 ) | 1 |
FIELD OF THE INVENTION
The present invention relates to a pulse generator which includes an optical or magnetic pattern provided on a rotor of a motor, a sensor detecting a movement of the pattern due to a rotation of the motor, and which generates pulses following to the rotation of the motor from the output of the sensor and, more particularly to a sector boundary signal generator for a disk such as a magnetic disk.
BACKGROUND OF THE INVENTION
Published Unexamined Japanese patent application (PUPA) No. 59-154630 (154630/84) discloses that an optical recording medium on which recorded clock pulse signals are recorded is fixed in a freely replaceable manner, on a rotary shaft to which a magnetic recording medium is fixed, and the surface of the recording medium is read by a combination of light source and optical sensor to generate clock pulses.
In accordance with this method, signals following the rotational characteristics, that is wow and flutter components, of a motor for driving the rotary shaft can be obtained.
However, if an error occurs in the optical sensor or a recording or mounting error occurs in the optical recording medium when the above-mentioned prior art is applied, an erroneous signal might be issued from the optical sensor It is preferable not to generate sector boundary signals for servo write operations based on such signals.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a pulse generator capable of generating pulses following the rotational characteristics, that is wow and flutter components of a motor even if there are sensor errors or pattern errors (including pattern mounting errors) when an optical or magnetic pattern is provided on a rotor of a motor and a movement of the pattern due to a rotation of the motor is detected through a sensor.
Another object of the present invention is to provide a sector boundary signal generator capable of following only the rotational characteristics, that is wow and flutter components, of a motor used for driving a disk such as a magnetic disk by eliminating sensor errors and pattern errors including pattern setting errors even if there are those errors.
The present invention is based on two principles: one is that a wow component of a motor is distributed over a first frequency band ranging for example from 2 Hz to 6 Hz, a flutter component of the motor and pattern errors are distributed over a second frequency band ranging, for example from 10 Hz to 300 Hz, and pattern errors and sensor errors are distributed over a third frequency band exceeding 300 Hz; the other is that the pattern errors have periodicity, whereas the sensor errors have irregularity. In accordance with the present invention the sensor error component, the pattern error component, and the motor flutter component are eliminated from the output of the sensor, the wow component of the motor is left, and first pulses with a frequency of, for example, 1620 Hz are generated, by a first pulse generating means consisting of a phase-locked loop (hereinafter PLL) circuit with its low frequency pass characteristic, with a cutoff frequency of, for example, 10 Hz. The error component of the sensor and the higher frequency error component of the pattern are eliminated from the output of the sensor. The lower frequency error component of the pattern and the wow and flutter components of the motor are left, and second pulses with a higher frequency, for example, 1.05 MHz, than the first pulses in synchronization with only the above remaining components are generated, by a second pulse generating means consisting of a PLL circuit with its low frequency pass characteristic, with a cutoff frequency of, for example, 300 Hz. The second pulses occurring between two succeeding first pulses are counted. Every such count value is stored at every first pulse period. The count value stored is read and a pulse is generated when the same number of the second pulse generated due to a rotation of that part of the pattern which corresponds to said count value are counted as the count value read.
When a disk sector boundary signal generator is constructed in accordance with the present invention, the first pulses serve as sector boundary reference pulses, the second pulses serve as pulses containing a pattern error contained pulses, each period of the first pulses corresponds to each sector, and the pulse finally generated serves as a sector boundary signal.
It has been established that the pattern should be set up with sufficient precision to provide a sensor output having a frequency at least ten times that of the flutter component of the motor when the pattern rotates with the motor. If a less precise pattern, such as the provision of a sensor output with a lower frequency than above, the sector boundary signal generator may not follow the wow and flutter components of the motor.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of the sector boundary signal generator of the present invention.
FIG. 2 is a pattern view of an optical pattern label.
FIG. 3 is an explanatory view of the optical label attachment error which is likely to lead to an optical pattern error component.
FIG. 4 is a graphic representation of the frequency distribution of each component which is likely to cause fluctuations in optical sensor output.
FIG. 5 is a graphic representation of fluctuations in the rotational speed of the motor which are attributable to the wow and flutter of the motor.
FIG. 6 is a graphic representation of the output of the optical pattern error generator in terms of rotational frequencies.
FIG. 7 is a timing chart of the operations of the sector boundary signal generator of FIG. 1.
FIG. 8 is a block diagram of a construction example of the sector boundary reference generator of FIG. 1.
FIG. 9 is a block diagram of a construction example of the optical pattern error generator of FIG. 1.
DETAILED DESCRIPTION
FIG. 1 shows a magnetic disk sector boundary signal generator as one embodiment of the present invention. Referring now to FIG. 1, an optical pattern label 8 is adhered on a rotor 6 of a spindle motor 4 driving a magnetic disk 2 as shown. Black patterns 8a and white patterns 8b which are extended in the radial direction are alternately printed over the optical pattern label 8. Light is radiated onto the optical pattern label 8 from a light source 10. Light reflected from the optical pattern label 8 is directed to an optical sensor 12.
Accordingly, the higher the speed of the motor 4 is, the higher the frequency of pulses generated from the optical sensor 12, and the lower the speed of the motor 4, the lower the frequency of pulses outputted from the optical sensor 12. That is, the pulses outputted from the optical sensor 12 represent the rotational characteristics of the motor 4, and thus include the wow and flutter components of the motor 4. The numbers of black patterns 8a and white patterns 8b in the circumferential direction on the label 8 are determined so that the sensor 12 develops an output with a frequency of at least ten times that of the flutter component of the motor 4 when the label 8 rotates with the rotor of motor 4. The output of the sensor 12 can thus follow the wow and flutter components of the motor 4. With a motor rotating at a rotational frequency of 60 cycles per minute, for example, it is adequate to provide about 100 radial segments of black pattern. FIG. 2 shows one example of the optical pattern where 112 radial segments of black pattern are provided in the circumferential direction.
Although it is ideal for the output pulses from the optical sensor 12 to show only the rotational characteristics of the motor 4 including the wow and flutter components of the motor 4, there may arise cases in which the center 8C of the optical pattern label 8 does not coincide with the center 6C of the rotor 6 of the motor 4, or a print error occurs on the optical pattern label 8, in which cases the output of the optical sensor 12 would include some optical pattern errors. Also, a malfunction of the optical sensor 12 would lead to an optical sensor error in the output of the optical sensor 12.
FIG. 4 shows the frequency distribution of each component to be a possible cause of fluctuations in the output of the optical sensor 12. The first fluctuation component 32 is the wow component of the motor 4, which is distributed over the frequency band of 2 Hz to 6 Hz. The wow component of the motor 4 takes place irregularly. The second fluctuation component 34 consists of the flutter component of the motor 4 and the optical pattern error component of the optical pattern label 8, which is distributed over the frequency band of 10 Hz to 300 Hz. The flutter component of the motor 4 takes place irregularly, whereas the optical pattern error component takes place periodically. The third fluctuation component 36 consists of the optical pattern error component of the optical pattern label 8 and the error component of the optical sensor 12, which is distributed over a frequency band higher than 300 Hz. The optical pattern error component takes place periodically, whereas the optical error component occurs irregularly.
FIG. 5 shows fluctuations in the rotational speed of the motor 4 due to the wow and flutter of the motor 4. Also, in FIG. 5. assuming the average rotational speed of the motor 4 to be N rad/s, the wow represents a slower rotational fluctuation observed over several revolutions to several ten revolutions of the motor 4, whereas the flutter represents a quicker fluctuation taking place in one revolution of the motor 4. As described above, the wow and flutter are aperiodic.
The sector boundary signal generator shown in FIG. 1 is designed to generate sector boundary signals including the wow and flutter components of the motor 4, but neither optical pattern error component nor optical sensor error component. The sector boundary reference generator 14, consisting of a PLL circuit, with low pass frequency characteristics of a 10 Hz cutoff frequency generates 1620-Hz sector boundary reference pulses synchronous with the only wow component of the motor 4, by eliminating from the output of the optical sensor 12 the error component of the sensor, i.e. the third fluctuation component 36 of the optical sensor shown in FIG. 3, the error component of the optical pattern, i.e. the second and third fluctuation components 34 and 36 of the optical sensor shown in FIG. 3, and the flutter component of the motor, i.e. the second fluctuation component 34 of the optical sensor shown in FIG. 3. and leaving uneliminated the wow component of the motor 4, i.e. the first fluctuation component 32 shown in FIG. 3.
The optical pattern error generator 16, consisting of a PLL circuit with low pass characteristics of 300 Hz cutoff frequency, eliminates from the output of the optical sensor 12 the error component of the sensor and the higher frequency error component of the optical pattern, i.e. the third fluctuation component 36 of the optical sensor shown in FIG. 4; leaves uneliminated the lower frequency error component of the optical pattern and the flutter component of the motor 4, i.e. the second fluctuation component 34 of the optical sensor shown in FIG. 4, and the wow component of the motor 4, i.e. the first fluctuation component 32 of the optical sensor shown in FIG. 4; and thus generates a 1.05-MHz optical pattern error contained pulses synchronous with only those remaining components, i.e. the wow and flutter components of the motor 4 and the lower frequency error component of the optical pattern.
FIG. 6 shows an example of the output of the optical pattern error generator 16 in terms of revolution number. As is evident from this figure, the output of the optical pattern error generator 16 is the sum of the aperiodic wow and flutter components of the motor 4 and a certain periodic optical pattern error component.
The first counter logic circuit 18 is put into operation by a start signal issued when the magnetic disk 2 starts from its initial position, receives the output of the sector boundary reference generator 14 and the output of the optical pattern error generator 16, and counts optical pattern error component contained pulses which are issued from the optical pattern error generator 16 in the interval between two successive sector boundary reference pulses. As specifically described the first counter logic circuit 18 receives a first sector boundary reference pulse from the sector boundary reference generator 14, the logic circuit 18 issues a signal indicative of the first sector to the address line 18A and starts counting optical pattern error component contained pulses. When the circuit 18 receives a second sector reference pulse from the sector boundary reference generator 14, the circuit 18 stops counting the optical pattern error component contained pulses and sends the resultant count value to a data line 18D. Then the first counter logic circuit 18 switches the signal to the address line, 18A from the signal indicative of the first sector to a signal indicative of the second sector, and resumes the counting of optical pattern error component contained pulses. When the circuit 18 receives a third sector reference pulse from the sector boundary generator 14, the circuit 18 stops counting optical pulse error component contained pulses and sends the resultant count value to the data line 18D. The first counter logic circuit 18 repeats such counting operations until the final sector, and sends the resultant count values of optical pattern error component contained pulses for the respective sectors along with their relevant values indicative of those sectors through the data lines 18D and 18A to the random access memory 20. Thus, the memory 20 contains only a certain value which is indicative of the wow and flutter components and the the lower frequency error component of the optical pattern minus the wow component of the motor 4, that is, a value reflecting only the flutter component of the motor 4 and the lower frequency error component of the optical pattern.
In an example where the number of sectors is 27, the count value of the optical pattern error component contained pulses may be 648 unless there is an optical pattern error, or otherwise a value falling between 640 and 655, for example, if there is an optical pattern error.
The random access memory 20 when a write command is received, from outside, receives signals indicative of a particular sector and the count value of the optical pattern error contained pulses from the first counter logic circuit 18 through the address line 18A and the data line 18D, and stores at every sector the count value of the corresponding optical pattern error contained pulses. When the count value of the optical pattern error component contained pulses have been stored for all sectors, for example 27 sectors, a read command is issued from outside to the random access memory 20, instead of the write command.
The second counter logic circuit 22 begins its operation with a start signal given when the magnetic disk 2 begins to move from its initial position, issues a signal indicative of the first sector though the address line 22A to the random access memory 20, reads the count value of the optical pattern error component contained pulses for the first sector which is stored in the memory 20 and presets itself to that count. Then the count value of the second counter logic circuit 22 is decreased each time an optical pattern error component contained pulse arrives which is generated from the optical pattern error generator 16 due to a rotation of that part of the optical pattern 8 which corresponds to the first sector of the magnetic disk 2, and issues a sector boundary signal indicative of the boundary between first sector and second sector when the count value of the circuit 22 reaches zero.
As described above, the optical pattern error component containing pulses normally include not only the wow and flutter components of the motor 4, but also a certain optical pattern error component. Because the wow and flutter components of the motor 4 are of irregular occurrence, whereas the optical pattern error component has periodicity the optical pattern error component can be eliminated from the sector boundary signal if sector boundary signals are generated by counting the optical pattern error component containing pulses generated from the optical pattern error generator 16 due to a new rotation of that part of the optical pattern 8 which corresponds to the first sector of the magnetic disk 2 by the number of the optical pattern error component contained pulses generated from the optical pattern error generator 16 due to the previous rotation of that part of the optical pattern 8 which corresponds to the first sector of the magnetic disk 2. Also, the output of the first counter logic circuit 18 stored in the random access memory 20 includes not only an optical pattern error but also a flutter component. However, as shown in FIG. 6, since the flutter component is very small in comparison with the optical pattern error, it is permissible to include the flutter component in the optical pattern error. i.e., the repetitive error.
For example, if the frequency of the optical pattern error component containing pulses becomes higher in the first sector because of an optical pattern error, the count value of the first counter logic circuit 18 is incremented. The second counter logic circuit 16, however, counts the optical pattern error component contained pulses with the same higher frequency by the count value counted by the first counter logic circuit 18. Therefore, the time taken for the circuit 16 to count one pulse becomes shorter, and hence the optical pattern error has no effect on the time taken to count the optical pattern error component contained pulses over the first sector. Thus, the sector boundary signal issued by the second counter logic circuit 16 includes the wow and flutter components of the motor 4, but includes neither the optical pattern error component nor the optical sensor error component.
The second counter logic circuit 22, after issuing a signal indicative of the boundary between the first sector and the second sector, issues a signal indicative of the second sector to the address line 22A, reads and presets itself the count value of the optical pattern error component contained pulses for the second sector, decrements the count value each time an optical pattern error component contained pulse arrives from the optical pattern error generator 16 due to a rotation of that part of the optical pattern 8 corresponding to the second sector of the magnetic disk 2, and generates a sector boundary signal indicative of the boundary between the second sector and the third sector.
Likewise, the second counter logic circuit 22 reads from the random access memory 20 the count value of the optical pattern error component containing pulses for every sector, counts optical pattern error component contained pulses generated by the optical error pattern generator 16, due to a rotation of the part of optical pattern 8 corresponding to the sector being processed by the count value read above, generates each sector boundary signal, outputs all sector boundary signals, and terminates the operation.
FIG. 7 is a timing chart of the operation of the sector boundary signal generator shown in FIG. 1 when there is a flutter in the motor 4 and an error in the optical pattern. We assume here the following conditions: the frequency of pulses from the optical sensor 12 and the optical pattern error generator 16 becomes lower because an optical pattern error occurs in the first sector; in the second sector, neither optical pattern error nor flutter in the motor 4 occurs, the frequencies of the pulses from the optical sensor 12 and optical pattern error generator 16 each indicate a nominal value, and the period of those pulses is constant within the sector. Because there is the same optical pattern error in the third sector as in the first sector, the frequencies of pulses from the optical sensor 12 and the optical pattern error generator 16 become lower, and the period of said output pulses varies because a flutter component exists in the motor 4.
Thus, since there is an optical pattern error in the first sector, the count outputted from the first counter logic circuit 18 is 640, which is smaller than the counter value 648 outputted in the second sector which is free from any optical pattern error. However, since the optical pattern error has periodicity, the pulse pattern outputted from the optical sensor 12 and the optical pattern error generator 16 in the first and second sectors during a certain rotation of the magnetic disk 2 agree with the pulse pattern which the optical sensor 12 and the optical pattern error generator 16 output in the first and second sectors during another rotation of the magnetic disk 2, unless a flutter occurs in the motor 4. The period of pulses issued in the first sector by the optical pattern error generator 16 is always 648/640 times the period of pulses issued in the second sector by the optical pattern error generator 16. Accordingly, the time for the second counter logic circuit 22 to count the output pulses from the optical pattern error generator 16 in the first sector during a particular rotation of the magnetic disk 2 by the count value of the output pulses from the optical pattern error generator 16 in the first sector during the previous rotation of the magnetic disk 2 is the same as the time for the second counter logic circuit 22 to count the output pulses from the optical pattern error generator 16 in the second sector during a particular rotation of the magnetic disk 2 by the count value of the output pulses from the optical pattern error generator 16 in the second sector during the previous rotation of the magnetic disk 2. (In the example of FIG. 4, the time is 617 micro seconds.) The optical pattern error is thus eliminated.
In the third sector, there occurs not only an optical pattern error, but also a fluttering in the motor 4. Any such optical pattern error could easily be eliminated because of its periodicity, as described above, whereas since the flutter of the motor 4 is irregular, the counting time of the second counter logic circuit 22 varies with the state of flutter. FIG. 7 shows a case where the second counter logic circuit 22 takes a relatively long time of 618 microseconds to generate a sector boundary signal because of the flutter of the motor 4.
FIG. 8 shows one example of a specific structure of the sector boundary reference generator 14, which consists of a PLL circuit. In FIG. 8, a phase comparator 54 compares the output of the optical sensor 12 provided through a line 13 and a 1/2 frequency divider 52, with the output from a 1/2 frequency divider 64 of a feedback circuit in terms of their phases by exclusive-OR the output of the sensor 12 and the output of the 1/2 frequency divider 64, and outputs the phasal difference between the above two outputs to a low pass filter 56. The low pass filter 56, which has a cutoff frequency of 10 Hz, smooths the output of the phase comparator 54 and sends the resultant output to a voltage control oscillator 58. The voltage control oscillator 58 changes its frequency according to an output voltages of the low pass filter 56. The cutoff frequency of the low pass filter 56 corresponds to said smoothness: that is, the higher the cutoff frequency becomes, the less the smoothness becomes. The cut off frequency of the filter 56 changes the output frequencies of the voltage control oscillator 58. The output of the voltage control oscillator 58 is frequency-divided by a 1/N 10 frequency divider 60 and 1/N 11 frequency divider 62, each consisting of a loop counter, then be fed back to the phase comparator 54 through the 1/2 divider 64.
Provided that N 1 =N 10 ×N 11 , the central output frequency of the voltage control oscillator 58 is N 1 times that of the optical sensor 12. Accordingly, if the cutoff frequency of the low band pass filter 56 is set at 10 Hz, for example, so that the filter 56 should pass only the frequency band covering the wow component of the motor, fluctuations in the oscillation frequency of the voltage control oscillator 58 reflect only the wow component of those in the output of the optical sensor 12. The 1/2 dividers 52 and 64 are provided so that the two inputs to the phase comparator 54 should be 50% in duty factor.
FIG. 9 is one example of a specific construction of the optical pattern error generator 16, which consists of a PLL circuit. In FIG. 9, a 1/2 frequency divider 72, a phase comparator 74, a low pass filter 76 9 voltage control oscillator 78, a 1/N 20 frequency divider 80, a 1/N 21 frequency divider 82, and a 1/2 frequency divider 84 correspond to the 1/2 divider 52, the phase comparator 54, the low pass filter 56, the voltage control oscillator 58, the 1/N 10 divider 60, the 1/N 11 divider 62, and the 1/2 divider 64, respectively. The construction in FIG. 9 is distinguished from the construction in FIG. 8 only in that the cutoff frequency of the low pass filter 76 in FIG. 9 is set at 100 Hz to 300 Hz so that the filter 76 passes both the wow component and the flutter component of the motor, and that the frequency dividing ratios N 20 and N 21 of the dividers 80 and 82 are different from the frequency dividing ratios N 10 and N 11 of the dividers 60 and 62.
Although in the above-mentioned embodiment the sector boundary reference generator 14 and the optical pattern error generator 16 consist of PLL circuits, the present invention is not limited to this embodiment and frequency modulators and frequency demodulators can also be used, because an output wave from the sensor may be regarded as a result of frequency-modulating a certain fluctuation component on carriers given as the product of the revolution number of the motor and the number of radial optical pattern segments. Specifically stated, that sensor output is frequency-demodulated, its error component is eliminated by the above-mentioned low pass filter and memory, and the resultant signal is frequency-modulated to generate sector boundary signals, a function similar to the PLL circuits. In other words, the sector boundary reference generator 14 may be of any construction as long as it can fulfil the following functions: on receiving the output of the optical sensor 12, the sector boundary reference generator 14 eliminates from that output the error component of the optical sensor 12, the error component of the optical pattern, and the flutter component of the motor, leaves the wow component of the motor 4 uneliminated, and generates pulses synchronized with the wow component with a frequency corresponding to a particular sector number on the magnetic disk 2. Likewise, the optical pattern error generator 16 may be of any construction if it can fulfill the following functions: on receiving the output of the optical sensor 12, the optical pattern error generator 16 eliminates from that output the error component of the optical sensor 12 and the higher frequency error component of the optical pattern, leaves uneliminated the lower frequency error component of the optical pattern and the flutter and wow components of the motor, and generates pulses with a frequency higher than that of those sector boundary reference pulses in synchronization with the remaining components.
Although the above-mentioned embodiment relates to magnetic disks, it is also applicable to other types of disks, such as optical disks.
Moreover, the present invention is not limited in scope to generation of disk sector boundary signals, but is also widely applicable to any devices that detect through an optical sensor the movement of optical patterns with the rotation of a motor and generate pulses from the output of the sensor corresponding to the rotation of the motor.
Furthermore, such patterns are not limited to labels on which black and white segments are printed, but may be anything that provides signals indicative of the rotation of a motor, such as magnetic patterns whose state of magnetization inverts alternately along the circumference. Optical sensors may be used to read magnetic patterns written on a magnetic optical disk, whereas magnetic sensors are usually used to read magnetic patterns. However, it is more convenient and advantageous particularly in respect of cost, to apply optical pattern labels.
As evident from the above description, the present invention enables sensor error components and pattern error components to be eliminated, and also pulse signals, such as sector boundary signals, to be generated following the wow and flutter components of a motor. | A pulse generator and a disk sector boundary signal generator are implemented using an optical pattern of alternating light and dark radial lines or segments which are adhered to and rotate in unison with the rotor of a motor and are sensed by an optical sensor. The output of the optical sensor includes error conditions including sensor error, pattern error component, the wow component of the motor and the flutter component of the motor. A first pulse generating means eliminates sensor and pattern error components and the flutter component leaving only the wow component of the sensor output. A second pulse generating means that eliminates the higher frequency error components leaving pattern error components, wow components and flutter components, where the system is designed to generate flutter components with a frequency at least ten times the frequency of the wow component. The first pulses serve as disk sector boundary reference pulses. The second pulses, at a higher frequency, between first pulses contain pattern error pulses corresponding to the sector and the final pulse serves as a sector boundary pulse. | 6 |
RELATED APPLICATIONS
[0001] This application is a continuation under 35 U.S.C. §120 of U.S. patent application Ser. No. 12/179,769, filed 25 Jul. 2008, which claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 60/952,053, filed 27 Jul. 2007.
TECHNICAL FIELD
[0002] This disclosure generally relates to proximity sensors.
BACKGROUND
[0003] Capacitive position sensors have recently become increasingly common and accepted in human interfaces and for machine control. For example, in the fields of portable media players it is now quite common to find capacitive touch controls operable through glass or plastic panels. Some mobile telephones are also starting to implement these kinds of interfaces.
[0004] Many capacitive touch controls incorporated into consumer electronic devices for appliances provide audio or visual feedback to a user indicating whether a finger or other pointing object is present or approaches such touch controls. A capacitive sensing microprocessor may typically be comprised in touch-controlled devices which are arranged to provide an “on” output signal when a finger is adjacent to a sensor and an “off” output signal when a finger is not adjacent to a sensor. The signals are sent to a device controller to implement a required function dependent on whether a user's finger is in proximity with or touching an associated touch control.
[0005] Some touch-controlled devices remain “on” or “active” despite the user having moved away from the device or a particular function no longer being required. This results in the device consuming a large amount of power which is not efficient.
OVERVIEW
[0006] Particular embodiments provide a sensor for determining the presence of an object comprising: a sensing element; a capacitance measurement circuit operable to measure the capacitance of the sensing element; and a control circuit operable to determine whether an object is in proximity with the sensor based on a measurement of the capacitance of the sensing element, the control circuit further being operable to provide an output signal to control a function of an apparatus when it is determined that an object has not been in proximity with the sensor for a predetermined time duration.
[0007] The control circuit may be configured so that the predetermined time duration is selectable from a number of different predefined time durations.
[0008] The control circuit may include a time input terminal and the predetermined time duration may selectable from the number of different predefined time durations according to a voltage applied to the time input terminal.
[0009] The control circuit may include a delay multiplier terminal and be configured so that a selected one of the number of different predefined time durations is multiplied by a multiplication factor according to a voltage applied to the delay multiplier terminal so as to provide the predetermined time duration.
[0010] The control circuit may be configured so that the predetermined time duration is programmable by a user to provide a user-selected time duration.
[0011] The sensor may comprise a resistor-capacitor (RC) network coupled to the control circuit and the predetermined time duration may depend on a time constant of the RC network.
[0012] The control circuit may include a delay multiplier terminal and be configured so that the user-selected time duration is multiplied by a multiplication factor according to a voltage applied to the delay multiplier terminal to provide the predetermined time duration.
[0013] The control circuit may be configured such that the provision of the output signal to control a function of an apparatus after the predetermined time duration may be overridden so the output signal is not provided when it is determined that an object has not been in proximity with the sensor for a predetermined time duration. For example, the control circuit may be operable to receive an override pulse and on receipt of the override pulse to retrigger the predetermined time duration to so as to extend the time before the output signal to control a function of an apparatus is provided.
[0014] The control circuit may be configured such that the provision of the output signal to control a function of an apparatus after the predetermined time duration may be overridden so the output signal is provided before it is determined that an object has not been in proximity with the sensor for a predetermined time duration. For example, the control circuit may be operable to receive an override pulse and on receipt of the override pulse to provide the output signal to control a function of an apparatus.
[0015] The sensor may be configured to perform a recalibration when the sensor is powered up, when an object is determined to be in proximity with the sensor for more than a timer setting, and/or when an override is released.
[0016] The control circuit may be configured such that the output signal is toggled between a high state and a low state when an object is determined to be in proximity with the sensor.
[0017] The function of an apparatus controlled by the output signal may be a switch-off function.
[0018] The capacitance measurement circuit may employ bursts of charge-transfer cycles to acquire measurements.
[0019] The capacitance measurement circuit may be configured to operate in one of more than one acquisition modes depending on the output signal, for example a low-power mode or a fast mode.
[0020] The capacitance measurement circuit and the control circuit may be comprised in a general purpose microcontroller under firmware control.
[0021] The capacitance measurement circuit and the control circuit may be comprised within a six-pin integrated circuit chip package, such as an SOT23-6.
[0022] Particular embodiments provide an apparatus including a sensor as described above.
[0023] Particular embodiments provide a method for controlling a function of an apparatus comprising: determining whether an object is in proximity with a sensor based on a measurement of the capacitance of a sensing element and providing an output signal to control the function of the apparatus when it is determined that an object has not been in proximity with the sensor for a predetermined time duration.
[0024] The function of the apparatus controlled by the output signal may be a switch-off function.
[0025] Particular embodiments provide a sensor for determining the presence of an object comprising: a sensing element, a capacitance measurement circuit operable to measure the capacitance of the sensing element, and a control circuit operable to determine whether an object is in proximity with the sensor based on a measurement of the capacitance of the sensing element, the control circuit also being operable to provide an output signal to control a function of an apparatus based on an object not being in proximity with the sensor and the output signal being produced after a predetermined time duration.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Reference is now made by way of example to the accompanying drawings in which:
[0027] FIG. 1 schematically shows sense electrode connections for an example chip for implementing an auto-off function in particular embodiments;
[0028] FIG. 2 schematically represent an application of drift compensation in the chip of FIG. 1 ;
[0029] FIG. 3 schematically shows a basic circuit configuration for providing a 15 minute auto switch-off function in an active high output implementation of particular embodiments;
[0030] FIG. 4 schematically shows a series of fast mode bursts on the SNSK pin of the chip shown in FIG. 1 where in an on condition;
[0031] FIG. 5 schematically shows a series of low-power mode bursts and a switch to fast mode power bursts on the SNSK pin of the chip shown in FIG. 1 when switching from an off condition to an on condition;
[0032] FIG. 6 schematically shows use of an output configuration resistor Rop to configure the chip of FIG. 1 to have an active high or an active low output;
[0033] FIG. 7 schematically shows an example circuit configuration for the chip shown in FIG. 1 with the output connected to a digital transistor;
[0034] FIG. 8 schematically shows an example circuit configuration for the chip shown in FIG. 1 configured to provide a predefined auto-off delay;
[0035] FIG. 9 schematically shows an example circuit configuration for the chip shown in FIG. 1 configured to provide a programmable auto-off delay;
[0036] FIG. 10 schematically shows an example pulse applied to the chip shown in FIG. 1 to override an auto-off delay;
[0037] FIG. 11 schematically shows another example pulse applied to the chip shown in FIG. 1 to override an auto-off delay;
[0038] FIG. 12 schematically shows example voltage levels for the chip shown in FIG. 1 in overriding of an auto-off delay;
[0039] FIGS. 13 and 14 schematically show typical values of RC divisor K as
a function of supply voltage VDD for the chip shown in FIG. 1 with active high output and active low output respectively;
[0041] FIG. 15 schematically shows typical curves of auto-off delay as a function of timing resistor value for different capacitor values and different supply voltages for an active high output configuration;
[0042] FIG. 16 schematically shows typical curves of auto-off delay as a function of timing resistor value for different capacitor values and different supply voltages for an active low output configuration;
[0043] FIG. 17 schematically shows an example application of the chip shown in FIG. 1 in an active low output configuration driving a PNP transistor with an auto-off time of 3.33 hours;
[0044] FIG. 18 schematically shows another example application of the chip shown in FIG. 1 in an active high output configuration driving a high impedance with an auto-off time of 135 seconds;
[0045] FIG. 19 schematically shows an implementation of the chip shown in FIG. 1 in an SOT23-6 package; and
[0046] FIG. 20 schematically shows a pin diagram for an implementation of the chip shown in FIG. 1 in an SOT23-6 package.
DESCRIPTION OF EXAMPLE EMBODIMENTS
[0047] Particular embodiments may be implemented in an integrated circuit chip providing a proximity sensor function. The integrated circuit chip may thus be incorporated into a device or apparatus to provide and control a proximity sensor functionality for the device or apparatus in particular embodiments. For the purposes of explanation, a specific integrated circuit chip providing the functionality of an example embodiment will be described further below. The chip will in places be referred to by product name QT102. However, it will be appreciated that the QT102 chip is merely a specific example application of an example embodiment. Particular embodiments need not be implemented in a chip in this way, and furthermore, particular embodiments may be provided in conjunction with all, some or none of the additional features of the QT102 chip described further below.
[0048] Before turning specifically to the QT102 chip embodiment, a summary is provided.
[0049] It is known that a touch sensitive sensor may comprise a sensor element, such as an etched copper electrode mounted on a PCB substrate, and a control circuit for measuring a capacitance of the sensor element to a system reference potential. The sensor element may be referred to as a sense electrode. The capacitance of the sense electrode is affected by the presence of nearby objects, such as a pointing finger. Thus the measured capacitance of the sense electrode, and in particular changes in the measured capacitance, may be used to identify the presence of an object adjacent the sense electrode. The control circuit may be configured to provide an output signal, e.g. by setting an output logic level as high or low, indicating whether or not an object is deemed to be adjacent the sense electrode. A controller of a device in which the touch sensitive sensor is implemented may receive the output signal and act accordingly.
[0050] There are various known technologies for measuring capacitance of a sense electrode in a capacitive touch sensor. Particular embodiments may be implemented in conjunction with any of these technologies or measurement circuits. For example, the fundamental principles underlying the capacitive sensors described in U.S. Pat. No. 5,730,165, U.S. Pat. No. 6,466,036, and U.S. Pat. No. 6,452,514 could be used.
[0051] In particular embodiments, the control circuit of the sensor can determine whether an object or a user's finger is no longer in proximity with the sensor and based on a predetermined time duration, the control circuit can produce an output signal automatically to prevent the capacitance measurement circuit from continually measuring changes in capacitance due to, for example, the perceived presence of an object in proximity with the sensor.
[0052] Therefore, the control circuit is able to deactivate, turn-off, or power down the capacitance measurement circuit where an apparatus has inadvertently been left on or with the erroneous perception that a user is still present. This may, for example, be referred to as an “auto-off” feature. The signal for preventing the capacitance measurement circuit from continually measuring changes in capacitance may be referred to as an auto-off signal. The capacitance measurement circuit and the auto-off control circuit may be comprised in a general-purpose microcontroller under firmware control, for example, such as the QT102 chip described further below.
[0053] As described in Section 3.5 of the below numbered sections, and in conjunction with the drawings, the control circuit of the sensor may be implemented by different methods—for example, the auto-off signal output may be produced automatically after different predetermined time durations to effect powering down the capacitance measurement circuit due to no presence of the user; the control circuit may be programmed by a user so that it may power down an apparatus based on a user-selected time duration; the control circuit output signals may be overridden, for example, to extend time durations before an apparatus is turned-off or to immediately turn-off an apparatus when a user is no longer present.
[0054] The sensor of particular embodiments may be useful in various applications, for example in kitchen appliances, light switches, headsets, and other electronic consumer devices. For example, a coffee machine incorporating a sensor of particular embodiments may be programmed to power-down after a time period of, say, 30 minutes, where the coffee machine has been left on inadvertently. This will beneficially conserve energy use and minimize the possibility of damage or accidents caused by the coffee machine or glass container(s) overheating.
[0055] Aspects of the QT102 chip referred to above will now be described in the following numbered sections.
[0056] The numbered sections may be considered to relate generally to features of the QT102 chip as follows: Section 1—Overview (including 1.1 Introduction, 1.2 Electrode Drive, 1.3 Sensitivity, 1.3.1 Introduction, 1.3.2 Increasing Sensitivity, 1.3.3 Decreasing Sensitivity, 1.4 Recalibration Timeout, 1.5 Forced Sensor Recalibration, 1.6 Drift Compensation, 1.7 Response Time, 1.8 Spread. Spectrum). Section 2—Wiring and Parts (including 2.1 Application Note, 2.2 Cs Sample Capacitor, 2.3 Rs Resistor, 2.4 Power Supply, PCB Layout, 2.5 Wiring). Section 3—Operation (including 3.1 Acquisition Modes, 3.1.1 Introduction, 3.1.2 OUT Pin “On” (Fast Mode), 3.1.3 OUT Pin “Off” (Low Power Mode), 3.2 Signal Processing, 3.2.1 Detect Integrator, 3.2.2 Detect Threshold, 3.3 Output Polarity Selection, 3.4 Output Drive, 3.5 Auto Off Delay, 3.5.1 Introduction, 3.5.2 Auto Off—Predefined Delay, 3.5.3 Auto Off—User-programmed Delay, 3.5.4 Auto Off—Overriding the Auto Off Delay, 3.5.5 Configuring the User-programmed Auto-off Delay, 3.6 Examples of Typical Applications). Section 4—Specifications (including 4.1 Absolute Maximum Specifications, 4.2 Recommended Operating Conditions, 4.3 AC Specifications, 4.4 Signal Processing, 4.5 DC Specifications, 4.6 Mechanical Dimensions, 4.7 Moisture Sensitivity Level (MSL)).
1 Overview
1.1 Introduction
[0057] The QT102 is a single key device featuring a touch on/touch off (toggle) output with a programmable auto switch-off capability.
[0058] The QT102 is a digital burst mode charge-transfer (QT) sensor designed specifically for touch controls; it includes hardware and signal processing functions to provide stable sensing under a wide variety of changing conditions. In examples, low cost, non-critical components are employed for configuring operation.
[0059] The QT102 employs bursts of charge-transfer cycles to acquire its signal. Burst mode permits power consumption in the microampere range, dramatically reduces radio frequency (RE) emissions, lowers susceptibility to electromagnetic interference (EMI), and yet permits good response time. Internally the signals are digitally processed to reject impulse noise, using a “consensus” filter which in this example requires four consecutive confirmations of a detection before the output is activated.
[0060] The QT switches and charge measurement hardware functions are all internal to the QT102.
1.2 Electrode Drive
[0061] FIG. 1 schematically shows the sense electrode connections (SNS, SNSK) for the QT102.
[0062] For improved noise immunity, it may be helpful if the electrode is only connected to the SNSK pin.
[0063] In examples the sample capacitor Cs may be much larger than the load capacitance (Cx). E.g. typical values for Cx are 5 to 20 pF while Cs is usually 1 or 2 to 50 nF. (Note: Cx is not a physical discrete component on the PCB, it is the capacitance of the touch electrode and wiring. It is shown in FIG. 1 to aid understanding of the equivalent circuit.)
[0064] Increasing amounts of Cx destroy gain, therefore it is important to limit the amount of load capacitance on both SNS terminals. This can be done, for example, by minimizing trace lengths and widths and keeping these traces away from power or ground traces or copper pours.
[0065] The traces and any components associated with SNS and SNSK will become touch sensitive and so may need to be considered to help in limiting the touch-sensitive area to the desired location.
[0066] A series resistor, Rs, may be placed in line with SNSK to the electrode to suppress electrostatic discharge (ESD) and Electromagnetic Compatibility (EMC) effects.
1.3 Sensitivity
1.3.1 Introduction
[0067] The sensitivity of the QT102 is a function of such things as:
the value of Cs electrode size and capacitance electrode shape and orientation the composition and aspect of the object to be sensed the thickness and composition of any overlaying panel material the degree of ground coupling of both sensor and object
1.3.2 Increasing Sensitivity
[0074] In some cases it may be desirable to increase sensitivity; for example, when using the sensor with very thick panels having a low dielectric constant. Sensitivity can often be increased by using a larger electrode or reducing panel thickness. Increasing electrode size can have diminishing returns, as high values of Cx will reduce sensor gain.
[0075] The value of Cs also has an effect on sensitivity, and this can be increased in value with the trade-off of slower response time and more power. Increasing the electrode's surface area will not substantially increase touch sensitivity if its diameter is already significantly larger in surface area than the object being detected. Panel material can also be changed to one having a higher dielectric constant, which will better help to propagate the field.
[0076] Ground planes around and under the electrode and its SNSK trace may lead to high Cx loading and destroy gain. Thus in some cases the possible signal-to-noise ratio benefits of ground areas may be more than negated by the decreased gain from the circuit, and so ground areas around electrodes may be discouraged in some circumstances. Metal areas near the electrode may reduce the field strength and increase Cx loading and so it may be helpful if these are avoided if possible. It may be helpful to keep ground away from the electrodes and traces.
1.4 Recalibration Timeout
[0077] If an object or material obstructs the sense electrode the signal may rise enough to create a detection, preventing further operation. To help reduce the risk of this, the sensor includes a timer which monitors detections. If a detection exceeds the timer setting (known as the Max On-duration) the sensor performs a full recalibration. This does not toggle the output state but ensures that the QT102 will detect a new touch correctly. The timer is set to activate this feature after ˜30 seconds. This will vary slightly with Cs.
1.5 Forced Sensor Recalibration
[0078] The QT102 has no recalibration pin; a forced recalibration is accomplished when the device is powered up, after the recalibration timeout or when the auto-off override is released.
[0079] However, supply drain is low so it is a simple matter to treat the entire IC as a controllable load; driving the QT102's VDD pin directly from another logic gate or a microcontroller port will serve as both power and “forced recal(ibration)”. The source resistance of most CMOS gates and microcontrollers are low enough to provide direct power without problems.
1.6 Drift Compensation
[0080] Signal drift can occur because of changes in Cx and Cs over time. It may be helpful if drift is compensated for, otherwise false detections, nondetections, and sensitivity shifts may follow.
[0081] Drift compensation is schematically shown in FIG. 2 . Drift compensation is performed by making a reference level track the raw signal at a slow rate, but only while there is no detection in effect. It may be helpful if the rate of adjustment is performed relatively slowly, otherwise there may be a risk that legitimate detections may be ignored. The QT102 drift compensates using a slew-rate limited change to the reference level; the threshold and hysteresis values are slaved to this reference.
[0082] Once an object is sensed, the drift compensation mechanism ceases since the signal is legitimately high, and therefore should not cause the reference level to change (as indicated in FIG. 2 during the period between the vertical dotted lines).
[0083] The QT102's drift compensation is “asymmetric”; the reference level drift-compensates in one direction faster than it does in the other. Specifically, it compensates faster for decreasing signals than for increasing signals. It may be helpful if increasing signals are not compensated for quickly, since an approaching finger could be compensated for partially or entirely before approaching the sense electrode.
[0084] However, an obstruction over the sense pad, for which the sensor has already made full allowance, could suddenly be removed leaving the sensor with an artificially elevated reference level and thus become insensitive to touch. In this latter case, the sensor will compensate for the object's removal more quickly, for example in only a few seconds.
[0085] With relatively large values of Cs and small values of Cx, drift compensation will appear to operate more slowly than with the converse. Note that the positive and negative drift compensation rates are different.
1.7 Response Time
[0086] The QT102's response time is dependent on burst length, which in turn is dependent on Cs and Cx. With increasing Cs, response time slows, while increasing levels of Cx reduce response time.
1.8 Spread Spectrum
[0087] The QT102 modulates its internal oscillator by ±7.5 percent during the measurement burst. This spreads the generated noise over a wider band reducing emission levels. This also reduces susceptibility since there is no longer a single fundamental burst frequency.
2. Wiring and Parts
[0088] FIG. 3 schematically shows a basic circuit configuration for an implementation of particular embodiments.
2.1 Application Note
[0089] Although not necessarily relevant to particular embodiments, for completeness, reference may be made to Application Note AN-KDO2 (“Secrets of a Successful QTouch™ Design”), included herein in its entirety by reference, and downloadable from the Quantum Research Group website, for information on example construction and design methods. Go to http://www.qprox.com, click the Support tab and then Application Notes.
2.2 Cs Sample Capacitor
[0090] Cs is the charge sensing sample capacitor. The required Cs value depends on the thickness of the panel and its dielectric constant. Thicker panels require larger values of Cs. Typical values are 1 or 2 nF to 50 nF depending on the sensitivity required; larger values of Cs may demand higher stability and better dielectric to ensure reliable sensing.
[0091] The Cs capacitor may be a stable type, such as X7R ceramic or PPS film. For more consistent sensing from unit to unit, 5 percent tolerance capacitors are recommended. X7R ceramic types can be obtained in 5 percent tolerance for little or no extra cost. In applications where high sensitivity (long burst length) is required, the use of PPS capacitors is recommended.
[0092] Series resistor Rs is in line with the electrode connection and may be used to limit electrostatic discharge (ESD) currents and to suppress radio frequency interference (RFI). It may be approximately 4.7 kΩ to 33 kΩ, for example.
[0093] Although this resistor may be omitted, the device may become susceptible to external noise or RF 1. For more details of how to select these resistors see the Application Note AN-KD02 referred to above in Section 2.1.
2.4 Power Supply, PCB Layout
[0094] The power supply (between VDD and VSS/system ground) can range between 2.0V and 5.5V for the QT102 implementation. If the power supply is shared with another electronic system, it may be helpful if care is taken to ensure that the supply is free of digital spikes, sags, and surges which can adversely affect the device. The QT102 will track slow changes in VDD, but it may be more affected by rapid voltage fluctuations. Thus it may be helpful if a separate voltage regulator is used just for the QT102 to isolate it from power supply shifts caused by other components.
[0095] If desired, the supply can be regulated using a Low Dropout (LDO) regulator. See Application Note AN-KD02 (see Section 2.1) for further information on power supply considerations.
[0096] Suggested regulator manufacturers include:
Toko (XC6215 series) Seiko (S817 series) BCDSemi (AP2121 series)
[0100] Parts placement: The chip may be placed to minimize the SNSK trace length to reduce low frequency pickup, and to reduce Cx which degrades gain. It may be helpful if the Cs and Rs resistors (see FIG. 3 ) are placed close to the body of the chip so that the trace between Rs and the SNSK pin is relatively short, thereby reducing the antenna-like ability of this trace to pick up high frequency signals and feed them directly into the chip. A ground plane can be used under the chip and the associated discretes, but it may be helpful if the trace from the Rs resistor and the electrode do not run near ground, to reduce loading.
[0101] For improved Electromagnetic compatibility (EMC) performance the circuit may be made entirely with surface mount technology (SMT) components.
[0102] Electrode trace routing: It may be helpful to keep the electrode trace (and the electrode itself) away from other signal, power, and ground traces including over or next to ground planes. Adjacent switching signals can induce noise onto the sensing signal; any adjacent trace or ground plane next to, or under, the electrode trace will cause an increase in Cx load and desensitize the device.
[0103] Note: a 100 nF (0.1 μF) ceramic bypass capacitor (not shown in FIG. 3 ) might be used between VDD and VSS in cases where it is considered appropriate to help avoid latch-up if there are substantial VDD transients; for example, during an ESD (electrostatic discharge) event. It may furthermore be helpful if the bypass capacitor is placed close to the device's power pins.
[0000]
TABLE 2.1
QT102 Pin Descriptions
(referring to the pin numbering shown in FIG. 3)
PIN
NAME
TYPE
DESCRIPTION
1
OUT
O
To switched circuit and output polarity
selection resistor (Rop)
2
VSS
P
Ground power pin
3
SNSK
IO
To Cs capacitor and to sense electrode
4
SNS
IO
To Cs capacitor and multiplier configuration
resistor (Rm). Rm connected to either VSS or
VDD. Refer to Section 3.5 for details.
5
VDD
P
Positive power pin
6
TIME
I
Timeout configuration pin, connected to either
VSS, VDD, OUT or an RC
network. Refer to Section 3.5 for details.
Type:
P—Ground or power;
IO—Input and output;
OD—Open drain output;
O—Output only, push-pull;
I—Input only
[0104] Regarding FIG. 3 , the following sections provide guidance for some example component values: Section 2.2 for Cs capacitor (Cs); Section 2.3 for Sample resistor (Rs); Section 2.4 for Voltage levels; Section 3.5.2 for Rm; and Section 3.3 for Rop.
3. Operation
3.1 Acquisition Modes
3.1.1 Introduction
[0105] The polarity for the OUT pin of the QT102 can be configured to be “active high” or “active low” (see Section 3.3). If configured active high, then “on” is high and “off” is low. If configured active low, then “on” is low and “off” is high.
[0106] The QT102 has more than one acquisition mode with the mode depending on the state of the OUT pin (on or off) and whether a touch is detected. In the following text “on” is when the output is in its active state (which could be high or low depending on how the polarity for the OUT pin is configured).
3.1.2 OUT Pin “On” (Fast Mode)
[0107] The QT102 runs in a “Fast mode” when the OUT pin is on. In this mode the device runs at maximum speed at the expense of increased current consumption. The delay between bursts in Fast mode is approximately 2.6 ms. FIG. 4 schematically shows bursts on the SNSK pin during fast mode acquisition.
3.1.3 OUT Pin “Off” (Low Power Mode)
[0108] The QT102 runs in Low Power (LP) mode if the OUT pin is off. In this mode it sleeps for approximately 85 ms at the end of each burst, saving power but slowing response. On detecting a possible key touch, it temporarily switches to Fast mode until either the key touch is confirmed or found to be spurious (via the detect integration process). If the touch is confirmed the QT102 will switch to Fast mode. If a touch is denied the device will revert to normal LP mode operation automatically. FIG. 5 schematically shows bursts on the SNSK pin during a touch detection event. Also schematically represented is the output signal on the OUT pin. A key touch occurs around halfway along the figure. Prior to the key touch, the OUT pin is off (schematically shown here as a low logic level) and the QT102 is running in Low Power mode with sleep periods between bursts. The capacitance measured during the first burst after the key touch is higher and this triggers Fast mode acquisition. Following four burst in which the higher capacitance is seen (see Section 3.2.1), the OUT pin switches to on (schematically shown here as a high logic level) and Fast mode acquisition continues.
3.2 Signal Processing
3.2.1 Detect Integrator
[0109] It is desirable to suppress detections generated by electrical noise or from quick brushes with an object. To accomplish this, the QT102 incorporates a “detect integration” (DI) counter that increments with each detection until a limit is reached, after which the output is activated. If no detection is sensed prior to the final count, the counter is reset immediately to zero. In the QT102, the required count is four. The DI can also be viewed as a “consensus” filter, that requires four successive detections to create an output.
3.2.2 Detect Threshold
[0110] The device detects a touch when the signal has crossed a threshold level, in this example the threshold level is fixed at 10 counts.
3.3 Output Polarity Selection
[0111] The output (OUT pin) of the QT102 can be configured to have an active high or active low output by means of the output configuration resistor Rop. The resistor is connected between the output an output configuration voltage Vop, which may be either VSS or VDD as schematically shown in FIG. 6 . For the QT102, if Vop is VSS, the output polarity is configured active high. If Vop is VDD, the output polarity is configured active low
[0112] It is noted that some devices, such as Digital Transistors, have an internal biasing network that will naturally pull the OUT pin to its inactive state. If these are being used then the resistor Rop is not required, as schematically shown in FIG. 7 .
3.4 Output Drive
[0113] The OUT pin in the QT102 embodiment can sink or source up to 2 mA. When a relatively large value of Cs (e.g. >20 nF) is used, it may be helpful if the OUT pin current is limited to <1 mA to reduce the risk of gain-shifting side effects. These may happen when the load current creates voltage drops on the die and bonding wires; in some cases these small shifts can materially influence the signal level to cause detection instability.
3.5 Auto Off Delay
3.5.1 Introduction
[0114] In addition to toggling the output on/off with key touch, the QT102 can automatically switch the output off after a specific time. This feature can be used to save power in situations where the switched device could be left on inadvertently.
[0115] The QT102 has:
three predefined delay times (Section 3.5.2) the ability to set a user-programmed delay (Section 3.5.3) the ability to override the auto off delay (Section 3.5.4)
[0119] The QT102 chip is programmed such that the TIME and SNS pins may be used to configure the auto-off delay t o and may be connected in one of the ways described in Sections 3.5.2, 3.5.3 and 3.5.4 to provide different functionality.
3.5.2 Auto Off—Predefined Delay
[0120] To configure a predefined delay t o the TIME pin may be wired to a voltage V t , as schematically indicated in FIG. 8 . Voltage V t may be VSS, VDD or OUT. These provides nominal values of t o =15 minutes, 60 minutes or infinity (remains on until toggled off) as indicated in Table 3.2 for an active high output configuration and in Table 3.3 for an active low output configuration.
[0121] Furthermore, also as shown in FIG. 8 , a resistor Rm (e.g. a 1 MΩ resistor) may be connected between the SNS pin and the logic level Vm to provide three auto off functions: namely delay multiplication, delay override and delay retriggering. On power-up the logic level at Vm is assessed and a delay multiplication factor is set to ×1 or ×24 accordingly (see Table 3.4). At the end of each acquisition cycle the logic level of Vm is monitored to see if an Auto off delay override is required (see Section 3.5.4).
[0122] Setting the delay multiplier to ×24 will decrease the key sensitivity. Thus in some cases it may be appropriate to compensate for this by increasing the value of Cs.
[0000]
TABLE 3.2
Predefined Auto-off Delay
(Active High Output)
Vt
Auto-off delay (t o )
VSS
Infinity (remain on until toggled to off)
VDD
15 minutes
OUT
60 minutes
[0000]
TABLE 3.3
Predefined Auto-off Delay
(Active Low Output)
Vt
Auto-off delay (t o )
VSS
15 minutes
VDD
Infinity (remain on until toggled to off)
OUT
60 minutes
[0000]
TABLE 3.4
Auto-off Delay Multiplier
Vm
Auto-off delay multiplier
VSS
t o * 1
VDD
t o * 24
3.5.3 Auto Off—User-Programmed Delay
[0123] If a user-programmed delay is desired, a resistor Rt and capacitor Ct can be used to set an auto-off delay (see Table 3.5 and FIG. 9 ). The delay time is dependent on the RC time constant (Rt*Ct) the output polarity (i.e. whether active high or active low), and the supply voltage. Section 3.5.5 gives more details of how to configure the QT102 to have auto-off delay times ranging from 1 minute to up to 24 hours.
[0000]
TABLE 3.5
Programmable Auto Off Delay
Output type
Auto Off Delay (seconds)
Active high
(Rt * Ct * 15)/42
Active low
(Rt * Ct * 15)/14.3
[0124] Notes: The RC divisor values K(42 and 14.3) may be obtained from FIGS. 13 and 14 . In this example the values are for a supply voltage VDD=3.5 volts. For the parameterization shown in Table 3.5, Rt is in kΩ and Ct is in nF.
3.5.4 Auto Off—Overriding the Auto Off Delay
[0125] In normal operation the QT102 output is turned off automatically after the auto-off delay. However, in some applications it may be useful to extend the auto-off delay (“sustain” function), or to switch the output off immediately (“cancel” function). This can be achieved by pulsing the voltage on the delay multiplier resistor Rm as schematically shown in FIG. 10 (positive-going pulse from VSS to VDD for delay multiplier ×1 configuration) and FIG. 11 (negative-going pulse from VDD to VDD for delay multiplier ×24 configuration). The pulse duration tp may determine whether a retrigger of the auto-off delay or a switch of the output to off is desired. To help ensure the pulse is detected it may be present for a time greater than the burst length as shown in Table 3.6.
[0000]
TABLE 3.6
Time Delay Pulse
Pulse Duration
Action
tp > burst time +
Retrigger (reload auto-off delay
10 ms (typical
counter)
value 25 ms)
tp > burst time +
Switch output to off state and
50 ms (typical
inhibit further touch detection until
value 65 ms)
Vm returns to original state
[0126] While Vm is held in the override state (i.e. the duration of the pulse) the QT102 inhibits bursts and waits for Vm to return to its original state (at the end of the pulse). When Vm returns to its original state the QT102 performs a sensor recalibration before continuing in its current output state.
[0127] FIG. 12 schematically shows override pulses being applied to a QT102 with delay multiplier set to ×1 (i.e. Vm normally at VSS with positive going pulses). The QT102 OUT signal is shown at the top of FIG. 12 . Vm is shown in the middle. Acquisition bursts on SNSK are shown at the bottom. Each short pulse P on Vm causes a sensor recalibration C and a restart of the auto-off timer. During the long pulse applied to Vm (i.e. where tp>t off ), the output is switched off at O. When the pulse finishes, the output remains switched off and a sensor recalibration C is performed.
3.5.5 Configuring the User-Programmed Auto-Off Delay
[0128] As described in Section 3.5.3 the QT102 can be configured to give auto-off delays ranging from minutes to hours by means of a simple CR network and the delay multiplier input.
[0129] With the delay multiplier set at ×1 the auto-off delay is calculated as follows:
[0000] Delay value=integer value of ( Rt*Ct/K )*15 seconds. (i.e. Rt*Ct=Delay value (in seconds)*K/15 Note: Rt is in kΩ, Ct is in nF.
[0132] In some applications improved operation may be achieved if the value of Rt*Ct is between 4 and 240. Values outside this range may be interpreted as the hard wired options TIME linked to OUT and TIME linked to “off” respectively, causing the QT102 to use the relevant predefined auto-off delays (see Tables 3.2 and 3.3).
[0133] FIGS. 13 and 14 show typical values of K versus supply voltage for a QT102 with active high or active low output.
Example Using the Formula to Calculate Rt and Ct
[0134] Requirements/Operating Parameters:
Active high output (Vop connected to VSS) Auto-off delay 45 minutes VDD=3.5 v
[0138] Proceed as Follows:
1. Calculate Auto-off delay in seconds 45*60=2700 2. Obtain K from FIG. 13 (active high): K=42 for VDD=3.5 v 3. Calculate Rt*Ct=2700*42/15=7560 4. Select a value for Ct (or conversely Rt). E.g. Ct=47 nF 5. Calculate Rt (or conversely Ct)=7560/47=160 kΩ
[0144] As an alternative to calculation, Rt and Ct values may be selected from pre-calculated curves such as shown in FIGS. 15 and 16 . FIGS. 15 and 16 show charts of typical curves of auto-off delay against resistor and capacitor values for active high ( FIG. 15 ) and active low ( FIG. 16 ) outputs at various values of VDD and for delay multiplier=×1.
Example Using Plot Shown in FIG. 15 or 16 to Calculate Rt and Ct
[0145] Requirements/Operating Parameters:
Active low output (Vop connected to V55) Auto-off delay 10 hours VDD=4V
[0149] Proceed as Follows:
1. Calculate Auto-off delay in seconds 10×60×60=36000. This value is outside of the range of the charts so use the ×24 multiplier (connect Rm to VDD). Note: this will decrease the key sensitivity, so in some circumstances it may be helpful to increase the value of Cs. 2. Find 36000/24=1500 on the 4V chart in FIG. 16 3. Read across to see appropriate Rt/Ct combinations. This example shows the following Rt/Ct combinations to be appropriate: 100 nF/10 kΩ, 47 nF/27 kSΩ, 22 nF/60 kΩ, and 10 nF/130 kΩ
[0154] Of course the Auto-off delay times given here are nominal and will vary slightly from chip to chip and with capacitor and resistor tolerance.
3.6 Examples of Typical Applications
[0155] FIG. 17 shows a first example application of a QT102 chip in particular embodiments. Here the QT102 is in an active low configuration and is shown driving a PNP transistor with an auto off time of 500 s×24 (3.33 hours)
[0156] The auto off time for the circuit configuration shown in FIG. 16 may be obtained from the VDD=3V chart in FIG. 16 . Setting the delay multiplier to ×24 will decrease the key sensitivity, so it may be helpful in some cases to increase the value of Cs.
[0157] FIG. 17 shows a second example application of a QT102 chip in particular embodiments. Here the QT102 is in an active high configuration and is shown driving high impedance with an auto off time of 135 s×1 (2.25 minutes).
[0158] The auto off time for the circuit configuration shown in FIG. 18 may be obtained from the VDD=5V chart in FIG. 15 .
4. Example Specifications for an Example QT102 Chip
[0159] An example chip incorporating particular embodiments may have the following specifications.
4.1 Suggested Maximum Operating Specifications
[0000]
Operating temperature: −40° C. to +85° C.
Storage temperature: −55° C. to +125° C.
VDD: 0 to +6.5V
Maximum continuous pin current, any control or drive pin: ±20 mA
Short circuit duration to VSS, any pin: infinite
Short circuit duration to VDD, any pin: infinite
Voltage forced onto any pin: −0.6 to (VDD+0.6) Volts
4.2 Recommended Typical Operating Conditions
[0000]
VDD: +2.0 to 5.5V
Short-term supply ripple+noise: ±5 mV
Long-term supply stability: ±100 mV
Cs value: 1 or 2 nF to 50 nF
Cx value: 5 to 20 pF
4.3 AC Specifications
[0172] VDD=3.0V, Cs=10 nF, Cx=5 pF, Ta=recommended range, unless otherwise noted
[0000]
Parameter
Description
Min
Typ
Max
Units
Notes
T RC
Recalibration time
250
ms
Cs and Cx dependent
T PC
Charge duration
2
μs
±7.5% spread spectrum
variation
T PT
Transfer duration
2
μs
±7.5% spread spectrum
variation
T
Time between end of
2.6
ms
burst and start of the
next (Fast mode)
T GZ
Time between end of
85
ms
Increases with reducing
burst and start of the
VDD
next (LP mode)
T BL
Burst length
20
ms
VDD, Cs and Cx
dependent. See Section
2.2 for capacitor
selection.
T R
Response time
100
ms
4.4 Signal Processing
[0173]
[0000]
Description
Min
Typ
Max
Units
Notes
Threshold differential
10
counts
Hysteresis
2
counts
Consensus filter length
4
samples
Recalibration timer
40
secs
Will vary with
VDD
4.5 DC Specifications
[0174] VDD=3.0V, Cs=10 nF, Cx=5 pF, Ta=recommended range, unless otherwise noted
[0000]
Parameter
Description
Min
Typ
Max
Units
Notes
V pp
Supply voltage
2
5/5.5
V
I DD
Supply current
5
60
μA
Depending on
supply and run
mode
IddI
Supply current, LP
23
μA
2 V
Mode
37
3 V
90
5 V
V DDS
Supply turn-on
100
V/s
Required for
slope
proper start-up
V IL
Low input logic
0.8
V
level
V HL
High input logic
2.2
V
level
V OL
Low output
0.6
V
OUT, 4TA sink
voltage
V OH
High output
VDD-0.7
V
OUT, 1 mA source
voltage
I IL
Input leakage
±1
μA
current
Cx
Load capacitance
0
100
pF
range
A R
Acquisition
9
14
bits
resolution
4.6 Mechanical Dimensions
[0175] In one example embodiment a chip implementing the above-described QT102 chip functionality may be provided in an SOT23-6 package type. Referring to FIG. 19 , the chip may thus have the following dimensions.
[0000]
Package type: SOT23-6
Millimeters
Inches
Symbol
Min
Max
Notes
Min
Max
Notes
M
2.8
3.10
0.110
0.122
W
2.6
3.0
0.102
0.118
Aa
1.5
1.75
0.059
0.069
H
0.9
1.3
0.035
0.051
h
0.0
0.15
0
0.006
D
—
—
0.95 BSC
—
—
0.038 BSC
L
0.35
0.5
0.014
0.02
E
0.35
0.55
0.014
0.022
e
0.09
0.2
0.004
0.008
Φ
0°
10°
0°
10°
[0176] A QT102 chip provided in an SOT23-6 package type may have a pin arrangement as schematically indicated in FIG. 20 .
4.7 Moisture Sensitivity Level (MSL)
[0177] A chip implementing the above-described QT102 chip functionality may be rated as follows:
[0000]
Peak Body
MSL Rating
Temperature
Specifications
MSL1
260° C.
1PC/JEDEC J-STD-020C
[0178] Thus, in particular embodiments, the QT102 charge-transfer (QT) touch sensor is a self-contained digital IC capable of detecting near-proximity or touch. It may project a touch or proximity field through any dielectric like glass, plastic, stone, ceramic, and even most kinds of wood. It can also turn small metal-bearing objects into intrinsic sensors, making them responsive to proximity or touch. This capability, coupled with its ability to self calibrate, can lead to entirely new product concepts. It may be implemented in human interfaces, like control panels, appliances, toys, lighting controls, or anywhere a mechanical switch or button may be found.
[0179] The QT102 example embodiment may be seen as a single key chip combining a touch-on/touch-off toggle mode with timeout and timing override functions, oriented towards power control of small appliances and battery-operated products, for example. With a small low-cost SOT-23 package, this device can suit almost any product needing a power switch or other toggle-mode controlled function.
[0180] An environmentally friendly (“green”) feature of the QT102 is the timeout function, which can turn off power after a specified time delay ranging from minutes to hours. Furthermore, external “sustain” and “cancel” functions permit designs where the timeout needs to be extended further or terminated early. A user's interaction with a product might trigger a “sustain” input, prolonging the time to shutoff. A safety sensor, such as a tip-over switch on a space heater, can feed the “cancel” function to terminate early.
[0181] The QT102 embodiment(s) features automatic self-calibration, drift compensation, and spread-spectrum burst modulation. The device can in some cases bring inexpensive, easy-to-implement capacitive touch sensing to all kinds of appliances and equipment, from toys to coffee makers. The small, low cost SOT-23 package lets this unique combination of features reside in almost any product.
[0182] The QT102 chip embodying particular embodiments may be summarized as having the following operational features/application parameters:
Number of keys: One touch on/touch off (toggle mode), plus hardware programmable auto switch-off/switch-off delay and external cancel Technology: Spread-spectrum charge-transfer (direct mode) Example key outline sizes: 6 mm×6 mm or larger (generally panel thickness dependent); widely different sizes and shapes possible Example electrode design: Solid or ring electrode shapes PCB Layers required: One Example electrode materials: Etched copper, silver, carbon, Indium Tin Oxide (ITO), Orgacon® Example electrode substrates: PCB, FPCB, plastic films, glass Example panel materials: Plastic, glass, composites, painted surfaces (including relatively low particle density metallic paints) Example panel thickness: Up to 50 mm glass, 20 mm plastic (generally electrode size dependent) Key sensitivity: Settable via external capacitor Interface: Digital output, active high or active low (hardware configurable) Moisture tolerance: Good Power: 2V˜5.5V; drawing, for example, 23 μA at 2V Example package: SOT23-6 (3×3 mm) RoHS compliant Signal processing: Self-calibration, auto drift compensation, noise filtering Example Applications Power switch replacement in countertop appliances, irons, battery powered toys, heaters, lighting controls, automotive interior lighting, commercial and industrial equipment such as soldering stations and cooking equipment
[0199] In particular embodiments, the above-described sensors may be used in apparatus or devices with one touch key. In particular embodiments the sensing element of the sensor may include more than one key, for example two, three, or more keys.
[0200] Herein, “or” is inclusive and not exclusive, unless expressly indicated otherwise or indicated otherwise by context. Therefore, herein, “A or B” means “A, B, or both,” unless expressly indicated otherwise or indicated otherwise by context. Moreover, “and” is both joint and several, unless expressly indicated otherwise or indicated otherwise by context. Therefore, herein, “A and B” means “A and B, jointly or severally,” unless expressly indicated otherwise or indicated otherwise by context.
[0201] This disclosure encompasses all changes, substitutions, variations, alterations, and modifications to the example embodiments herein that a person having ordinary skill in the art would comprehend. Similarly, where appropriate, the appended claims encompass all changes, substitutions, variations, alterations, and modifications to the example embodiments herein that a person having ordinary skill in the art would comprehend. Moreover, reference in the appended claims to an apparatus or system or a component of an apparatus or system being adapted to, arranged to, capable of, configured to, enabled to, operable to, or operative to perform a particular function encompasses that apparatus, system, component, whether or not it or that particular function is activated, turned on, or unlocked, as long as that apparatus, system, or component is so adapted, arranged, capable, configured, enabled, operable, or operative. | In one embodiment, a method includes monitoring detection by a sensing element of a key touch on a touch screen; determining an amount of time that has elapsed since the sensing element last detected a change of capacitance indicative of a key touch on the touch screen; and, if the amount of time that has elapsed exceeds a predetermined time duration, then initiating a particular function of an apparatus. | 7 |
RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. patent application Ser. No. 09/511,421, filed Feb. 22, 2000, and incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention is broadly concerned with methods of forming antireflective coating (ARC) layers on silicon and dielectric materials as well as the resulting integrated circuit precursor structures. More particularly, the inventive methods comprise providing a quantity of a highly strained antireflective compound and vaporizing that compound. The resulting vapor is then pyrolized to form stable diradicals which are subsequently polymerized on the surface of a substrate. A photoresist layer is applied to the formed ARC layer, and the remaining microphotolithographic process steps carried out.
[0004] 2. Description of the Prior Art
[0005] Integrated circuit manufacturers are constantly seeking to maximize silicon wafer size and minimize device feature dimensions in order to improve yield, reduce unit case, and increase on-chip computing power. Device feature sizes on silicon chips are now submicron in size with the advent of advanced deep ultraviolet (DUV) microlithographic processes. However, reducing the substrate reflectivity to less than 1% during photoresist exposure is critical for maintaining dimension control of these submicron features. Therefore, light absorbing organic polymers are formed into antireflective coating (ARC) compositions which are applied beneath photoresist layer in order to reduce the reflectivity normally encountered from the semiconductor substrates during the photoresist DUV exposure. These organic ARCs are typically applied to the semiconductor substrates by a process called spincoating. While spincoated ARC layers offer excellent reflectivity control, their performance is limited by their nonuniformity, defectivity and conformability constrictions, and other inefficiencies inherent within the spincoating process. As the industry approaches adoption of eight-inch or even twelve-inch semiconductor substrates, the inherent inefficiencies of the spincoating process will become increasingly magnified.
[0006] Another problem with the current ARC application processes is inadequate coating uniformity across the wafer. The formed layers are typically lacking in uniformity in that the thickness of the layer at the edges thereof is greater than the thickness at the center of the substrate.
[0007] Spincoated ARC layers also tend to planarize or unevenly coat surface topography rather than form highly conformal layers (i.e., layers which evenly coat each aspect of the substrate and the features). For example, if an ARC with a nominal layer thickness of 1000 Å is spincoated over raised features having feature heights of 0.25 microns, the layer may prove to be only 350 Å thick on top of the features, while being as thick as 1800 Å in the troughs located between the raised features.
[0008] When planarization occurs with these ultra microscopic feature sizes, the ARC layer is too thin on the top of the features to provide the desired reflection control at the features. At the same time, the layer is too thick in the troughs to permit efficient layer removal during subsequent plasma etch. That is, in the process of clearing the ARC deposit from the troughs by plasma etch, the sidewalls of the resist features become eroded, producing microscopically-sized, but significant, changes in the feature shape and/or dimensions. Furthermore the resist thickness and edge acuity maybe lost, which can lead to inconsistent images or feature patterns as the resist pattern is transferred into the substrate during subsequent etching procedures.
[0009] Other problems can occur as well due to the fact that spincoating of these ultra thin ARC layers takes place at very high speeds in a dynamic environment. Accordingly, pinholes, voids, striations, bubbles, localized poor adhesion, center-to-edge thickness variations, and other defects occur as a consequence of attendant rapid or non-uniform solvent evaporation, dynamic surface tension, and liquid-wavefront interaction with surface topography. The defects stemming therefrom become unacceptable with increased wafer size (e.g., 8″-12″) and when patterning super submicron (0.25 μm or smaller) features.
[0010] There is a need for an improved process of depositing ARC on various substrates which overcomes the drawbacks inherent in spincoating.
SUMMARY OF THE INVENTION
[0011] The present invention overcomes these problems by broadly providing improved methods of applying antireflective coatings to silicon and dielectric materials or other substrates (e.g., Al, W, WSi, GaAs, SiGe, Ta, TaN, and other reflective surfaces) utilized in circuit manufacturing processes.
[0012] In more detail, the inventive methods comprise depositing an antireflective compound in a layer on the substrate surface by chemical vapor deposition (CVD) processes. A layer of photoresist is then preferably applied to the antireflective layer to form a precursor structure which then be subjected to the remaining steps of the circuit manufacturing process (i.e., applying a mask to the photoresist layer, exposing the photoresist layer to radiation at the desired wavelength, developing and etching the photoresist layer).
[0013] In one embodiment the antireflective compound comprises respective light attenuating compounds comprising two cyclic moieties joined via a linkage group bonded to a first location (either directly to a member of the cyclic ring, or to a functional group bonded to the cyclic ring) on one of the cyclic moieties and further bonded to a first location on the other of the cyclic moieties. Preferably, the two cyclic moieties are joined by more than one such linkage group, and even more preferably the two selected moieties are joined by two such linkage groups, with each additional linkage group being bonded to second, third, etc. locations on the respective cyclic moieties.
[0014] The light attenuating compounds should be highly strained so that they can be cleaved into stable diradicals upon exposure to energy (e.g., heat, UV light). Thus, the strain energy of the light attenuating compounds should be at least about 10 kcal/mol, preferably at least about 20 kcal/mol, and more preferably from about 30-50 kcal/mol.
[0015] It is preferred that at least one of the cyclic moieties be aromatic or heterocyclic, with preferred aromatic moieties being those selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, and pyrene. Preferred heterocyclic moieties include those selected from the group consisting of pyridine, pyridazine, pyrimidine, pyrazine, thiazole, isothiazole, oxazole, isooxazole, thiophene, furan, and pyrrole.
[0016] Formula I schematically depicts the preferred light attenuating compound structure.
[0017] wherein:
[0018] R represents a linkage group and each R is preferably individually selected from the group consisting of alkyl groups (preferably at least C 2 , and more preferably from about C 2 -C 4 ); and
[0019] each X is individually selected from the group consisting of the hydrogen, the halogens, substituted and unsubstituted phenyl groups, substituted and unsubstituted alkyl groups (preferably C 1 -C 8 ), nitro groups, substituted and unsubstituted amino groups, acetamido groups, substituted and unsubstituted cyclic and heterocyclic groups, and COR 1 , where R 1 is selected from the group consisting of hydrogen, substituted and unsubstituted phenyl groups, substituted and unsubstituted alkyl groups (preferably C 1 -C 8 ), cinnamoyl, naphthoyl, acryloyl, methacryloyl, furoyl, and thiophenecarbonyl groups.
[0020] The most preferred R is an ethyl, propyl, or butyl group. The most preferred X is selected from the group consisting of phenyl, methyl phenyl, methoxy phenyl, nitroxy phenyl, cinnamoyl, naphthoyl, naphthoyl, acryloyl, methacryloyl, furoyl, and thiophenecarbonyl groups.
[0021] In one embodiment, the light attenuating compound is formed by reacting at least two cyclic compounds with a halogenating agent (e.g., a brominating or chlorinating agent) in the presence of a catalyst (such as benzoyl peroxide or cetyltrimethylammoniumbromide) and a solvent (such as carbon tetrachloride) so as to halogenate the cyclic compounds. The halogenated cyclic compounds are then reacted with a “bridging” compound (such as sodium iodide) so as to yield an antireflective compound comprising two cyclic moieties joined via a linkage group bonded both to a first location on one of the cyclic moieties and to a first location on the other of the cyclic moieties. In another embodiment, an alkyl-donating compound (e.g., paraformaldehyde) capable of reacting with the cyclic compounds so as to add a C 1 or higher alkyl group to each of said cyclic compounds is also present during the reaction.
[0022] In another embodiment, the light attenuating compound is 1,4-dixylylene. In yet another embodiment, the antireflective compound comprises 1,4-dixylylene having two to four halogen atoms (e.g., chlorine) bonded thereto, or xylenes having at least one functional group bonded thereto, wherein the functional group is readily cleaved during the CVD process. Formula II schematically depicts the monomer of this embodiment.
[0023] where each X is individually selected from the group consisting of:
[0024] where each R 2 is individually selected from the group consisting of hydrogen and alkyl groups (preferably C 1 -C 4 ) and the “*” designates the atom which is bonded to the CH 2 group which, in turn, is bonded to the benzene ring as depicted in Formula II.
[0025] The chemical vapor deposition process to which the antireflective compound is subjected comprises subjecting the compound to sufficient temperatures and pressures so as to cause the solid compound to sublime to form a vapor. This is preferably accomplished by heating the compound to a temperature of from about 35-250° C., and more preferably from about 60-150° C., at a base pressure of from about 2-50 mTorr, and more preferably from about 5-25 mTorr, over the course of the entire process. Even more preferably, this heating is accomplished by running a temperature gradient wherein the temperature is raised about 10° C. about every 5 minutes followed by a dwell time at the particular temperature for about another 5 minutes. When the temperature is close to the melting point of the cyclic moiety (e.g., within about 2° C.), the temperature is raised about 5° C. during the course of about 5 minutes after which the temperature is maintained for about 4-6 minutes.
[0026] The resulting vapor is then subjected to a process whereby the light attenuating compounds in the vapor are cleaved. Preferably, this cleavage is effected by pyrolizing the light attenuating compound by heating it to a temperature of from about 580-1000° C., and more preferably from about 900-960° C. The light attenuating compounds should be cleaved at the bond between two carbon atoms on each linkage group so as to yield stable diradicals.
[0027] Finally, the cleaved compounds or diradicals are caused to polymerize on the surface of the substrate. This is preferably accomplished by introducing the cleaved compounds into an ambient-temperature, deposition chamber in the presence of the desired substrate where the cleaved compounds are simultaneously adsorbed and polymerized on the substrate surface. This step is preferably accomplished at a temperature of from about 20-25° C., with the spin speed of the rotating shelf on which the substrate is situated preferably being revolved from about 2-10 rpm, and more preferably from about 2-5 rpm.
[0028] The equipment utilized to carry out the foregoing CVD process can be any conventional CVD equipment so long as the above-described temperatures can be attained by the equipment. The primary modification required for conventional CVD equipment is that the deposition chamber must be modified to accommodate the particular size of the substrate (e.g., an 8-inch silicon wafer), and it must include a mechanism for rotating the substrate (such as a rotating shelf) at a speed of about 2 rpm.
[0029] The resulting precursor structures have antireflective coating layers which are surprisingly defect-free. Thus, there are less than 0.1 defects/cm 2 of antireflective layer (i.e., less than about 30 defects per 8-inch wafer), and preferably less than 0.05 defects/cm 2 (i.e., less than about 15 defects per 8-inch wafer), when observed under an optical microscope. Furthermore, these essentially defect-free films can be achieved on 6-12 inch substrates having super submicron features (less than about 0.25 μm in height). As used herein, the term “defects” is intended to include pinholes, dewetting problems where the film doesn't coat the surface, and so-called “comets” in the coating where a foreign particle contacts the substrate surface causing the coating to flow around the particle.
[0030] The antireflective layers prepared according to the invention can be formulated to have a thickness of from about 300-5000 Å, and can also be tailored to absorb light at the wavelength of interest, including light at a wavelength of from about 150-500 nm (e.g., 365 nm or i-line wavelengths, 435 nm or g-line wavelengths, 248 nm deep ultraviolet wavelengths, and 193 nm wavelengths), and preferably from about 190-300 nm. Thus, the antireflective layers will absorb at least about 90%, and preferably at least about 95%, of light at wavelengths of from about 150-500 nm. Furthermore, the antireflective layers have a k value (the imaginary component of the complex index of refraction) of at least about 0.1, preferably at least about 0.35, and more preferably at least about 0.4 at the wavelength of interest.
[0031] The deposited antireflective layer is also substantially insoluble in solvents utilized in the photoresist which is subsequently applied to the antireflective layer. That is, the thickness of the layer will change by less than about 10%, and preferably less than about 5% after contact with the photoresist solvent. As used herein, the percent change is defined as:
100·{fraction (|(thickness prior to solvent contact)−(thickness after solvent contact)|/(thickness prior to solvent contact))}
[0032] The antireflective layers deposited on substrate surfaces according to the invention are also highly conformal, even on topographic surfaces (as used herein, surfaces having raised features of 1000 Å or greater and/or having contact or via holes formed therein and having hole depths of from about 1000-15,000 Å). Thus, the deposited layers have a percent conformality of at least about 85%, preferably at least about 95%, and more preferably about 100%, wherein the percent conformality is defined as:
100·{fraction (|(thickness of the film at location A)−(thickness of the film at location B)|/(thickness of the film at location A),)}
[0033] wherein: “A” is the centerpoint of the top surface of a target feature when the target feature is a raised feature, or the centerpoint of the bottom surface of the target feature when the target feature is a contact or via hole; and “B” is the halfway point between the edge of the target feature and the edge of the feature nearest the target feature. When used with the definition of percent conformality, “feature” and “target feature” is intended to refer to raised features as well as contact or via holes. As also used in this definition, the “edge” of the target feature is intended to refer to the base of the sidewall forming the target feature when the target feature is a raised feature, or the upper edge of a contact or via hole when the target feature is a recessed feature.
[0034] Finally, in addition to the aforementioned antireflective layer properties, the instant invention has a further distinct advantage over prior art spin-coating methods which utilize large quantities of solvents. That is, the instant methods avoid spin-coating solvents which often require special handling. Thus, solvent waste is minimized and so are the negative effects that solvent waste can have on the environment. Furthermore, overall waste is minimized with the inventive process wherein substantially all of the reactants are consumed in the process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] [0035]FIG. 1 is a graph depicting the ultraviolet-visible (UV-Vis) spectrum of a [2.2](1,4)-naphthalenophane film deposited on a quartz slide;
[0036] [0036]FIG. 2 is a graph showing the reflectance curve of [2.2](1,4)-naphthalenophane on various substrates;
[0037] [0037]FIG. 3 is a scanning electron microscope (SEM) photograph illustrating the film conformality of an 850 Å thick film of [2.2](1,4)-naphthalenophane on 2000 Å topography;
[0038] [0038]FIG. 4 is an SEM photograph of the resist profile cross-section of a [2.2](1,4)-naphthalenophane-based organic antireflective coating of 930 Å thick film using a commercially available photoresist;
[0039] [0039]FIG. 5 is a graph depicting the UV-Vis spectrum of a [2.2](9,10)-anthracenophane film deposited on a quartz slide;
[0040] [0040]FIG. 6 is a graph showing the reflectance curve of [2.2](9,10)-anthracenophane on various substrates;
[0041] [0041]FIG. 7 is an SEM photograph illustrating the film conformality of a 360 Å thick film of [2.2](9,10)-anthracenophane on a 2000 Å topography; and
[0042] [0042]FIG. 8 is an SEM photograph showing the resist profile cross-section of a [2.2](9,10)-anthracenophane-based organic antireflective coating of a 900 Å thick film using a commercially available photoresist.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLES
[0043] The following examples set forth preferred methods in accordance with the invention. It is to be understood, however, that these examples are provided by way of illustration and nothing therein should be taken as a limitation upon the overall scope of the invention.
Example 1
Synthesis of [2.2](1,4)-Naphthalenophane
[0044] A mixture of 1,4-dimethylnaphthalene (12.5 g, 0.08 mol), N-bromosuccinimide (30.6 g, 0.17 mol—a brominating agent), and benzoyl peroxide (0.4 g—a catalyst) in carbon tetrachloride (70 ml) was stirred and refluxed for 1 hour. The reaction mixture was cooled to room temperature, and the precipitate was filtered and washed with carbon tetrachloride. A suspension was formed by stirring this solid with water (500 ml) for 45 min. followed by filtering, washing with water, and drying. Recrystallization from ethyl acetate furnished pure 1,4-bis(bromomethyl)naphthalene in 86% yield and with a melting point of 188° C.
[0045] Next, 1,4-bis(bromomethyl)naphthalene was extracted (Soxhlet) into a refluxing solution of sodium iodide (15 g) in acetone (250 ml) for 24 hrs. The solvent was evaporated on a rotary evaporator until the overall reaction mixture volume was around 50 ml, and then the mixture was poured into 150 ml of water. Sodium thiosulfate was added until the color changed to white followed by filtering and drying. Recrystallization from dichloromethane furnished pure [2.2](1,4)-naphthalenophane in 61% yield and having a melting point of 296-300° C. (see Structure A). 1 H-NMR (CDCl 3 ); δ 2.99-3.02 (m, 4H, CH 2 ), 3.72-3.74 (m, 4H, CH 2 ), 7.39-7.42 (m, 6H aromatic), 7.71-7.74 (m, 6H, aromatic) ppm. The elemental analysis calculated for C 24 H 20 : C—93.50 and H—6.49; found: C—93.24 and H—6.48.
Example 2
Synthesis of 4-Substituted-[2.2](1,4)-Naphthalenophane
[0046] A mixture of anhydrous, finely powdered aluminum chloride (0.004 mol) was stirred in dichloromethane (100 ml), followed by slow addition of the corresponding aryl orheteroaryl acid chloride (0.0037 mol) over a period of 30 min. Next, [2.2](1,4)-naphthalenophane (0.003 mol) was slowly added. The reaction mixture was stirred and refluxed for 5-9 hrs. The mixture was cooled to room temperature and poured over a mixture of ice water and 20 ml of concentrated hydrochloric acid. The mixture was poured into a separatory funnel. The organic layer was washed with dilute sodium hydroxide solution, then washed with water, and finally dried over anhydrous magnesium sulfate. Finally, the organic layer was evaporated on a rotary evaporator to isolate pure 4-substituted-[2.2](1,4)-naphthalenophane (see Structure B) in a 63-89% yield. The respective structures of the compounds were confirmed by IR, NMR, and elemental analyses.
[0047] wherein, R is C 6 H 5 , 4—Me—C 6 H 4 , 4—MeO—C 6 H 4 , 4—NO 2 —C 6 H 4 , cinnamoyl, 1-naphthoyl, 2-naphthoyl, acryloyl, methacryloyl, 2-furoyl, or 2-thiophenecarbonyl.
Example 3
Synthesis of [2.2](2,6)-Naphthalenophane
[0048] A mixture of 2,6-dimethylnaphthalene (12.5 g, 0.08 mol), N-bromosuccinimide (30.6 g, 0.17 mol), and benzoyl peroxide (0.4 g) in carbon tetrachloride (70 ml) was stirred and refluxed for 1 hour. The reaction mixture was cooled to room temperature and the precipitate was filtered and then washed with carbon tetrachloride. A suspension was formed by stirring this solid with water (500 ml) for 45 min. followed by filtering, washing with water, and drying. Recrystallization from ethyl acetate furnished pure 2,6-bis(bromomethyl)naphthalene.
[0049] Next, 2,6-bis(bromomethyl)naphthalene was extracted (Soxhlet) into a refluxing solution of sodium iodide (15 g) in acetone (250 ml) for 24 hrs. The solvent was evaporated on a rotary evaporator until the overall reaction mixture volume was around 50 ml, and then the mixture was poured into 150 ml of water. Sodium thiosulfate was added until the color changed to white, followed by filtering and drying. Recrystallization from dichloromethane furnished pure [2.2](2,6)-naphthalenophane (see Structure C) in a 78% yield and with a melting point of 150-152° C. 1 H-NMR (CDCl 3 ); δ 4.61-4.65 (m, 8H, CH 2 ), 7.46-7.49 (m, 6H, aromatic), 7.72-7.78 (m, 6H aromatic), ppm. The elemental analysis calculated for C 24 H 20 : C—93.50 and H—6.49; found: C—93.11 and H—6.41.
Example 4
Synthesis of [2.2](9,10)-Anthracenophane
[0050] A mixture of anthracene (0.1 mol), paraformaldehyde (0.1 mol), cetyltrimethylammoniumbromide (0.4 g), and glacial acetic acid (25 ml) was stirred at room temperature. Next, 60 ml of aqueous HBr (containing 47% HBr gas) was slowly added dropwise to the reaction mixture over a period of 1 hour. The reaction mixture was stirred and heated to 80° C. for 5 hrs., cooled, filtered, washed with water, and then dried. Recrystallization from toluene furnished pure 9,10-bis(bromomethyl)anthracene in a 93% yield and with a melting point of 201° C.
[0051] Next, 9,10-bis(bromomethyl)naphthalene was extracted (Soxhlet) into a refluxing solution of sodium iodide (15 g) in acetone (250 ml) for 24 hrs. The solvent was evaporated on a rotary evaporator to isolate the crude product. Recrystallization from chloroform furnished pure [2.2](9,10)-anthracenophane (see Structure D) in a 97% yield and having a melting point of 275° C. 1 H-NMR (CDCl 3 ); δ 2.94 (s, 8H, CH 2 ), 6.90-6.92 (q, 8H, aromatic), 7.12-7.26 (q, 8H, aromatic) ppm. The elemental analysis calculated for C 32 H 24 : C,94.11; H, 5.88; found: C, 94.79; H, 5.43.
Example 5
Synthesis of 4-Substituted-[2.2](9,10)-Anthracenophane
[0052] A mixture of anhydrous, finely powdered aluminum chloride (0.004 mol) was stirred in dichloromethane (100 ml), followed by slow addition of the corresponding aryl or heteroaryl acid chloride (0.0037 mol) over a period of 30 min. Next, [2.2](9,10)-anthracenophane (0.003 mol) was slowly added. The reaction mixture was stirred and refluxed for 5-9 hrs. The mixture was then cooled to room temperature and poured over ice-water and concentrated hydrochloric acid (20 ml). The mixture was poured into a separatory funnel, and the organic layer was washed with dilute sodium hydroxide solution, then washed with water, and finally dried over anhydrous magnesium sulfate. The organic layer was evaporated on a rotary evaporator to isolate pure 4-substituted-[2.2](9,10)-anthracenophane (see Structure E) in a 59-84% yield. The respective structures of the compounds were confirmed by IR, NMR, and elemental analyses.
[0053] wherein R is C 6 H 5 , 4—Me—C 6 H 4 , 4—MeO—C 6 H 4 , 4—NO 2 —C 6 H 4 , cinnamoyl, 1-naphthoyl, 2-naphthoyl, acryloyl, methacryloyl, 2-furoyl, 2-thiophenecarbonyl.
Example 6
Characteristic Properties
[0054] Part 1
[0055] Two major families of compounds were studied as potential chromophores for antireflective coating layers. Those families were [2.2](1,4)-naphthalenophanes and [2.2](9,10)-anthracenophanes. The antireflective coating layers prepared according to Example 1, using [2.2](1,4)-naphthalenophane were CVD polymerized on six- or eight-inch flat silicon wafers, topography wafers, quartz slides, aluminum substrates, tantalum (Ta) substrates, and tantalum nitride (TaN) substrates.
[0056] The film thickness of each sample was optically measured by ellipsometry at 25 points on a planar silicon wafer to estimate the mean thickness. The films generated uniform coats, without pinholes, voids, or particles and having a preferred thickness of 1000 Å. The films exhibited thickness uniformities of greater than 98% on the various substrates. The film thickness uniformity data is set forth in Table 1.
TABLE 1 Film Thickness Uniformity Mean Thickness Standard Thickness Sample Number (Å) Deviation (Å) Uniformity (%) 63-154-1A 828 8.17 1.00 63-154-1B 828 8.17 1.00 63-154-1C 828 5.56 1.00
[0057] The deposited antireflective layer was also substantially insoluble in typical photoresist solvents. The solvents evaluated included ethyl lactate and propylene glycol monomethyl ether acetate (PGMEA). No thickness loss was observed with either ethyl lactate and PGMEA. The stripping data is set forth in Table 2.
TABLE 2 Stripping Test Sample Initial Final Stripping Number Solvent (Å) Thickness (Å) Thickness (Å) Estimate (%) 63-152-1A Ethyl lactate 380 381 0.00
[0058] The ability of the films to remain chemically inert to the photoresist was tested using UV-6 photoresist (manufactured by Shipley Company, Inc.). The photoresist was coated on the antireflective coating layer, exposed, and then developed with LDD26W developer (manufactured by Shipley Company, Inc.). Excellent profiles were obtained using UV-6 photoresist during photolithography.
[0059] [0059]FIG. 1 is a graph showing the UV-Vis spectrum of the deposited film according to Example 1, using [2.2](1,4)-naphthalenophane on quartz slide. The λ max was at 233 nm demonstrating that the [2.2](1,4)-naphthalenophane-based antireflective film is useful for deep UV (248 nm) applications. The optical density was 6.46/μm at 248 nm.
[0060] The optical constants were measured by VASE analysis. The average real portion of the refractive index (n) and the imaginary index (k) were determined. The values of real and imaginary refractive index were n=2.29 and k=0.29 at 248 nm. The optical density calculated from the optical constants was 6.46/μm at 248 nm. FIG. 2 is a graph showing the reflectance curve of this film. The first minimum thickness was 775 Å, and the second minimum thickness was 1300 Å.
[0061] Film conformality was also tested by depositing [2.2](1,4)-naphthalenophane prepared according to Example 1 onto 2000 Å topography wafers. An examination of the SEM photograph indicated that the film was nearly 98% conformal to the substrates over a topography of 2000 Å in height. FIG. 3 is an SEM photograph showing the film conformality of an 850 Å thick film of [2.2](1,4)-naphthalenophane on a 2000 Å topography.
[0062] A coating of [2.2](1,4)-naphthalenophane was vapor deposited on a silicon wafer to form a film having a thickness of 930 Å, followed by patterning of a UV-6 photoresist over the BARC and developing with LDD26W. The wafers were then cross-sectioned, and the resist features were examined with a SEM. FIG. 4 is an SEM photograph showing an excellent resist profile cross-section of the [2.2](1,4)-naphthalenophane-based organic antireflective coating of a 930 Å thick film using UV-6 photoresist. Resist profiles as small as 100 nm dense lines and 90 nm isolated lines were achieved.
[0063] Part 2
[0064] Antireflective coating layers were prepared according to the procedure described in Example 4 using [2.2](9,10)-anthracenophane. These layers were CVD polymerized on six- or eight-inch flat silicon wafers, topography wafers, quartz slides, aluminum substrates, tantalum (Ta) substrates, and tantalum nitride (TaN) substrates.
[0065] The film thickness was optically measured by ellipsometry at 25 points on a planar silicon wafer to estimate the mean thickness. The films resulted in a uniform coat, without pinholes, voids, or particles and having a preferred thickness of 1000 Å. The films exhibited a thickness uniformity of greater than 94% on various substrates. The film thickness uniformity data is set forth in Table 3.
TABLE 3 Film Thickness Uniformity Mean Thickness Standard Thickness Sample Number (Å) Deviation (Å) Uniformity (%) 63-167-1A 377 3.55 1.00 63-167-1B 377 2.21 1.00
[0066] The deposited antireflective layer was also substantially insoluble in typical photoresist solvents. The solvents evaluated included ethyl lactate and propylene glycol monomethyl ether acetate (PGMEA). The thickness loss observed using ethyl lactate and PGMEA was well within the target of 50 Å (less than 20%). This stripping data is set forth in Table 4.
TABLE 4 Stripping Test Sample Initial Final Stripping Number Solvent (Å) Thickness (Å) Thickness (Å) Estimate (%) 63-152-1A Ethyl lactate 233 191 18.00 63-152-1A PGMEA 191 165 14.00
[0067] The ability of the film to remain chemically inert to the photoresist was also tested using the UV-6 photoresist. The photoresist was coated on the antireflective coating layer, exposed, and then developed with LDD26W developer. Excellent profiles were obtained using the UV-6 photoresist during photolithography. The antireflective coating layers prepared according to the procedure described in Example 4 exhibited excellent adhesion to silicon, aluminum, tantalum, tantalum nitride substrates.
[0068] [0068]FIG. 5 is a graph showing the UV-Vis spectrum of the deposited film according to Example 4 using [2.2](9,10)-anthracenophane on quartz slide. The λ max was at 267 nm, thus demonstrating that the [2.2](9,10)-anthracenophane-based antireflective film is useful material for deep UV (248 nm) applications. The optical density was 5.80/μm at 248 nm.
[0069] The optical constants were measured by VASE analysis. The values of real and imaginary refractive index values were n=1.55 and k=0.36 at 248 μm. The optical density calculated from optical constants was 6.46/μm at 248 nm. FIG. 6 is a graph showing the reflectance curve of this film. The first minimum thickness was 570 Å, and the second minimum thickness was 1300 Å.
[0070] The film conformality was also tested by depositing [2.2](9,10)-anthracenophane (prepared according to the procedure described in Example 4) onto 2000 Å topography wafers. An examination of the SEM photograph indicated that the film was nearly 100% conformal to the substrates over a topography of 2000 Å in height. FIG. 7 is an SEM photograph showing the film conformality of 815 Å thick film of [2.2](9,10)-anthracenophane on a 2000 Å topography.
[0071] The coating of [2.2](9,10)-anthracenophane was vapor deposited on a silicon wafer to form a film having a thickness of 900 Å, followed by patterning of a UV-6 photoresist over the BARC and developing with LDD26W. The wafers were cross-sectioned, and then the resist features were examined with an SEM. FIG. 8 is an SEM photograph showing the excellent resist profile cross-section of the [2.2](9,10)-anthracenophane-based organic antireflective coatings of a 900 Å thick film using UV-6 photoresist. Resist profiles as small as 170 nm dense lines were achieved.
[0072] In conclusion, it will be appreciated that a number of antireflective compounds can be prepared according to the invention and applied to substrates via chemical vapor deposition processes. These compounds include:
[0073] [2.2](1,4)-naphthalenophane and derivatives thereof such as 4-bromo-[2.2](1,4)-naphthalenophane, 4-chloro-[2.2](1,4)-naphthalenophane, 4-fluoro-[2.2](1,4)-naphthalenophane, 4-nitro-[2.2](1,4)-naphthalenophane, 4-amino-[2.2](1,4)-naphthalenophane, 4-acetamido-[2.2](1,4)-naphthalenophane, 4-(1-naphthylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(2-naphthylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(phenylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(4′-methyl-phenylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(4′-methoxy-phenylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(4′-nitro-phenylcarbonyl)-[2.2](1,4)-naphthalenophane, 4 -(cinnamylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(acrylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(methacrylcarbonyl)-[2.2](1,4)-naphthalenophane, 4-(2′-furylcarbonyl)-[2.2](1,4)-naphthalenophane, and 4-(2′-thienylcarbonyl)-[2.2](1,4)-naphthalenophane;
[0074] [2.2](2,6)-naphthalenophane and its monosubstituted derivative; and
[0075] [2.2](9,10)-anthracenophane and derivatives thereof such as 4-bromo-[2.2](9,10)-anthracenophane, 4-chloro-[2.2](9,10)-anthracenophane, 4-fluoro-[2.2](9,10)-anthracenophane, 4-nitro-[2.2](9,10)-anthracenophane, 4-amino-[2.2](9,10)-anthracenophane, 4-acetamido-[2.2](9,10)-anthracenophane, 4-(1-naphthylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(2-naphthylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(phenylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(4′-methylphenylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(4′-methoxyphenylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(4′-nitrophenylcarbonyl)-[2.2](9,10)-anthracenophane , 4-(cinnamylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(acrylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(methacrylcarbonyl)-[2.2](9,10)-anthracenophane, 4-(2′-furylcarbonyl)-[2.2](9,10)-anthracenophane, and 4-(2-thienylcarbonyl)-[2.2](9,10)-anthracenophane). | An improved method for applying organic antireflective coatings to substrate surfaces and the resulting precursor structures are provided. Broadly, the methods comprise chemical vapor depositing (CVD) an antireflective compound on the substrate surface. In one embodiment, the compound is highly strained (e.g., having a strain energy of at least about 10 kcal/mol) and comprises two cyclic moieties joined to one another via a linkage group. The most preferred monomers are [2.2](1,4)-naphthalenophane and [2.2](9,10)-anthracenophane. The CVD processes comprise heating the antireflective compound so as to vaporize it, and then pyrolizing the vaporized compound to form stable diradicals which are subsequently polymerized on a substrate surface in a deposition chamber. The inventive methods are useful for providing highly conformal antireflective coatings on large substrate surfaces having super submicron (0.25 μm or smaller) features. | 8 |
FIELD OF THE INVENTION
The present invention relates to an apparatus, method and system for protecting hips from fracture, and for providing immediate response to hip fracture events.
BACKGROUND INFORMATION
Hip fractures may cause morbidity and mortality in persons, including, for example, elderly persons. With the progressive increase in the number of elderly persons in the United States, a concurrent surge in hip fractures is occurring. Hip fracture in elderly persons may result from a fall on the hip area. For example, Cummings et al. in “A Hypothesis: The Causes of Hip Fractures”, Journal of Gerontology: Medical Sciences, Vol. 44, No. 4 (1989), state that about 80 to 90% of hip fractures in elderly persons are due to falls, and that fewer than 10% occur before the fall. Consequently, hip protecting devices have been advocated to reduce the risk of sustaining a hip fracture.
Hip protective devices should provide both an effective and cost-saving strategy for reducing the risk of hip fractures. To be effective, however, a hip protecting device must be worn. A major issue is patient non-compliance and/or non-adherence with wearing of such hip protecting devices. It is has been found that the non-compliance in community and institutional settings ranges from 37% to 72%.
There may be several reasons why persons do not always wear a hip protecting device when instructed to do so. Reasons for non-compliance may include, for example, discomfort (e.g., too tight and/or a poor fit), and the extra effort and time required to put on and adjust the hip protecting device. It is believed that patient compliance would be substantially increased if hip protecting devices were more comfortable and provided a better fit. Patient compliance may be increased if hip protecting devices are presented in a form that those in need of such devices would be less inclined to resist the wearing of the device, due to, for example, vanity concerns or not wanting to admit the time has come to wear such a device.
There are hip protecting devices, for example, in which the device is worn underneath clothing because the wearer may not consider the protecting device aesthetically pleasing. However, in the past 10 years or so, it is understood that a very large proportion of the wearers need to be able to take the device off, sometimes urgently, such as in a need to visit the toilet, and this cannot be done with the type of the hip protector that is worn in or as underwear. This even applies if the caregiver has to take off the garment.
Wearers of hip protectors may have different capabilities with respect to possible movements of their limbs and agility. Certain existing hip protectors may not accommodate such individual needs and/or capabilities of the wearer, particularly if the wearer cannot move certain body parts in a particular direction, in agile fashion. For example, the wearer may have arthritis or muscular weakness in the hands. It has also been understood that certain existing hip protecting devices are not easily removed or put on by the wearer or the care giver.
The material of certain existing hip protecting devices using pads can stretch and therefore allow for undesired movement of the pads with respect to a particular desired area to be protected (e.g., pads that are included in a sweatpants arrangement). For example, if a person falls off a couch, the friction from contact with the couch may cause the padding of the hip protecting device to slide away from the point to be protected.
U.S. Pat. No. 5,545,128 purports to relate to a garment worn underneath clothing for bone fracture prevention during impact from a fall, in which the undergarment has an horseshoe-shaped pad arrangement for shunting a substantial portion of impact energy from the vulnerable region to the soft tissue region. However, such a design rests on the faulty notion that only falls with an impact at right angles to the greater trochanter cause hip fractures, which is not accurate. There are many other angles at which persons may fall. At some angles, contact will not be made near the greater trochanter. For example, one may fall flat backwards or half sideways on the buttocks. Accordingly, unless the fall occurs directly on the entire horseshoe-shaped pad, the thixotropy (hardening due to impact on the protective fluid/solid) will not occur fast enough, and the device is likely to do more harm than good. Moreover, the pads, which are about one inch thick, increase the perceived width of the wearer and thus may be esthetically unacceptable to the wearer. Moreover, the horseshoe-shaped design and the direct adherence to the skin is considered an impractical solution. Hence, the device discussed in U.S. Pat. No. 5,545,128 is understood to be functionally deficient, uncomfortable, or impractical for certain wearers, such as, for example, older persons.
Furthermore, another pad arrangement, in which the pads are fixed in a tight undergarment with straps around the legs and waist so that the pads can be held precisely over the greater trochanter, is not likely to be usable by an older person with arthritic fingers.
Certain hip protecting devices, which are designed to be worn underneath clothing, may include plastic shields or foam pads that may be held in place at the hips with specially designed underwear. However, such pads may provide only limited protection. For example, such pads do not protect from a rearward fall. In the human pelvis there are two large hip bones, each consisting of three fused bones, the illium, ischium, and pubis. The hip bones form a ring around a central cavity. The fused terminal segments of the spine, known as the sacrum and coccyx, connect the hip bones at the back of the central cavity; a fibrous band connects them at the front. A backward fall may cause injury or fracture of sacrum and/or coccyx. Moreover, with the internal force transmission occurring from bone to bone, falling backwards can not only hurt the sacrum and coccyx but hard impact on them can be passed onto other bones.
SUMMARY OF THE INVENTION
The present invention provides a device for protecting a hip bone or limiting a severity of a hip bone injury. In this regard, the device may include, for example, at least one pad arranged to protect the hip bone, and a wearable garment to hold the at least one pad with respect to the hip bone, in which the garment is configured to be worn over clothing and the pad configured to wrap around an area of the hip bone in a circumferential manner.
According to an exemplary embodiment and/or exemplary method of the present invention, the hip protecting device is configured to be more easily removed as compared to other existing hip protecting devices. This may be particularly important when the wearer encounters an urgent need to remove the device, such as a toilet visit. It is essential for many older people who require incontinence pads, because the device may be used in conjunction with them. In particular, the wrap-around aspect of the hip protecting device of the present invention provides a unique solution to the problem of wearing both a hip protecting device and incontinence pads.
According to an exemplary embodiment and/or exemplary method of the present invention, the hip protecting device is put on by laying the device flat on a bedside, and the wearer sits or slides on to the device, which may then be wrapped around and fastened. If the wearer has the capability, the device may also be donned in a standing position.
According to an exemplary embodiment and/or exemplary method of the present invention, a hip protecting device includes a wrap-around pad on each side so that protection may be provided for a rearward or partially rearward fall, in addition to a sideways fall. In this regard, a hip protecting device according to the present invention may provide protection against injury or fracture to certain hip bones, or other bones in the vicinity of the hip, including, for example, the sacrum and coccyx bones.
According to an exemplary embodiment and/or exemplary method of the present invention, a hip protecting device is easily adapted to the specific protections of a variety of wearers. In particular, the hip protecting device provides a fastening device that can accommodate multiple sized and shaped wearers. Accordingly, the hip protecting device may be provided in a one-size-fits all, or essentially a one-size-fits all, configuration.
According to an exemplary embodiment and/or exemplary method of the present invention, a hip protecting device may be worn over clothing, including, for example, all types of clothing, to provide improved comfort and/or convenience. The hip protecting device of the present invention may also be provided in a one-size fits all mode, which allows the user to personally adjust the device to improve the fit that may be obtained therewith. The hip protecting device may also include a pocket to hold a variety of fall/injury avoidance electronic devices, and help summoning devices, such as, for example, a postural sensor, personal emergency response system, etc.
According to an exemplary embodiment and/or exemplary method of the present invention, the hip protecting device includes at least one pad of about 7/16′ in thickness, which includes a closed cell material, such as, for example, polyvinyl chloride (PVC)-nitrile. The hip protecting device may also include two extended panels, which are configured to be self-fastening to each other so as to provide an one size fits essentially all wearers of the device. In this regard, the two panels may be fastened in various positions so as to accommodate a range of circumference of about 32 to 49 inches. Here, it is noted that to manufacture extremely large sizes, adjustments may also be made in the back of the garment in the area between the pads. The hip protecting device may further include an impact detector configured to signal for help upon detecting a fall or sudden impact.
According to an exemplary embodiment and/or exemplary method of the present invention, the hip-protecting device may be fastened by rotating two panels of the hip-protecting device around of an axis perpendicular to a fastening plane, overlapping the two panels, and pressing the two panels together. Here, the rotation is important because is makes the fastener adaptable to slight variations in an individual's anatomy. Moreover, the facing panels may be brought together at various angles with respect to the fastening plane
According to an exemplary embodiment and/or exemplary method of the present invention, the hip protecting device includes an impact detector to detect a fall. In this regard, the impact detector may include, for example, an accelerometer to detect a deceleration change, and a first processing arrangement to determine if the deceleration change is within a range in which a fracture may occur.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 AA shows an exemplary method to protect a hip bone from fracture.
FIG. 1A shows a front view of an exemplary device for protecting the hip area in a human.
FIG. 1B shows an exemplary fastening device for securing the exemplary device of FIG. 1A to the hip area of the human.
FIG. 1C shows exemplary double seams of the exemplary fastening device of FIG. 1B , at which a length of the fastening device may be removed using scissors to better accommodate a particular sized individual wearer.
FIG. 1D shows a rear view of the exemplary device of FIG. 1A .
FIG. 2 shows an exemplary electronic device that may be provided with the exemplary device of FIG. 1A .
DETAILED DESCRIPTION
FIG. 1 AA shows an exemplary method to protect a hip bone from fracture or to limit a severity of a hip bone injury. In step S 101 , at least one pad is provided to protect the hip bone. For example, two pads may be provided, each pad approximately rectangular in shape with rounded edges and constructed to absorb a shock.
In step S 102 , the at least one pad is configured to wrap around an area of the hip bone. In particular, the at least one pad is configured to wrap around the area of the hip bone in a circumferential manner so as to conform to the particular wearer's shape.
In step S 103 , a one size fits all device is provided, which includes at least one pad to protect the hip bone, and which is configured to be worn over clothing. Here, the one size fits all aspect of the device may accommodate, for example, 95% of adult wearers, which may be important, for example, in terms of the application of the device in health institutions, such as nursing homes, because without such a one size fits all feature the device may be unnecessarily expensive with respect to storage and providing different sizes of the device to persons having differing sizes. Additionally, the configuration of the device so as to be worn over clothing provides certain benefits with respect to convenience and ease of use of the device. For instance, if a wearer decides to sit in once place for a particular time period, the device may be easily unfastened during this time and fastened again before rising.
In step S 102 , a pocket is provided on the device to hold an arrangement to notify a non-wearer of a fall occurrence. Here, the non-wearer may be, for example, a caregiver, who may assist the wearer of the device should he or she need assistance after a fall. The pocket may be configured to accommodate a wide variety of devices so that a customized solution may be provided to each wearer, if required.
In step S 103 , the arrangement to notify a non-wearer is provided so that both the device and the notification arrangement can be provided in one commercially available package so as to reap further economies of scale with respect to mass production of the device. Indeed, having a device that both protects hips from fracture and notifies a caregiver when the wearer falls or experiences a sudden impact to the hip area should be desirable in the context of elderly and/or injury-prone individuals who would otherwise not have access to such features with other existing hip protecting devices.
FIGS. 1A and 1D show a front and rear view of a human from slightly above the waistline to slightly below the buttocks, and a device 100 for protecting the hip area of a human. The protection may include, for example, protection against fracture, contusions, injuries to the skin and tissues lying below, which may occur, for example, from a fall. The device 100 includes a garment piece 106 , an electronic device 101 , a fastening device 103 , at least one pad 105 , and a slot/pocket 105 a to hold the pad 105 .
The garment 106 surrounds the human torso over the hip area to hold the device 100 in a suitable position. The garment 106 may be worn, for example, over clothing. In this regard, the garment 106 may be easily secured and/or removed. The garment 106 may be provided in a “one-size-fits-all” configuration, and may be made of an elastic spandex material, which may include a woven material from section to section as well, or any other suitably appropriate material.
The garment 106 may be provided in a color or pattern that is suitable for wearing over clothing. In particular, the garment 106 may be provided in a dark gray and/or brown color pattern. It is believed that the dark gray and/or brown color may be a desirable color since those who may wear the garment 106 , including elderly persons, may tend to dress in darker shades and thus the dark gray and/or brown color may not contrast so greatly. Moreover, a dark gray and/or brown color may not show dirt or stains or other discolorations as noticeably. Moreover still, a dark gray and/or brown color may improve compliance—that is, the tendency of the wearer to accept the recommendation by a physician and a caregiver, to wear the device. Any color may, however, be used.
The device 100 includes a fastening device 103 , which may be easily manipulated to adjust the device 100 to suit the particular needs of the wearer. In this regard, the device is configured for a wearer in a sitting position to be able to unfasten and refasten the device without rearrangement of the device with respect to the hips. Of course, the device may be unfastened and refastened in other positions as well, including the standing or lying down position.
The fastening device 103 may be provided in the form of two facing velcro panels 103 a and 103 b . In this regard, the overlap of the velcro panels 103 a / 103 b is such that the garment 106 may be opened widely or less widely to accommodate wearers of multiple sizes. Instead of being fastened with both panels in an aligning axial position they may also be fastened in a manner where the longitudinal axis of one pad is at an angle to the longitudinal axis of the other panel, which may provide a more snug fit to accommodate the wearer's unique shape. In this regard, the width of the two panels may be configured to increase an overlapping area of the panels when the panels are fastened in a non-parallel manner.
In one exemplary embodiment, the velcro panels 103 a / 103 b may be configured to accommodate nearly all potential wearers of the device. For example, certain potential wearers of the device may have a circumference at the hip area that is relatively large or, alternatively, relatively small as compared with the general population. Accordingly, providing a device that accommodates a wide variety of circumferences is believed to be desirable. In this regard, it is found that the potential wearers of the device include individuals whose circumference is as small as 32 inches or possibly even less, or as a large as 49 inches. Here, it is noted that the number of individuals whose circumference is less than 32 inches is expected to be quite small. It is also noted that most elderly people tend to lose weight as they age so that it is expected that most elderly wearers tend not to have a circumference that is nearly as large as 49 inches. Indeed, it is believed that most of the potential wearers who are elderly required a device that accommodates a much lesser circumference than 49 inches. Therefore, according to one exemplary embodiment, the velcro panels 103 a / 103 b may be configured to include a section 103 d that is easily removed or detached such that the potential wearer or caretaker may eliminate that portion of the panels that is not required to accommodate his circumference. For example, the velcro panels 103 a / 103 b may include a double seam 103 c to subdivide the velcro panel in such a way that a section 103 d of the velcro panels may be cut off using a pair of scissors, for example. (Note the double seam 103 c allows the end the velcro panels that remains after cutting to have an appearance of being quite reasonably neatly finished). Hence, potential wearers of the device can more easily customize the fit. This is what enables the “one-size-fits-all” feature.
The “one-size-fits-all” configuration may also provide certain benefits with respect to cost, distribution and/or stocking of the device. For example, nursing homes or other similar care facilities may more easily maintain an adequate stock of the devices for expected and unexpected needs of the residents since a supply of only one type of device is needed to accommodate all or nearly all its residents.
The body of the device 100 includes materials that are expandable and non-expandable. The expanding materials in conjunction with the velcro closure serve to adjust the device 100 to the form of the body of the wearer, both for comfort and retension of the protective pads in their operative location. Expanding material is provided particularly between the pads 105 and around the front areas where the pads 105 are held fastened.
The device 100 includes at least one pad 105 , which is constructed of a protective material within certain industry standards. In sports safety, automotive and other safety fields, a measure of protection that has become widely established is “G-max”, which describes the maximum number of multiples of the force of gravity that result from a reversal of momentum caused by an object hitting the protective material. For protection against human bone fracture, a G-max value of 200 or less is believed to be desirable so as to prevent the most fractures and yet not be too thick. In this regard, a 7/16″ thickness of, for example, the AMC material made by Armacell, is a closed cell polyvinyl chloride (PVC)-nitrile material that tests at this range.(Materials that absorb more force of impact are still being developed). In particular, the AMC material performs adequately when subjected to the ASTM F-355 prop Test, in which a steel cylinder is dropped on a sample of the material, which is situated on a steel surface connected to equipment which measures the impact over a period of time.
The at least one pad 105 may be constructed of a closed cell material that does not absorb body fluids such as urine and cleaning water when the pad is sponged or immersed in water.
Accordingly, the at least one pad 105 may provide certain benefits with respect to maintaining its cleanliness.
The at least one pad 105 may be shaped and/or adapted to the human torso in a wrap-around manner so as to protect certain bones of the human pelvis, including, for example, the greater trochanter or the two large hip-related bones, each consisting of three fused bones, the illium and ischium, which partially form a ring around a central cavity. The wrap-around construction additionally protects the fused terminal segments of the pelvis, known as the sacrum and coccyx. Accordingly, the at least one pad 105 may protect the wearer in the event of a backward or partially backward fall, which might otherwise cause injury or fracture of sacrum and coccyx, for example.
The at least one pad 105 may have an additional section that folds underneath the buttocks when the wearer assumes a sitting position. Accordingly, the at least one pad 105 is constructed to provide flexibility and protection at the same time.
The body device 100 includes an electronic device 101 to warn of risky movement and immediately alert the wearer, and also to detect a possible impending fall. In this regard, an alert may also be directed to a caregiver, such as, for example, a nurse at a nursing station, etc. If a person falls and fractures a hip, help cannot arrive too soon. Even if there is no hip fracture, help may nonetheless be needed and/or desired to provide prompt attention and aid to the patient, who may be distressed by the fall and/or may not be able to get up or even press a pendant button, such as has been provided in certain devices for various medial alerts, including those not connected with hip protecting features.
The electronic device 101 may include an inertial component 101 a to detect a change in position. In this regard, the detected change in position may indicate, for example, that the wearer has experienced a fall. The electronic device 101 may also include a transmitter 101 b to transmit a signal to a receiver (e.g., monitoring station, a nursing station, a home care giver, etc.), a receiver 101 c to receive a signal from a transmitter (e.g., a broadcast station, etc.) and a speaker 101 d to provide an audible alarm to the wearer of the device 100 .
The electronic device 101 may also include a haptic component 101 e to provide a vibration sensation to the wearer of the device 100 to indicate, for example, an impending fall or dangerous condition. In this regard, the haptic component 101 e may provide a desired feature for those individuals whose hearing is impaired, or where an audible signal may be disturbing to the wearer or others in the vicinity of the wearer.
The electronic device 101 may be fixedly arranged in the device 100 , or may be inserted or held in a pocket 107 of the garment 106 . In this regard, the electronic device 101 may be easily removed when desired; for example, when the garment 106 is to be washed. The pocket 107 may be located, for example, where it is least exposed to outside impact. For example, the pocket 107 may be located above the hip and slightly anterior with respect to the torso.
The electronic device 101 may also be arranged in a slot 105 a of the pad 105 . In particular, the electronic device 101 may be arranged, for example, in an upper outermost corner of the pad 105 . For this purpose, the garment need not require additional sewing operations. Moreover, the pad 105 may better protect the electronic device 101 .
The electronic device 101 may also include a power source to provide power. Here, the power source may be, for example, a battery.
The electronic device 101 may also include a manual alert mechanism 101 f so the wearer may manually activate an alarm condition to a nursing-station or a telephone line. In this regard, the telephone line may be, for example, a wireless connection, such as, for example, a cellular or mobile phone connection. The manual alert mechanism 101 f may be, for example, in the form of a button, a dial, switch, microphone, or any other suitable form for enabling manual activation by the wearer or any other nearby person. In this regard, the microphone may be used, for example, to provide a voice-activated manual alert.
The manual alert mechanism 101 f may be used to alert the nursing station to a fall, a fear of a fall, or any other condition that may require attention. In this regard, the wearer may alert, for example, that he or she may be experiencing a discomforting and/or life-threatening condition, such as, for example, a heat attack.
The manual alert mechanism 101 f may include an element to deactivate it so that wearers or others may prevent unintended alerts and alerts from patients or wearers that occur with excessive frequency because the wearer is regarded to have not the capacity to properly judge when an activation is required and/or necessary. | A method and device for protecting a hip bone or limiting a severity of a hip bone injury, which includes at least one pad arranged to protect the hip bone, and a wearable garment to hold the at least one pad with respect to the hip bone, the garment configured to be worn over clothing, the pad configured to wrap around an area of the hip bone in a circumferential manner, the garment including two fastening panels, each configured to face and overlap with the other fastening panel, and fastenable together in a rotatable manner around an axis perpendicular to a fastening plane, a length of the two fastening panels configured to provide a one size fits essentially all wearers. | 0 |
This is a continuation of application Ser. No. 08/070,977 filed Jun. 4, 1993 now abandoned, which is a continuation of application Ser. No. 07/447,072, filed on Dec. 7, 1989, now issued into U.S. Pat. No. 5,227,668.
The present invention relates to electrical fault detecting devices, and in particular to such devices for use with a mains alternating current electricity supply.
The illegal tampering with electricity supplies to obtain electricity without cost, or at a reduced cost, is a widespread problem, particularly with respect to domestic electricity supplies. Three main methods of obtainng electricity illegally are used.
Firstly, the live or the live and neutral wires of the supply are bridged. This is done by connecting a pair of wires to the incoming supply wires and then bridging to the consumer fuse board, thereby by-passing current to the meter, causing it to under read. Secondly the live and neutral wires may be exchanged at the input to the meter, and the neutral can be switched to earth. Since the meter is driven normally by an inductive coil connected to the live cable only, this method again causes the meter to under read since the meter driving coil is only slightly energised. Thirdly, a device which supplies a small A.C. voltage directly to the meter can be connected, but in the opposite phase, thus causing the meter to wind backwards.
It is an object of the present invention to provide an apparatus for detecting when electricity is being abstracted illegally from the supply.
Thus, in accordance with the present invention, apparatus for detecting, incorrect usage of an alternating current electricity supply comprises first signal generating means, disposed at a first location in the supply, for generating a first signal which varies with a property of the electricity supply in the vicinity of the first location, second signal generating means, disposed at a second location in the supply, for generating a second signal which varies with a property of the electricity supply in the vicinity of the second location and monitoring and actuator means adapted to monitor the two signals and to produce a third, actuating signal when the first and second signals are inconsistent with a correct electricity supply.
Preferably, the first and/or second signal generating means comprise a coiled portion of conductive leads forming part of the supply, and the signals comprise magnetic flux signals generated by the passage of current. The monitoring device may comprise a detecting coil adapted and positioned to detect flux produced by one or both of the first and second coiled portions. Preferably, the currents carried by the conductive leads are in antiphase.
In a correctly-used electricity supply, the live and neutral currents are exactly in antiphase, and thus the detecting coil described above would only detect a negligible amount of flux, since the flux induced by the live and neutral coils would cancel each other out. However, when one of the above three methods of illegal abstraction of electricity is used, the amplitude of the live and neutral signals is no longer equal, producing a net field which is detected by the detecting coil. The signal thus induced in the detecting coil is used to actuate the indicating means to indicate that illegal abstraction of electricity has occurred.
In a preferred embodiment, the first and second inductive coils and the detecting coil are mounted on a common core, preferably a ferrite core. Advantageously, signals from the detecting coil are amplified by an amplifier before being used to actuate the indicating means.
Preferably, the apparatus further comprises a field effect transistor, the actuating signal being fed to the gate of the field effect transistor. Advantageously, the gate of the field effect transistor is actuated by means of a capacitor charged by the signal from the detecting coil. The effect of this is that temporary, accidental aberations in the electricity supply do not actuate the indicating means.
The indicating means may, for example, comprise a light source, which is preferably extinguished in response to an actuating signal from the detecting coil, or may comprise an electrically-actuable counter or meter, for example an electronic counter.
In another embodiment, the first and/or second signal generating means may comprise detecting coils located around a respective conductive lead of the electricity supply, the first and second signals comprising the electrical signals induced in the coils by the passage of current through the leads.
Instead of balancing the flux produced by coils of the actual input cable, electrical signals produced as a result of the passage of electrical current are balanced against each other continuously. Any tampering with the supply between the first and second coils causes an imbalance in the electrical signals produced thereby, and this imbalance is used to actuate the indicator means. The apparatas is of particular benefit when one of the coils is situated at the entry point of the electrical cable into a dwelling and the other coil is situated within the meter housing. This is particularly advantageous since most illegal abstraction of electricity involves forming a bridge between the input and output cables of the electricity meter. The apparatus in accordance with the second aspect of the present invention would detect any such interference.
SUMMARY OF THE INVENTION
Preferably, the apparatus comprises two comparators for comparing the signals, the output of each comparator being connected to the indicator means.
Preferably, the output of each comparator is connected to the indicator means via a blocking diode.
The indicator means may, for example, comprise an electrically actuable counter or meter, for example, an electronic counter, which thus indicates the length of time for which illegal abstraction of electricity has occurred.
Preferably, the signals produced in each of the first and second coils is rectified to form D.C. voltages which are then compared.
As well as so-called electrical interference, which involves making electrical connections, for example to bypass the meter, a further method of illegally abstracting electricity is to interfere with the meter itself, or so-called mechanical interference. A conventional electricity meter comprises a rotatably mounted disc which is driven by an induction coil through which the live supply passes. Thus, as electric current passes through the meter, the meter disc rotates, and the rotations of the meter disc are counted by a conventional mechanical, or more recently electronic, counter, thus giving a reading of the total amount of electricity supplied. However, if rotation of the meter disc is stopped or slowed down, the meter will read much less than it ought to, and consequently the consumer will pay less.
Thus, in another embodiment, the second signal generating means comprises means for producing a signal which varies with the rotation of an electricity meter disc whose rotational speed varies with the electricity supply under normal operating conditions.
In this way, under correct operating conditions, the apparatus effectively checks whether the rotational speed of the meter disc is correct for the amount of electricity passing into the meter, and if this is found to be incorrect the tamper indicating means is actuated by the actuating means.
In a preferred embodiment, the actuating means comprises a capacitor, the signal from the coil acting to charge the capacitor up to an actuating voltage, and the signal from the detecting means acting so as to limit the charge on the capacitor to a level lower than the actuating voltage, thereby rendering the capacitor inactive under correct operating conditions.
In one embodiment, the detecting means comprises a light source and a light sensitive element, either disposed upon opposite sides of the disc which is provided with through apertures, or arranged such that the light sensitive element receives light reflected from reflecting portions situated on the disc. In either case, a pulsed signal is produced by the light sensitive element, which is used to limit the maximum voltage on the said capacitor.
The tamper indicating means may, for example, comprise an electrically-actuable counter, such as an electronic counter, and/or may comprise a light emitting diode which is arranged to light or extinguish, as desired, under conditions of illegal abstraction of electricity.
The present invention further provides apparatus for determining incorrect usage of an alternating current electricity supply, comprising first and second coils formed by coiling live and neutral supply cables respectively to form first and second magnetic flux signals which vary with the electricity supply in the live and neutral cables respectively, a magnetic flux detecting coil magnetically coupled to the first and second inductive coils to detect flux produced thereby, and indicating means responsive to an actuating signal induced in the detecting coil and actuable when the flux detected by the detecting coil induces an actuating voltage therein.
The present invention further provides apparatus for determining incorrect usage of alternating current electricity supply, comprising a first coil disposed in relation to a mains input cable to have induced therein a first electrical signal upon passage of current through the cable, a second coil disposed in relation to a mains input cable to have induced therein a second electrical signal upon passage of current through the cable, comparator means for comparing the said first and second electrical signals and indicator means actuable by an imbalance of said first and second signals.
The present invention further provides apparatus for determining incorrect usage of an alternating current electricity supply, comprising a coil adapted to have induced therein a signal which varies with the passage of current through the cable, detecting means for producing a signal resulting from the rotation of a disc forming part of an electricity meter, and which signal varies with the rotational speed of the disc, tamper indicating means and actuating means for actuating the tamper indicating means, the signals from the coil and from the detecting means acting in opposite senses on the actuating means to render it inoperative under correct operating conditions, but to operate it and actuate the tamper indicating means when the signal received from the detecting means is insufficient to counteract the effect on the actuating means of the signal from the coil.
BRIEF DESCRIPTION OF THE DRAWINGS
By way of example only, specific embodiments of the present invention will now be described, with reference to the accompanying drawings, in which:
FIG. 1 is a view of an embodiment of device in accordance with the present invention, fitted to a domestic mains electricity supply unit;
FIG. 2 is a circuit diagram showing the construction of the device of FIG. 1;
FIG. 3 is a portion of a circuit diagram showing a modification to the circuit of FIG. 2;
FIG. 4 is a circuit diagram showing the construction of a further embodiment of device in accordance with the present invention;
FIGS. 5 and 6 are plan views of alternative meter discs for use with the embodiments of FIGS. 4, 7, 8 and 9;
FIG. 7 is a schematic view of a third embodiment of device in accordance with the present invention;
FIG. 8 is a circuit diagram of the embodiment of FIG. 4; and
FIG. 9 is a portion of a circuit diagram showing a modification of the circuit of FIG. 8.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring firstly to FIG. 1, a domestic mains electricity supply unit comprises an incoming mains cable 10 which feeds current via a main fuse 12 (usually rated at 60 A or 100 A) into an electicity meter 14. Output leads 16, 18 feed the metered current into the property, via a fuse box or contact breaker unit 20. The device 22 in accordance with the first embodiment of the present invention is situated in use between the main fuse 12 and the meter 14. Externally, it comprises a cuboidal box 24 having two apertures to allow two light emitting diodes LED1, LED2 within the device to be visible therethrough. Also, there is an aperture in the face of the box adjacent to the main fuse 12 and another aperture in the face of the box adjacent the meter 14, to allow electric cable to pass into and out of the box. The height h of the box is such that it is a snug fit between the main fuse 12 and the meter 14, abutting each of them when in use, thereby preventing access to the electricity supply between the main fuse 12 and the meter 14. The box 24 itself is encased in a tough transparent resin, e.g. epoxy resin, the apertures for the LEDs thereby being closed off, but the LEDs are still visible through the resin.
The two LEDs are provided to enable the state of the system to be evaluated very simply, as will be explained. LED 1 is intended to be permanently lit, in order to indicate that the device 22 is operating correctly. LED2 is normally lit, but is extinguished if some fault is present in the system, for example, if the supply has been tampered with or if a genuine fault is present in the supply.
The construction of the device is shown in FIG. 2. The incoming mains lead 10 comprises an insulated live cable L and a neutral cable N, each of 16 mm 2 cross-section. Each of these cables is formed into a respective coil 26, 28 of a single turn each about an electromagnetic core 30 in the form of an elongate, cylindrical soft iron bar. A third, detecting, coil 32 comprising 200 turns of insulated 18 SWG wire is also provided on the core 30.
The primary coil P of an iron-core transformer 34 is connected via a 1 A quick blow fuse F 1 across the live and neutral cables L, N of the incoming mains supply. The current induced in the circuit connected to the secondary coil S of the transformer 34 is substantially half-wave rectified by means of two Type BY 126 diodes D 1 , D 2 , and the current is fed to a 1.4 V light emitting diode LED 1 in series with a 2 kΩ, 0.5 W resistor 36 connected across the secondary coil S. The LED 1 is thus always lit whenever current flows in the incoming mains supply. Capacitors C 1 and C 2 , each being 470 μF, 40 V capacitors, are also connected across the secondary coil, with a view to smoothing out the rectified signal.
A second light emitting diode LED 2 is also connected across the secondary coil S, the LED 2 being connected in series with a 2 kΩ, 0.5 W resistor 38 and 100 mA quick blow fuse F 2 . Thus, LED2 is also always lit, whenever current flows in the incoming mains supply and whenever fuse F 2 has not blown.
A depletion mode metal oxide semiconductor field effect transistor FET 1 is also connected across the secondary coil S of the transformer 34 between the fuse F 2 and the second LED2. This is normally held open by the gate G to which no voltage, or an insufficient voltage to close it, is applied, as will be explained.
A Fairchild Type 741 operational amplifier OA 1 is provided, and one output X from the detecting coil 32 is connected to the non-inverting input thereof. The other output X of the detecting coil 32 is connected to the secondary coil S along a return lead 40. The actual position of the connection of the return lead 40 on the secondary coil is determined during the construction of the circuit, and is that position where the output of the amplifier is zero for zero input. The power for the operational amplifier is provided by connections to the V+ and V- connections which are connected across the secondary coil S.
The output of the amplifier OA 1 is connected via a 0.01 μF 100 V capacitor C 3 , a type IN 1418 diode 44 and a 1MΩ 0.5 W resistor 46 to a 47 μF 25 V Tantilum capacitor C 4 , the other side of the capacitor being connected to the diode D 2 . The gate G of the FET 1 is connected between the resistor 46 and the capacitor 48.
The output of the amplifier OA is also connected by means of the return lead 40 to the secondary coil S via a 100 kΩ 0.5 W resistor 50 and a 1 kΩ 0.5 W resistor 52. A feedback loop 54 leads from between the two resistors 50 and 52 into the inverting input of the operational amplifier OA 1 . The return lead 40 is also connected to the output of the amplifier in between the capacitor 42 and the diode 44 via a type IN 1418 diode 54.
In normal operation, the magnetic fluxes produced by the coils 26, 28 cancel each other out, since the currents in the two coils are in antiphase. Thus, the current induced in coil 32, which is wound on the same core as the coils 26, 28 will be zero or negligible. Thus, the input into the operational amplifier OA 1 will be zero or negligible. The result of this is that the output of the operational amplifier will also be zero or negligible, but will certainly not supply a sufficiently large voltage to capacitor C 4 to render the field effect transistor FET 1 conductive. Thus, both light emitting diodes LED 1 , LED 2 will be lit during normal operation.
If it is attempted to obtain electricity illegally by interferring with the supply leads L, N then the flux created in the core 30 by the leads 26, 28 connected to the live and neutral leads L, N respectively will not be exactly equal in amplitude, and hence a net flux will be created. The net flux will be detected by the detecting coil 32, in which a current will be induced. The induced current is amplified by the operational amplifier OA 1 whose output charges the capacitor C 4 controlling the gate of the field effect transistor FET. When the capacitor C 4 has reached a certain voltage (approximately 4 V) the gate of the field effect transistor is actuated, thus causing the field effect transistor to assume a conducting state. A large current thus flows through the transistor, causing the fuse F2 to blow, and thus extinguishing the second light emitting diode LED 2 . Thus, when tampering with the supply has occurred, only the first light emitting diode LED 1 is lit, the other light emitting diode LED 2 being extinguished and thus indicating that tampering with the supply has occurred.
The values of the capacitor C 4 and resistor 46 are chosen such that the capacitor does not charge sufficiently to actuate the gate G of the field effect transistor FET until several seconds (approximately 7 or 8 seconds) have elapsed. This ensures that very short-lived changes in the electricity supply (e.g. a spike in the waveform or an accidental grounding by a consumer) do not cause the FET to conduct and do not extinguish the second light-emitting diode LED 2 . Only when a relatively long-lived or permanent interference has occurred will the second light emitting diode LED 2 extinguish. The values of the capacitor C 4 and resistor 46 can be varied to vary the time required for the actuation of the gate. This period can be anything up to, for example, one minute.
This apparatus also has the advantage that if there is a relatively large, accidental leakage of current to earth, causing an imbalance in the current in the live and neutral leads, then this will cause the second light emitting diode LED 2 to extinguish, since the imbalance will be detected by the detection coil 32. Thus, a consumer or an electricity supply official will be aware that a potentially dangerous fault exists and can take action to rectify it.
A modification of this embodiment is illustrated in FIG. 3. The modified apparatus is almost identical to that shown in FIGS. 1 and 2, and only the modified part is shown, with identical components being identified with the same reference numerals as those shown in FIG. 2. The modification involves connecting the actuating coil 55 of a conventional solenoid trip with 56 in the line leading from the FET1 to the secondary coil S of the transformer, the trip unit 56 being connected to the live input lead L of the electricity supply.
The operation of the FIG. 3 embodiment is almost identical to that of the first embodiment. Under correct operating conditions, the detecting coil 32 will detect a zero or negligible magnetic flux, and thus the output signal from the amplifier OA1 will be zero or negligible, as will the charge on the capacitor C 4 . Thus, the FET1 will normally be open and will therefore be non-conductive. The LED 2 will thus still be lit, but no current will flow through the actuating coil of the solenoid trip 56.
Under incorrect operating conditions, the capacitor C 4 will become charged, and eventually will cause the FET1 to become conductive as in the first embodiment. The current which flows through the FET will also flow through the coil 55 and thus will actuate the solenoid trip unit 56, cutting off the electricity supply. Also, the large current through the FET1 will cause the fuse F 2 to blow, thus extinguishing the LED2 and giving a visual indication that the supply is incorrect, even if no electricity is being drawn from the supply.
A further embodiment of the present invention is illustrated in FIG. 4. This embodiment has the advantage that not only does it detect electrical interference, but it also detects so-called mechanical interference, i.e. interference with the meter itself to stop or reduce its rotation so that it gives a lower reading than it should. The two types of tampering with the supply will hereinafter be referred to as "electrical interference" and "mechanical interference" respectively.
As in the first embodiment, the supply is provided along live and neutral leads L, N. Dealing firstly with electrical interference, each input lead L, N is coiled once around a first common ferrite core L 2 so that the magnetic flux produced by the two coils cancel each other out under normal operating conditions. As in the first embodiment, a detection coil 60 formed by 150 turns of insulated SWG 18 wire is formed about the ferrite core L 2 . The output from the detection coil 60 is fed into a type 741 operational amplifier OA 2 , the inverting input of the operational amplifier also being connected to earth. The input to the non-inverting input is fed through a 100 kΩ resistor 62 and a feedback loop extends between the output and the non-inverting input of the amplifier via a 1MΩ resistor 64. A 0.01 μF capacitor 66 is connected across the output of the detecting loop 60 to remove any effects resulting from radio interference which might otherwise produce spurious signals. The operational amplifier is powered by a 10 V input obtained by connecting leads 68, 70 across the input leads L, N and to a transformer T and a bridge rectifier 72. Two 470 μF 25 V capacitors 74, 76 extend between the negative output and ground and the positive output and ground to smooth the rectified signal.
The output of the amplifier OA 2 is connected via a 1.5 μF tantalum capacitor 78, a IN 1418 diode 80 and a 100KΩ resistor 82 to the gate G of an N-channel power metal oxide semiconductor field effect transistor (MOSFET) FET 2 . A further IN 1418 diode 84 and a 47 μF tantalum capacitor 86 are connected to ground from in between the capacitor 78 and diode 80 and from in between the resistor 82 and gate G respectively.
In normal use, the flux produced in the core L 2 by the coils of the live L and neutral N cables amounts to zero, since the two coils produce equal and opposite fluxes. Thus, the detection coil 60 has no current induced in it, and consequently the output of the amplifier OA 2 is zero and the gate G of the field effect transistor FET 2 is not actuated. Even if the fluxes produced by the coiled live L and neutral N wires do not exactly cancel each other out, resulting in a small induced current in the detection coil 60, the output of the amplfier OA 2 will not be sufficiently large to actuate the gate G.
If, however, electricity is illegally abstracted, the fluxes produced by the live L and neutral N coils in the core L 2 are no longer in balance, and a current is induced in the detection coil 60. The induced current is amplified and charges the capacitor 86. When a sufficient voltage (4 V) is on the capacitor, the gate G of the field effect transistor FET is actuated, thus rendering the transistor conductive. (As before, the values of the resistor 82 and the capacitor 86 are chosen such that the capacitor takes about 9 or 10 seconds to reach the voltage required for actuating the gate G, thus preventing actuation of the gate G as a result of short-lived spikes or other temporary abberations in the supply). As before, the values of the capacitor 86 and resistor 82 may be varied to vary the period required to actuation of the gate.
When the field effect transistor FET 2 is rendered conductive, a relay 88, which is normally open, closes and supplies a 20 V signal to a solenoid trip unit 90 located in the live supply lead L, thus cutting off the normal supply to the meter M. At the same time, the relay connects the +10 V supply via a BY126 diode 92 and a 9 V 1 W Zener diode 94 to an electronic counter 96 which is already connected to a -10 V supply. The 20 V supply thus activates the counter 96 which is conventional and which advances one unit every 36 seconds. The counter 96 thus gives an indication of for how long illegal abstraction of electricity has-occurred. Since the live lead L is now effectively disconnected from the meter M, there will always be a net flux induced in the coil L 2 by the neutral wire coil, and consequently the detection coil 60 will continuously supply a signal to the amplifier OA 2 , thus continuously actuating the gate G. Thus, once the solenoid trip unit 90 is actuated, any use of electricity is noted on the electronic counter 96.
Turning now to mechanical interference, in order to detect this it is necessary to have means for detecting rotation of the meter disc and means for detecting the input of electricity. The input means comprises a single turn of the input live lead L around a further ferrite core L 3 . A detecting coil 98 of 100 turns of insulated SWG 18 wire is also wound onto the core L 3 , and is connected to the inputs of a type 741 operational amplifier OA 3 . The inverting input of the amplifier is also connected to earth and a 100 kΩ resistor 100 is located between the detection coil 98 and the non-inverting input. A 1MΩ resistor 102 is provided in a feedback loop to the non-inverting input, to provide a gain of 10 in the amplifier. The power for the amplifier is obtained from the bridge rectifier unit 72.
The output of the amplifier is fed to a D.C. block in the form of a 1.5 μF tantalum capacitor 104 and thence to a bridge rectifier in the form of two IN 1418 diodes 106, 108, diode 106 being connected in series with the capacitor 104 and the other diode 108 being connected to ground. A 5 kΩ resistor 110 is connected in series with the capacitor 104 and leads to the gate G of a metal oxide semiconductor field effect transistor FET 3 . The resistor is also connected to a 22 μF tantalum capacitor 112.
Thus, since only the live input lead L is coiled around the core L 3 , the detection coil continually produces a current which is amplified, rectified and fed to the capacitor 112. In the absence of any other apparatus, the capacitor 112 would quickly reach a voltage at which the gate G of a field effect transistor FET 3 would be actuated, thus rendering the transistor conductive. In this state, a +10 V input is supplied to the electronic counter 96 which is already connected to a -10 V supply and the counter thus advances one unit every 36 seconds, as before. However, the capacitor 112 is not normally allowed to reach the actuating voltage as will now be explained (it would normally take about 9 to 10 seconds so to do, and the values of the resistor 110 and the capacitor are chosen accordingly).
The conventional electricity meter M comprises a rotatably mounted disc 114 which is rotated in the normal way as a result of input current passing through an inductive coil 116 of the live lead L. The disc 114 is provided with a plurality of equally angularly spaced through apertures 117 (see FIG. 5) and an opto-electronic coupling device is provided, comprising a light emitting diode 118 on one side of the disc and a phototransistor 120 on the opposite side of the disc. Under normal circumstances, as the meter disc 114 rotates and the light path between the light emitting diode and the photo transistor is alternately blocked and opened, the phototransistor 120 outputs a pulsed, flip-flop signal, which is connected to a 10 microfarad tantalum capacitor 122. (The 10 volt supply from the bridge rectifier 72 is used to power the LED 118 and is also connected across the phototransistor 120, each one via respective 1.5 kΩ resistor 124, 126).
The capacitor 122 is connected to the base of a BC 171 npn transistor 128. The base B and the collector C are each connected to ground by means of a 100 kΩ resistor 130 and a 5.6 kΩ resistor 132 respectively, the emitter E being connected to a -10 V supply supplied from the bridge rectifier 72. The collector C of the transistor 128 is also connected, via a 100 kΩ resistor 134 to the base B of a second BC 171 npn transistor 136. The collector C of the transistor 136 is connected to one side of the aforementioned 10 microfarad capacitor 112, the other side of the capacitor 112, and the emitter E of the transistor 136, being connected to the -10 volt supply.
The pulsed flip-flop signal fed into the capacitor 122 from the phototransistor 120 momentarily removes the bias voltage from the base of the first transistor 128 when the phototransistor 120 detects light from the light emitting diode 118. The transistor 128 then switches off and its collector voltage rises sharply to 10 volts. Shortly afterwards, when the phototransistor 120 no longer detects the light emitting diode 118, a signal is no longer fed to the capacitor 112, and the capacitor therefore discharges via resistor 130, causing the transistor 128 to switch off, the collector voltage thereby falling to zero. This rising and falling of the collector voltage depends upon the rotational speed of the meter disc 114. The 10 V pulses formed at the collector C of the transistor 128 are fed via the current limiting resistor 134 to the base B of the second transistor 136, and during the pulses the transistor 136 is thereby switched on. As the transistor 136 is switched on, the collector voltage falls to zero, and the capacitor 112 which has previously been slightly charged as a result of the coil 98 about the core L3, discharges, and does not have the time to charge to the value required to actuate the field effect transistor FET 3 . Thus, as the coil 98 attempts to charge up the capacitor 112, the circuitry leading from the meter disc periodically discharges the capacitor 112, assuming the meter disc is rotating. Thus, during normal operation, the capacitor 112 cannot charge to a value sufficient to actuate the field effect transistor FET 3 .
If the disc in the meter is stopped by external interference, the amplifier OA 3 amplifies the signal from the coil 98 and acts to charge the capacitor 112, as described before. However, if the meter is no longer rotating or is rotating too slowly, no pulses, or insufficient pulses will be fed into the transistor 128 and there to the transistor 136, and the capacitor 112 will thereby be able to charge to a value (approximately 4 V) whereupon the field effect transistor FET 3 will switch on and supply voltage to the electronic counter 96, which, as before, advances one unit every 36 seconds. This gives a visual indication as to for how long interference with the supplier has occurred.
Instead of having holes in the meter disc, it would be possible to print alternate black and white portions B,W (FIG. 6) onto the disc and use a reflective type optocoupler with the light from LED 118 being projected towards the black and white portions and the photometer 120 being aligned to receive light reflected from the white portions W. This would also result in a flip-flop signal whose frequency varied with the speed of the disc. Alternatively, the output from FET 3 may used to fire a solenoid trip to cut off the supply to the consumer in the event that it is attempted to abstract electricity illegally.
A further embodiment of the present invention is illustrated in FIGS. 7 and 8 of the accompanying drawings.
As in the second embodiment, the incoming mains supply comprises live and neutral cables L, N. The live cable leads, via a main fuse 142 to a coil 144 which drives a rotatably mounted disc 146 of a meter M. This is shown schematically in FIG. 7. The incoming mains supply cables are tapped and fed to a centre-tapped step-down transformer 148. Opposite sides of the secondary coil S are connected to rectifying diodes 150, 152 to supply a low-voltage electricity supply for the components to be hereinafter described. As seen in FIG. 8, the two diodes 150, 152 are connected to earth via a 470 μF, 25 V D.C. smoothing capacitor 153.
A first detecting coil 154 comprises two hundred turns of insulated SWG 18 wire wound around a ferrite core, located before the main fuse 142. A second detecting coil 156 is located within the meter housing, and is of identical construction to the first detecting coil 154. The electrical construction of this embodiment is shown in FIG. 8. Connected across each detecting coil is a 0.33 μF tantalum capacitor 158 and two 0.25 W resistors 160, 162 of 100KΩ and 220KΩ value respectively. The two coils 154, 156 are also connected in series with each other, and two type IN 4148 rectifying diodes 164, 166 are connected to each of the detecting coils 154, 156 in the leads remote from the common lead 168 connected to each of the coils 154, 156. The full voltage produced across each of the detecting coils 154, 156 is fed in to the non-inverting input of a respective comparator 170, 172 of a type LM 339 integrated circuit 174. The voltage from between each pair of resistors 160, 162 is fed to the inverting input of the comparator associated with the opposite detecting coil. Under normal circumstances, the voltage at each non-inverting input will be greater than that at the associated inverting input, so that the output of the comparator would also be high. However, the output of the comparators 170, 172 is blocked by a respective type IN 4148 blocking diode 174, 176.
If the mains supply is by-passed across either of the coils 154, 156, or if the wires connecting the two coils are cut or short-circuited, then the voltage at the inverting input becomes greater than that at the non-inverting input. Current will be drawn through pin 1 of the comparator unit 174 if the first coil 154 is bridged and will be drawn through the other diode 176 if the second coil 156 is bridged. Thus, an imbalance is produced which causes an LED 180 (connected to the voltage supply via a 0.5 W 1.5KΩ resistor 182) to light up. Moreover, an elapsed time-counter 184 is also actuated, the counter being identical to that of the second embodiment, and advancing one unit every thirty-six seconds elapsed. Thus, if it is attempted to abstract electricity illegally by bridging the supply, the elapsed time-counter 184 is actuated and the LED 180 also lights, indicating to the consumer that the tampering has been detected.
Turning now to the mechanical interference with the meter, as in the second embodiment, a light emitting diode 186 is provided on one side of the meter disc 146 in series with a 0.5 W 1.5KΩ resistor 188, the LED 186 being connected in series with a 0.25 W 27KΩ resistor 190 and a phototransistor 192. As in the second embodiment, the meter disc 146 is provided with a plurality of through apertures, which produces a pulsed signal at the collector C of the phototransistor 192. The meter disc is identical to the meter disc 114 of FIG. 5. Also, the arrangement may be replaced with the reflective arrangement as described above and as illustrated in FIG. 6.
The collector of the phototransistor 192 is connected via a 0.68 μF tantalum capacitor 196 to the inverting input of a further comparator 198 in the integrated circuit 174. A reference voltage, produced by a potential divider formed by a 0.25 W 32KΩ resistor 200 and a 0.25 W 10KΩ resistor 202 connected across the voltage supply is fed into the non-inverting input of the non-inverting input of the comparator 198. A clamping action is thus produced on pin 13 of the comparator unit 174.
A 47 μF tantalum capacitor 204 is connected to the pin 13 (i.e. the output of comparator 198), and also to pin 12 of the comparator unit 174. Under normal circumstances, the capacitor 204 will not charge because its positive plate is connected to pin 13. Thus, every time a positive pulse is produced by the phototransistor 192 as a result of the rotation of the meter disc M, the voltage of the positive plate of the capacitor 204 is clamped to 0.6 V.
A sample of the signal from the detecting coils 154, 156 is fed into the inverting input of a type C741 operational amplifier 206 via a 0.25 W 10KΩ resistor 208. A reference voltage from the secondary coils S of the centre-tapped transformer 148 is fed into the non-inverting input of the amplifier, and also as a power supply to pin 4 of the amplifier. A power lead is also connected to pin 7 of the amplifier.
The output from pin 6 is fed to a 10 μF tantalum capacitor 210, and a 0.25 W 68KΩ resistor 212 bridges the inverting input and the input to the capacitor 210. The capacitor 210 is connected via a IN 4148 diode 214 and a 0.25 W 120KΩ resistor 216 to the positive plate of the aforementioned capacitor 204 and pin 13 of the comparator unit 174. The capacitor 210 is also connected to the power supply from the centre-tapped secondary coil S via a type IN 4148 diode 218.
The sampled signal from either or both of the detecting coils 154, 156 is amplified by the operational amplifier 206 and rectified by the two diodes 214, 218. The capacitor 210 blocks any direct current from the output (pin 6) of the operational amplifier 206 in standby mode.
The resistor 216 and the capacitor 204 form a long RC time constant, typically of 7 to 8 seconds. As stated previously, under normal conditions the capacitor 204 will not charge because its positive plate is clamped to the output voltage of 0.6 volts on pin 13 every time the meter disc produces a pulse. However, when the meter disc is not running, due to interference, then no clamping pulses are produced at pin 13. Capacitor 204 thus charges rapidly, and its voltage is fed to the inverting input of a further comparator 220 in the comparator unit 174. The non-inverting input of the comparator 220 is fed with a reference voltage produced by a 0.25 W 220KΩ resistor 222 and a 0.25 W 120KΩ resistor 224 connected in series across the voltage supply. As the voltage at the positive plate of the capacitor 204 exceeds the reference voltage at the non-inverting input (approximately 4 V), the comparator 220 is actuated. Pin 14 of the comparator unit 174 thus draws current through a further type IN 4148 diode 226, causing the LED 180 to light, and also actuating the electronic clock counter 184 as previously described.
Thus, any interference, be it mechanical or electrical, to the incoming mains supply causes the light emitting diode 180 to light, and also causes the electronic clock counter to advance. Thus, it is possible to estimate the total time elapsed during which illegal abstraction of electricity has occurred, and upon inspection by an official of the electricity supply company, the bill submitted to the consumer may be adjusted accordingly.
A modification of this embodiment is shown in FIG. 9, in which the electronic clock counter 184 is replaced with a conventional solenoid trip unit 228, identical to the solenoid trip unit 56 of FIG. 3. Thus, when electricity is supplied incorrectly, instead of the counter 184 registering the time for which incorrect use occurs, the solenoid trip unit opens and cuts off the entire electricity supply. As illustrated, the solneoid trip unit is connected in the live cable L, but for the sake of clarity in the drawing this is shown schematically rather than illustrating the actual connection in the live cable L.
In all the embodiments illustrated, instead of actuating an electronic clock-counter, the signal which would normally actuate the counter may be used to turn off the incoming electrical supply. For example, that signal may be connected to the base of a solenoid trip triac or other cut-out device which is inserted in the incoming mains supply. Production of a current at the base would thus switch off the triac and switch off the mains supply.
The invention is not restricted to the details of the foregoing embodiments. | An apparatus for detecting illegal tampering with an electricity meter which is adapted to record the amount of electricity supplied to the meter through cables has a first signal generating sensing coil situated externally of, and upstream of, the meter which generates a first signal representative of the current flowing through one of the supply cables and a second signal generating second sensing coil, located within the meter, which generates a second signal representative of the amount of electricity to be recorded by the meter. A Monitoring device monitors the first and second signals and produces a third actuation signal when one of the first and second signals differs from its correct value as a result of tampering. | 8 |
[0001] This application claims the benefit of the filing date of U.S. Provisional application serial No. 60/292,528 filed on May 23, 2001
FIELD OF INVENTION
[0002] The invention relates to the field of financial systems, and more particularly to a stored value instrument whose currency may be selected at time of loading, or at other times.
BACKGROUND OF THE INVENTION
[0003] A stored value card is a known type of instrument that may be used for purchasing goods or services via electronic payment systems, or for transporting cash value from one location to another. Stored value cards may be distinguished from credit cards and debit cards. Unlike credit or debit cards, for example, a stored value card may locally store a dollar amount or other representation of current value on the card itself. Each time a portion of the value is redeemed, the stored value may be decremented by the amount of redemption. In some stored value card implementations, the stored value card may be disposable—designed to be discarded once the stored value has been exhausted. In other applications, the stored value card may be reloadable. Telephone calling cards, bus fare cards, commuter train fare cards, meal cards and gift cards are all examples of applications that may be implemented as stored value platforms.
[0004] In modern society, persons frequently travel from one country to another for business or personal reasons. Moreover, persons often desire to use or send cash equivalents across national borders. Stored value cards that are purchased, or have value loaded, in one country may be physically compatible with card readers in another country. This may be possible, for example, where a single merchant or service provider such as the VISA™ network has implemented a substantially similar system in more than one country. Such a possibility may also be facilitated by industry efforts aimed at standardizing the stored value card-to-reader interfaces. Unfortunately, even where such compatibility exists between the stored value cards and hardware readers, cross-border use may not be possible where the currencies of the two countries are not the same. For example, a card that is loaded with U.S. dollars may not be redeemable for goods, services, or cash where the local currency is in Mexican pesos or other denominations.
[0005] Wire services and other types of electronic funds transfer, money orders, bank drafts, and other mechanisms or instruments are also currently used to transport cash or cash equivalents, from one country to another. Unfortunately for the sender and recipient, these alternatives are generally available only at a relatively high transaction cost, and often only at a relatively small number of fixed locations.
[0006] These and other drawbacks exist.
SUMMARY OF THE INVENTION
[0007] The invention overcoming these and other problems in the art relates to a system and method for a currency selectable stored value instrument, whose currency may be chosen or converted at the time value is loaded, after load but prior to redemption of value, at the time of redemption, or at other times. The stored value instrument may be in the form of a card made from plastic, paper, or other material.
[0008] In order to obtain the card, the user can walk into a bank branch and obtain the card directly from a bank teller. Alternatively, the user can obtain the card from equipment adapted to dispense a stored value card. This equipment could be located within a bank branch, at a retail location, or at any other location. As an additional alternative, the user can access a bank branch by a remote method, such as by email, over the Internet, or by phone to obtain the card. The bank or other issuing institution can issue the card directly upon receiving payment from a user. The payment may be in the form of cash, check, or credit card, or can be taken from an existing customer account.
[0009] The stored value instrument may be a plastic card with a magnetic stripe, compatible with card readers on Automated Teller machines (ATMs), point of sale (POS) terminals and other hardware. The system may further contain processors, databases and other resources which are a component of, or in communication with, ATMs and other terminals configured to effect currency conversions. One or more databases may store current account value, PINs (personal identification numbers) and other information related to an account or other facility. In one illustrative embodiment, U.S. dollars may be converted to Mexican pesos when the stored value instrument is loaded or read with a card reader, an ATM or a card dispensing machine. A user may subsequently redeem that value for legal tender in pesos it a card reader or an ATM located in Mexico, for example, or for goods or services. The account may be loaded with, or converted to, other desired currencies.
[0010] An object of the invention in one regard is to reduce the cost associated with the transfer of cash or cash equivalents across national borders, for instance where a person in the United States wishes to remit cash to family members or others located in Mexico.
[0011] Another object of the invention is to make such transfers more convenient for persons sending, receiving, or redeeming cash or cash equivalents.
[0012] Another object of the invention is to make the transport of cash or cash equivalents safe and secure from theft, fraud, or other abuses or difficulties.
[0013] Another object of the invention is to facilitate the growth of stored value instrument applications in border towns, resort areas, or other locations where travel between nations is widespread.
[0014] Yet another object of the invention is to expand business opportunities for banks or other financial institutions that provide currency exchange services. Other objectives may be realized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The invention will be described with reference to the accompanying drawings, in which like elements are referenced with like numbers.
[0016] [0016]FIG. 1 illustrates a system architecture diagram, according to one embodiment of the invention.
[0017] [0017]FIG. 2 illustrates a process flow diagram from the perspective of a stored value instrument user, according to one embodiment of the invention.
[0018] [0018]FIG. 3 illustrates a process flow diagram from the perspective of a provider of stored value instrument services, illustrating how value may be loaded onto or into a stored value instrument, according to one embodiment of the invention.
[0019] [0019]FIG. 4 illustrates a process flow diagram from the perspective of a provider of stored value instrument services, illustrating how value may be redeemed from a stored value instrument, according to one embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0020] [0020]FIG. 1 illustrates an overall architecture of a system through which the invention may be implemented, wherein a server 100 may be linked to clients 120 via a communications link 130 . In other embodiments, multiple servers or more than two clients may be deployed. The server 100 may be linked with a database 110 over the communication link 130 as shown. In some embodiments, clients 120 may be configured to perform some or all of processing and storage functions which might otherwise be performed in server 100 and database 110 , respectively. Accordingly, in this instance, connection to a server and database would be unnecessary.
[0021] Server 100 may host applications facilitating financial transactions for banks, merchants, or other entities. Such applications may be related to the transfer of funds between accounts or facilities, for the conversion of currency, or to perform other functions. Server 100 may be or include, for instance, a workstation running the Microsoft Windows™ NT™, Windows™ 2000, Unix, Linux, Xenix, IBM AIX ™, Hewlett-Packard UX™. Novell Netware™, Sun Microsystems Solaris™, OS/2™, BeOS™, Mach, Apache, OpenStep™ or other operating system or platform.
[0022] Additionally, server 100 may interface to database 110 . Database 110 may maintain financial account data, currency conversion rates, facilities for the storage of electronic cash, personal identification numbers (PINs) or other information. Database 110 may be, include or interface to, for example, the Oracle™ relational database sold commercially by Oracle Corp. Other databases, such as Informix™, DB2 (Database 2), Sybase or other data storage or query formats, platforms or resources such as OLAP (On Line Analytical Processing), SQL (Standard Query Language), a SAN (Storage Area Network), Microsoft Access™ or others may also be used, incorporated or accessed in the invention.
[0023] Clients 120 may include customer terminals located at a bank or other financial institution, or at other convenient locations, for example in the case where the stored value instrument is to be redeemed for cash. Clients 120 may also be located at the point of sale for goods or services. Furthermore, clients 120 may be fixed or portable terminals owned or used by users of the system and method and located at various locations. Clients 120 may be or include, for instance, an ATM (Automated Teller Machine) or other terminal equipped to dispense funds. Clients 120 may also be or include a PC (Personal Computer) running the Microsoft Windows™95, 98, Millenium™, NT™, or 2000, Windows™CE™, PalmOS™, Unix, Linux, Solaris™, OS/2™, BeOS™, MacOS™ or other operating system or platform. Clients 120 may include a microprocessor such as an Intel x86-based device, a Motorola 68K or PowerPC™ device, a MIPS, Hewlett-Packard Precision™, or Digital Equipment Corp Alpha™ RISC processor, an Intel pentium®, pentium® II, pentium® III or pentium® IV processor, a microcontroller or other general or special purpose device operating under programmed control. Clients 120 may furthermore include electronic memory such as RAM (Random Access Memory) or EPROM (Electronically Programmable Read Only Memory), storage such as a hard drive, CDROM or rewritable CDROM or other magnetic, optical or other media, and other associated components connected over an electronic bus, as will be appreciated by persons skilled in the art. Clients 120 may also be or include a network-enabled appliance such as a WebTV™ unit, radio-enabled Palm™ Pilot or similar unit, a set-top box, a networkable game-playing console such as Sony Playstation™ or Saga Dreamcast™, a browser-equipped cellular telephone, or other TCP/IP client or other device. Clients 120 may also be, include or interface to a wired digital or analog telephone, or a wireless digital or analog telephone such as a cellular telephone or a satellite telephone.
[0024] Different embodiments of the invention may vary as to the nature of stored value instrument 140 . For example, stored value instrument 140 may be a card, which may preferably be fabricated of plastic. Stored value instrument 140 may contain at least one resource for storing data. In one embodiment of the invention, the storage resource may be a magnetic stripe embedded in or attached to stored value instrument 140 . In another embodiment, the storage resource may be electronic or magnetic structures in the interior of a stored value instrument. Stored value instrument 140 may also include a processor, for example in a smart card configuration. Moreover, stored value instrument 140 may be physically or electronically configured in a way that is compatible with an industry standard, such as Proton, Mondex, CEPS (Common Electronic Purse Specifications), or other standard familiar to those skilled in the art.
[0025] In embodiments where stored value instrument 140 is implemented as a card, clients 120 may also be, include, or interface to readers 125 . Readers 125 may be adapted to communicate via link 150 with stored value instrument 140 . Together, readers 125 and link 150 may effectuate the transfer of value or other data from a client 120 to stored value instrument 140 . Reader 125 and link 150 may also read data from the memory of stored value instrument 140 . Some embodiments of the system may include more than two stored value instruments. Link 150 may be consistent with alternative embodiments of communication link 130 described below, with industry standards indicated above, or with other schemes recognized in the art. Alternatively, the stored value instrument 140 is inserted directly into the reader 125 , thereby rendering the link 150 an electronic, magnetic, optical, or other type of reading device.
[0026] In one embodiment or the invention, stored value instrument 140 may not be or include a card, but rather, stored value instrument 140 may include an index to an account or other facility, for example on database 110 , for storing value. In other embodiments, stored value instrument 140 may be or include both a card and an account or other facility, cooperating to execute the functions described herein.
[0027] Data stored on or in stored value instrument 140 may include, for example, an account holder's name, account number, a numerical representation of currently stored value, an indication of the type of currency stored on the instrument, a PIN, or other data, or any subset of data utilized by the method or methods disclosed herein.
[0028] Server 100 , database 110 , and clients 120 may communicate via communications link 130 . Communications link 130 may be, include or interface to any one or more of, for instance, the Internet, an intranet, a PAN (Personal Area Network), a LAN (Local Area Network), a WAN (Wide Area Network) or a MAN (Metropolitan Area Network), a SAN (Storage Area Network), a frame relay connection, an AIN (Advanced Intelligent Network) connection, a SONET (Synchronous Optical Network) connection, a digital T1, T3, E1 or E3 line, DDS (Digital Data Service) connection, DSL (Digital Subscriber Line) connection, an Ethernet connection, an ISDN (Integrated Services Digital Network) line, a dial-up port such as a V.90, V.34 or V.34 bis analog modem connection, a cable modem, an Asynchronous Transfer Mode connection, or an FDDI (Fiber Distributed Data Interface) or CDDI (Copper Distributed Data Interface). connection. Communications link 130 may furthermore be, include or interface to any one or more of a WAP (Wireless Application Protocol) link, a GPRS (General Packet Radio Service) link, a GSMI (Global System for Mobile Communication) link, a CDMA (Code Division multiple Access) or TDMA (Time Division Multiple Access) link such as a cellular phone channel, a GPS (Global Positioning System) link, CDPD (Cellular Digital Packet Data), a RIM (Research in Motion, Limited) duplex paging type device, a Bluetooth, BlueTeeth or WhiteTooth radio link, or an IEEE 802.11-based radio frequency link. Communications link 130 may yet further be, include or interface to any one or more of an RS-232 serial connection, an IEEE-1394 (Firewire) connection, a Fibre Channel connection, an IrDA (infrared) port, a SCSI (Small Computer Systems Interface) connection, a USB (Universal Serial Bus) connection or other wired or wireless, digital or analog interface or connection. Communications link 130 may further be, include, or interface to a PSTN (Public-Switched Telephone Network).
[0029] In embodiments of the invention, the type of communication between system components represented by communication link 130 may be implemented in different ways. Moreover, in embodiments, it may not be necessary that all components communicate directly with each other. For example, it may not be necessary that each of clients 120 communicate with each other.
[0030] Server 100 and clients 120 may utilize network enabled code in order to facilitate functionality in a network-based environment. Network enabled code may be, include or interface to, for example, Hyper text Markup Language (HTML), Dynamic HTML, Extensible Markup Language (XML), Extensible Stylesheet Language (XSL), Document Style Semantics and Specification Language (DSSSL), Cascading Style Sheets (CSS), Synchronized Multimedia Integration Language (SMLL), Wireless Markup Language (WML), Java™, Jini™, C, C++, Perl, UNIX Shell, Visual Basic or Visual Basic Script, Virtual Reality Markup Language (VRML), ColdFusion™, Common Gateway Interface (CGI) or other compilers, assemblers, interpreters or other computer languages or platforms.
[0031] [0031]FIG. 2 is a process flow diagram from the perspective of a stored value instrument user, according to one embodiment of the invention. In step 200 , a user may obtain or establish a stored value instrument 140 . In one embodiment of the invention, stored value instrument 140 may be obtained or established via remote application in step 200 . For example, an application may be sent to a service provider via conventional mail, electronic mail, or a Web-based utility. Alternatively, the application may be submitted in hard copy at a banking or other site. Upon approval, one or more of stored value instrument 140 may be mailed or delivered to the applicant or established on the applicant's behalf. Additionally, in embodiments a PIN may be sent via conventional mail, electronic mail, or other technique, but preferably separate from any mailing or delivery of stored value instrument 140 to that same applicant. Additionally, step 200 may be effectuated by a card dispensing machine, an ATM or other client 120 configured to dispense or establish stored value instrument 140 . In embodiments of the invention, stored value instrument 140 may be obtained or established in person, for example from a teller at a bank, financial institution, or other service provider in step 200 .
[0032] Step 210 , loading value onto or into stored value instrument 140 , may be performed subsequent to the time that stored value instrument 140 is obtained or established, as illustrated in FIG. 2. In another embodiment of the invention, step 210 may be performed coincident with step 200 obtaining or establishing a stored value instrument 140 , in a manner consistent with alternatives previously described. In step 210 , a person seeking to load value onto or into stored value instrument 140 may be required to specify, among other things, load currency in step 212 , load value in step 214 , and a funding source in step 216 . In step 212 , for instance, a user may specify that value is to be loaded in Mexican pesos, British pounds sterling, German marks, francs, euros, or any other currency or denomination. In step 214 , a user may specify the value of the load currency. In one embodiment of the invention, value expressed in step 214 may be in the same currency as the load currency. In another embodiment of the invention, value expressed in step 214 may be in a currency which is other than the load currency. In a case where Mexican pesos are specified as the load currency, and where 520 US dollars are specified as the load value, for instance, stored value instrument 140 may be loaded with 5,000 pesos (if appropriate under the exchange rate at the time of the transaction). In step 216 , the owner of the stored value instrument 140 may specify a funding source such as a checking account, savings account, money market account, brokerage account, credit account, or other account from which funds can be drawn. In another embodiment of the invention, a customer may provide actual cash or a credit card in step 216 to provide value for loading onto or into stored value instrument 140 .
[0033] Like step 200 related to obtaining or establishing a stored value instrument 140 , step 210 related to loading value onto or into a stored value instrument 140 may be performed remotely or in person. Remote operation might be implemented, for example, where client 120 is, includes, or interfaces to a wired telephone in communication with a PSTN, a wireless telephone, a PDA, or other wireless device with Internet access, a personal computer with Web access, or an ATM. Moreover, where the transaction is performed remotely, or where the funding source is held by other than the stored value instrument provider, there may be a delay between the time of the load request in step 210 , and the availability of funds on or in stored value instrument 140 . In another embodiment of step 210 , stored value instrument 140 may be loaded in person, for example by a teller at a bank, financial institution, or other service provider.
[0034] Subsequent processes to effectuate the load of value onto stored value instrument 140 are described in FIG. 3 and the accompanying text.
[0035] [0035]FIG. 2 illustrates that, once value has been loaded onto or into stored value instrument 140 in step 210 , a user of stored value instrument 140 may proceed to at least any of five steps represented by step numbers 210 , 220 , 230 , 240 , and 250 . Of course, in embodiments of the invention, all alternatives may not be available and in others, further alternatives presented.
[0036] A user may load value onto or into stored value instrument 140 , in step 210 , subsequent to an initial load. In one embodiment, additional value may be loaded in the same currency. In other embodiments, it may be possible in step 210 to load value onto or into stored value instrument 140 in a currency different from what has already been loaded onto or into stored value instrument 140 .
[0037] In one embodiment of the invention, a fee may be charged at issuance of the card or other instrument in step 200 . In another embodiment of the invention, a fee may be charged each time that value is loaded onto the stored value instrument in step 210 .
[0038] In step 220 , a user may check the balance of stored value. In one embodiment, inquiries may be made remotely in step 220 , for instance in the same way that balances are checked in conventional bank accounts. In embodiments where stored value instrument 140 is or includes a card, it may be necessary to interface stored value instrument 140 to reader 125 in order to perform step 220 . In the instance where stored value instrument 140 is a card containing a magnetic stripe, and where the magnetic stripe contains at least an indication of stored value, it may not be necessary for client 120 to be connected via link 130 , since, in one embodiment, client 120 and reader 125 may read the balance of stored value directly from stored value instrument 140 . In other embodiments, it may be necessary to the execution of step 220 for client 120 to communicate with server 100 or database 110 over link 130 , where, for example, stored value instrument 140 is not or does not include a card containing an indication of stored value, or where stored value instrument 140 is an account or other facility and does not include a card at all. In other embodiments of the invention, a user of stored value instrument 140 may check the remaining value in step 220 by making an in person inquiry at a bank, financial institution, or other service provider.
[0039] In step 230 , a user of stored value instrument 140 may convert the currency of stored value. An illustration is where Mexican pesos were loaded originally, and a user wishes to convert the currency of the loaded value to British pounds without redeeming value in exchange for goods, services, or cash.
[0040] In step 240 , a user may redeem some or all of the stored value on or in stored value instrument 140 in the loaded currency. For example, where the stored value is loaded in Mexican pesos, a user may redeem stored value for goods or services in Mexico City, where the local currency is also in pesos, or a user may redeem stored value for cash pesos at a Mexican ATM or card reader.
[0041] In step 250 , a user may redeem stored value from stored value instrument 140 in other, than the loaded currency. If, for instance, stored value instrument 140 was loaded with value in Mexican pesos in anticipation of a trip to Mexico that was subsequently cancelled, a user may redeem the stored value in exchange for US dollars at an ATM or a card reader in the U.S. A process for effectuating such a request is illustrated in FIG. 4.
[0042] In the steps set forth above, the user of the stored value instrument 140 may be the same person who purchased the card, if for instance, the purchaser has traveled to another country which uses different currency. Alternatively, the purchaser may transfer the stored value instrument 140 to an acquaintance in another to thereby easily, efficiently, and securely transport funds between countries.
[0043] [0043]FIG. 3 is a process flow diagram from the perspective of a provider of stored value instrument services, illustrating how value may be loaded onto or into stored value instrument 140 , according to one embodiment of the invention. In steps 300 , 305 , and 310 , the service provider or service provider system may receive the load currency selection, load value selection, and funding source information, respectively. Information in these steps may be the result of user input in step 210 , previously described.
[0044] In step 315 , the service provider or service provider system may decide whether the funding currency is the same as the load currency. If it is, then the process may advance to step 325 . If not, for example where the funding source is in US dollars, and Mexican pesos are to be loaded onto stored value instrument 140 , then the process may advance to step 320 .
[0045] In step 320 , a calculation may be made to convert the value of load currency into the funding currency. For example, if a user has requested a loaded value of 5,000 pesos, and the funding source is in US dollars, step 320 may calculate that 5,000 pesos is equivalent to 520 US dollars.
[0046] In step 325 , the service provider or service provider system may resolve the nature of the funding source. If the source of funds is cash, then the cash may be collected in step 330 , and the corresponding value may be loaded onto stored value instrument 140 in step 335 . In the example immediately above, 520 US dollars in legal tender would be collected, and 5,000 Mexican pesos would be loaded onto or into stored value instrument 140 . If, on the other hand, the funding source is a checking, savings, brokerage, credit, or other account, then authorization step 340 may be necessary to verify that the account has sufficient funds before loading value onto or into stored value instrument 140 . Where authorization step 340 is able to verify funds, value may be loaded onto or into stored value instrument 140 in step 335 , and the bank, financial institution, or other service provider may then settle or otherwise reconcile with the source account in step 345 . Where authorization step 340 is unable to verify sufficient funds, the loading process illustrated in FIG. 3 may be terminated in step 350 .
[0047] [0047]FIG. 4 is a process flow diagram from the perspective of a provider of stored value instrument services, illustrating how value may be redeemed from stored value instrument 140 , according to one embodiment of the invention. The process may start, in step 400 , when a bank, other financial institution, or merchant is presented with a stored value instrument 140 as payment for goods, services, or cash in local currency.
[0048] In step 410 , the bank, other financial institution, or merchant may check to see whether the stored value is in local currency. In one embodiment, step 410 may be an online transaction that may require communication with a funding source. In another embodiment of step 410 , a reader 125 may read an indication of currency from the memory of a stored value instrument 140 that is or includes a card.
[0049] If the stored value is in the local currency, then the process may be promoted to step 430 ; if the stored value is not in local currency, then the process may advance to step 420 . In step 420 , the value of goods, services, or cash to be purchased in local currency may be converted to the currency of the stored value. For example, if a user is seeking to exchange stored value in the currency of Mexican pesos for 200 British pounds sterling cash, step 420 may calculate that 200 British pounds sterling is equivalent to 2,800 Mexican pesos.
[0050] In step 430 , the value of goods, services, or cash may be compared to the stored value, in the currency of the stored value. Thus, in the immediately preceding example, it may be decided in step 430 that a stored value instrument 140 loaded with value of 5,000 Mexican pesos would be sufficient funds to purchase 200 British pounds sterling legal tender. Where the stored value funds are sufficient, the requested goods, services, or cash may be distributed in step 450 , and, in step 460 , the transaction may be settled or otherwise reconciled, for example by transferring 2,800 Mexican pesos from stored value instrument 140 to an account of the bank, other financial institution, or merchant. Of course, if stored value instrument 140 does not have sufficient funds to cover the transaction, then the transaction may be declined in step 440 .
[0051] The foregoing description of the invention is illustrative, and variations in configuration and implementation will occur to persons skilled in the art. For instance, stored value instrument 140 may be implemented in various physical and electronic formats other than those specifically described. Moreover, while the invention has been described with respect to loading or conversion from one original currency to one converted currency, in embodiments of the invention multiple currencies may be used or selected as originating currency, the currency which is converted into or both. The scope of the invention is accordingly to be limited only by the following claims. | The invention provides a currency selectable stored value instrument, whose currency may be chosen or converted at the time value is loaded, after load but prior to redemption of value, at the time of redemption, or at other times. One embodiment of the system is configured so that the stored value instrument may be a plastic card with a magnetic stripe, compatible with card readers on Automated Teller Machines (ATMs) or other terminals. In one embodiment, U.S. dollars may be converted to Mexican pesos when the stored value instrument is loaded at an ATM or other location in the United States. A user may subsequently redeem that value for legal tender in pesos at an ATM located in Mexico, for example, or for goods, services, or cash in other currencies. | 6 |
This is a continuation of application Ser. No. 448,693, filed Dec. 11, 1989, which is a continuation-in-part of application Ser. No. 192,225, filed May 10, 1988, now U.S. Pat. No. 4,887,003.
BACKGROUND OF THE DISCLOSURE
The invention is in the field of luminous displays and signs, and more particularly relates to gas plasma display devices.
The production of light by the passage of electricity through gases is a well known phenomenon. Devices utilizing this phenomenon have been widely developed in the form of plasma display devices which display specific numerals, characters, symbols, graphics, and the like. The neon sign is an example of a gas discharge display device, typically including an elongated glass tube filled with neon and a pair of excitation electrodes disposed at opposite ends of the tube. In this example, the rigid tube, or envelope, defines the shape of the illumination pattern. This shape is established at the time of manufacture, and cannot be changed.
Other prior art gas discharge display devices may include a plurality of shaped character electrodes in direct or close contact with an electroluminescent gas within a glass envelope, for example, Nixie tubes. In such devices, selected ones of the shaped electrodes may be energized to obtain a desired character display. Again, the shape of the illumination is predetermined by the shape of the electrode which is established at the time of manufacture of the device.
Still other forms of prior art gas discharge display devices include dielectric-bounded, gas-filled character-shaped channels within an envelope, with a suitable set of energizing electrodes. As in U.S. Pat. No. 3,621,332, a plurality of such channels may be established within a single envelope, with electrodes being arranged for selective activation of one channel at a time. Alternatively, as in U.S. Pat. No. 4,584,501, a single elongated channel may be formed in one plate of a two glass plate sandwich arrangement, with energizing channels in an adjacent plate. All of these arrangements are suitable for displaying indicia, but as with the earlier discussed prior art, the shape of the display, i.e. the channel configuration, is determined at the time of manufacture of the device.
Yet other prior art gas discharge devices include generally similar display configurations, but have an addressable matrix in which selected dot regions may be selectively energized. For example, as shown in U.S. Pat. No. 4,035,690, selected ones of overlapping orthongal sets of electrodes may be energized to generate a desired dot matrix character. In that patent, the electroluminescent gas is confined to the interior of a plurality of dielectric spheres disposed between the sets of electrodes. With the dot addressible matrix, substantial flexibility is provided in that any dot pattern graphics may be displayed, for example using conventional bit-mapped graphics techniques. However, as with the other above mentioned prior art, all possible display patterns, i.e. the electrode overlap regions, are established at the time of manufacture of the device.
Yet another form of prior art gas discharge device is disclosed in U.S. Pat. No. 3,629,654. As shown in that patent, a pair of opposed, spaced apart plates are mutually sealed at their perimeter to establish an electroluminescent gas filled cell. A transparent conductive coating is disposed on one outer surface of the cell. A movable external sheet having predetermined shaped conductive regions is pressed against the other outer surface of the cell and an ionizing signal is applied across the conductive coating and the conductive region of the external sheet to generate a visible discharge in the cell having the shape of the conductive regions of the external sheet. This two-element display thus requires a means for positioning the external sheet relative to the cell in order to establish a image.
It is an object of the present invention to provide an improved plasma display device.
Another object is to provide an improved plasma display device which may be user-programmed for the display of a desired image.
Yet another object is to provide an improved plasma display which may be economically and efficiently configured to display a desired image.
SUMMARY OF THE INVENTION
Briefly, the present invention is an electroluminescent gas filled double walled panel with the provision for electrode surfaces on both sides of the gas space, which will allow for a luminous gas (or plasma) discharge to be generated when suitably energized. The electrode surfaces may be indicia-(or other graphic image-)shaped, thus producing a like shaped pattern of light of sufficient visibility to be useful as a sign, indicator or other expression of visible information.
The pattern of at least one of the electrode surfaces may be provided by a secondary manufacturer, for example, a user, through the means of painting, stencilling, silkscreening, lithography or the like. By so providing the latter electrode surfaces, the inherent difficulties and costs of producing signage (for example, using a heat-bent gas discharge tube of conventional neon tube signs) are overcome, while still producing a luminous gas image. Thus, even a small signage producing enterprise, or home user, may readily utilize the display device of the present invention to display a user desired image.
Additionally, the display panel of the present invention is far more robust, durable and safe than its bent tube neon sign counterpart. In some configurations, the display device has transparent electrodes on both sides of the gas space, making the display device usable as a window or glass door simultaneously with its carrying images or information.
The display panel may also find general usage in the architectural and outdoor illumination field, much as its bent tube neon sign counterpart does currently. Similarly, much as artists and designers use light filled tubes as components of graphic and sculptural statements, the light producing display devices of the invention may be used, with or without patterns to the illuminosity, as an artistic and design medium.
More particularly, in accordance with the invention, a display device includes first and second non-conductive sheet members, each having front and back surfaces, which may be substantially parallel. At least one of the first and second sheet members is transparent.
In a preferred form, the sheet members are rigid and substantially planar, but alternative configurations could be employed, such as similar cylindrical or spherical configurations, or non-rigid configurations. By way of example, the sheet members may be planar sheets of glass. The first sheet member may be substantially transparent and has a coating region on its front surface adapted to receive a first conductive coating (a "pattern electrode") on portions thereof. Typically, this first conductive coating represents the image to be displayed. The first conductive coating may be removable in part to correspond to a modified form of the image. The second sheet member may also be transparent. The first conductive coating may be applied by painting, stencilling, silkscreening, lithography, or the like.
One or more spacer elements mutually position the first and second sheet members so that the back surface of the first sheet member is offset from and opposite the front surface of the second sheet member.
A discharge chamber is established by a gas impervious seal between portions of the back surface of the first sheet member and the front surface of the second sheet member. The discharge chamber defines a closed region in the gap between the back surface of the first sheet member and the front surface of the second sheet member. That closed region underlies at least in part the first conductive coating.
An electroluminescent gas is disposed within the closed region. While other gas mixtures may be used, in the preferred form the electroluminescent gas is a Penning gas mixture comprised substantially of 99% neon, 1% argon, and trace amounts (less than 0.1%) of mercury at a pressure of about 120 torr.
In one form of the invention, a second conductive coating (i.e. a conductive element or "charging electrode") is disposed on a portion of one of the front and back surfaces of the second sheet member underlying at least in part the closed region and a part of the coating region. In other forms, the charging electrode may not underlie the first conductive coating, while still being on one of the front and back surfaces of, or within, or adjacent to the second sheet member. By way of example, the charging electrode may be a wire (e.g. extending at least partially through the closed region, or embedded in the second sheet member), or it may have the form of a conductive portion of the seal which establishes the chamber.
An applied drive voltage may be coupled between the first conductive coating and the charging electrode to energize the device so that a luminous plasma image is established in the portions of the closed region adjacent to the first conductive coating.
In one form of the invention, the spacer includes at least one rigid spacer member disposed within the closed region and extending between the back surface of the first sheet member and the front surface of the second sheet member.
In various embodiments, either or both of the first and second conductive coatings may be substantially translucent, transparent, reflective or opaque. Further, the conductive coating forming the charging electrode may be disposed on the front surface of the second sheet member and at least in part within the closed region. Alternatively, the second conductive coating may be disposed on the back surface of the second sheet member and at least in part overlying the closed region. A third non-conductive sheet member may overlie the second conductive coating opposite the back surface of the second sheet member. A fourth non-conductive sheet member may overlie the first conductive coating. The latter non-conductive sheets may be used to ensure that a user does not contact the electrodes during use. Further, those added sheets provide increased resistance to breakage of the device as a whole. Also, those sheets, when laminated to the first and second sheets, provide increased stiffness of the chamber-defining walls so that relatively thin sheets may be used for the first and second sheet members, using relatively inexpensive (e.g. polycarbonate) material to form the third and/or fourth sheet members.
Various forms of the invention may be adapted to minimize radio frequency interference (RFI) by using shielded configurations, for example where a grounded, conductive element is disposed over the charging electrode. Dual back-to-back displays may be used where an opaque element is disposed between the illuminated regions, so that independent images may be established in those regions for viewing from opposite sides of the display device.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects of this invention, the various features thereof, as well as the invention itself, may be more fully understood from the following description, when read together with the accompanying drawings in which:
FIG. 1 shows in exploded form, a display device according to the present invention;
FIG. 1A shows, in section, the portion of the display device of FIG. 1 including the filling stem;
FIG. 1B show in exploded form an alternative plasma device configuration;
FIG. 2 shows in exploded form, an alternative plasma device configuration;
FIGS. 2A-2D show in perspective view alternative plasma device configurations;
FIG. 3 shows in perspective view, a plasma display device having a plurality of internal spacers;
FIG. 4 shows in section along lines 4--4, the plasma display device of FIG. 3;
FIG. 5 shows a perspective view of an alternative spacer for use with the device of FIGS. 3 and 4;
FIGS. 6-9 show sectional views of alternative spacers for use with the device of FIGS. 3 and 4;
FIG. 10 shows in exploded form, an alternative configuration for a plasma display device of the present invention; and
FIGS. 11 and 12 show in perspective view dual device configurations of plasma display devices embodying the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An exemplary luminous (plasma) panel display device 10 is shown in FIG. 1 in exploded form. The device 10 includes two flat and parallel non-conducting, transparent glass sheet members 12 and 14 having "front" surfaces 12a and 14a, respectively, and "rear" surfaces 14a and 14b, respectively. As shown, sheet members 12 and 14 are substantially planar, but other forms might also be used, such as cylindrical or conical.
An edge seal and spacer element 16 defines an enclosed hermetic volume (or region) 20 having an electroluminescent gas therein. Overlapping conductive coatings 26 and 28 are disposed on the front surface 12a of sheet member 12 and on the rear surface of 14b of sheet member 14, respectively. In alternative embodiments, a conductive element that generally corresponds to coating 28 may be used, where that element may not overlap any portion of a conductive coating corresponding to coating 26 (for example, as described below in conjunction with FIGS. 2A-2D), and where that element may not be a coating (for example, as described below in conjunction with FIGS. 2B-2D).
In the embodiment of FIG. 1, a filling stem 22, extending parallel to the principal plane of volume 20, passes between opposing portions of sheet members 12 and 14 and through spacer member 16 to provide access to chamber volume 20. The outer diameter of filling stem 22 is less than or equal to the distance between the front surface 12a and the back surface 14b. This filling stem 22 permits evacuation and back-filling of the volume 20 following assembly of sheet members 12, 14 and seal/spacer element 16. After back-filling is accomplished, the stem 22 is sealed off. In alternative embodiments, different filling stem configurations may be used. For example, the stem may be placed through a hole drilled through sheet member 12 and fused to the edges of that hole, with the central axis of the stem extending perpendicular to the principal plane of volume 20.
In the preferred embodiment, the sheet members 12 and 14 are non-conductive soda-lime planar glass sheets. The spacer element 16 is also soda-lime glass. The thickness of the sheets is determined to establish (1) a parallel orientation of the two sheets, producing a gas-enclosing space with uniform gap after filling, and (2) total mechanical and thermal stress on the glass sheet members during the assembly and evacuation of the device 10 which does not exceed the properties of the glass, causing breakage. The preferred embodiment has an enclosed volume which is 15 cm by 15 cm, with an intersheet gap in the range 0.25-1.0 mm, as established by spacer 16. The soda-lime glass sheet members 12 and 14 are 3.0 mm thick. With larger surface areas, thicker glass sheets may be used, and for smaller areas, thinner glass may be used. For glass with higher resistance to temperature stressing and higher mechanical strength, such as borosilicate glass, the thickness required for any specific surface area may also be reduced im comparison to the soda-lime glass sheets used in the illustrated embodiment. For example, a 15 cm by 15 cm chamber formed by Pyrex brand borosilicate glass sheets with a 1 mm gap, may have 2.5 mm sheet thickness without overstressing.
The embodiment of FIG. 1 is a three element construction (i.e. sheet members 12, 14 and spacer element 16). Other configurations might also be used, for example, two sheet members in a sandwich configuration where one or both of the adjacent surfaces includes an etched chamber-defining region In the latter configuration, the peripheral spacer is integral with at least one of the sheet members.
In general, spacing and sealing of the chamber 20 of device 10 is provided by a perimeter seal. Various means of hermetically sealing the sheets 12 and 14 and spacer 16 may be used. For example, vacuum epoxy and conventional sealing glasses are suitable In the illustrated embodiment, the 15 cm by 15 cm panel 10 uses a 1 mm thick, 1.5 cm wide spacer element 16 which is disposed about the periphery of chamber 20. The sealing is performed with unloaded, 100% solids, Type 360T vacuum epoxy formulated and sold by Epoxy Technology of Waltham, Mass. The epoxy seal is obtained with a 10 minute oven bake at 120 degrees C. With this seal, outgassing is less than 5×10 -9 cc/sec, giving the panel 10 a life on the order of at least 6 months.
As an alternative to vacuum epoxy, Corning Pyroceram brand sealing glass powder, code 7575, may be used to seal soda-lime sheets 10 and 12 to each other using 0.25 to 1.0 mm thick glass spacers. With this method of sealing, the powdered sealing glass is applied as a slurry with a nitrocellulose binder dissolved in a vehicle such as amyl acetate. The binder and vehicle are burned off at 350 degrees C., and the sealing is accomplished at 450 degrees C. during a 60 minute bake. Slow cooling is used to provide a relatively stress free panel with substantially no seal outgassing. Panel life of glass sealed panels is limited by the outgassing of the glass itself and sputtering and gas cleanup, some of which can be greatly reduced by vacuum baking and the inclusion of sputtering reducing vapors such as Hg into the gas fill.
Regardless of which sealing techniques are used, careful cleaning of all surfaces is performed, using conventional techniques prior to assembly and sealing of the sheets 12 and 14. For example, a sequence of water and solvent washes with detergents, distilled and deionized water rinses, vapor degreasing and warm air drying are perfectly performed prior to sealing of the panel 10.
Many gases, gas mixtures and gas pressures may be used in the volume 20 to achieve various colors and intensities of light output using ac drive voltages in the range of 280 to 1800 volts, from 5 kHz to 10 MHz, using sine and square wave signals and complex waveforms. Generally, the electroluminescent gas in chamber 20 is a mixture of noble gases with additions of small quantities of secondary gases to create Penning mixes. In the preferred embodiment, a very effective gas fill with maximum intensity of about 100 lumens at a drive power level of 1.5 watt/cm 2 is a Penning mixture made with 99% neon, 1% argon, and trace amounts (less than 0.1%) of mercury, filled to a pressure of about 120 torr. Nitrogen could be substantial for the argon in this exemplary mix. The color of the light output from this panel fill is orange-yellow at maximum brightness (using a photo-optically calibrated sensor) but may be varied slightly by changing the frequency and waveform of the driving ac signal, from yellow-orange to orange-red, with a loss in brightness.
To establish the electroluminescent gas in the enclosed volume 20, the panel 10 is first evacuated through the filling stem 22, as coupled to a vacuum pump through a gas filling system with the suitable filters, pressure and vacuum gauges and compressed gas regulators and valves. In the present embodiment, as the filling stem 22 is established prior to assembly of sheet members 12 and 14 and spacer element 16 by first milling matching conical void regions 23a and 23b in opposing portions of the periphery of sheet members 12 and 14, and a hole is cut in the corresponding portion of the spacer element 16. As shown in FIG. 1A, the tubular filling stem 22 is then placed into and sealed to the channel established by the conical void regions and spacer hole at the time of assembly and sealing of sheet members 12 and 22 and spacer element 16. The interior 22a of stem 22 is contiguous to volume 20. Thus, the stem 22 is sealed to the panel 10 with a through channel to the interior space (i.e. volume 20) formed by the combination of the sheet members 12 and 14 and the spacer element 16. In the preferred embodiment, filling stem 22 is attached to the device 10 with low vapor pressure epoxy or with sealing glass.
In alternate embodiments, the stem 22 may extend through one of sheet members 12 and 14 in a direction perpendicular to the sheet member. To establish such a filling stem, a small hole is diamond drilled through the sheet member and the stem end is flared and ground flat on the sealing surface prior to attachment. The stem is then attached using sealing glass or epoxy.
The use of conductive coatings 26, 28 on the glass sheets 12, 14 allows the panel 10 to illuminate when attached to a source of driving voltage. There are several ways to configure the conductive coatings, depending on the desired visual and operational properties of the final panel 10. The coatings may be overlapping, as shown in FIG. 1, or non-overlapping, as described below in conjunction with FIG. 2A. The panel 10, as shown in FIG. 1 has two conductive coatings 26 and 28, one attached to each of the outer surfaces of the transparent sheets 12, 14 with the electroluminescent gas located between the sheets and not in contact with either coating. Three basic types of conductive coatings identified by their optical properties may be used; namely, transparent, reflective, and opaque.
Transparent conductive coatings pass light, and have little or no color, thus making the coating invisible to the eye. Examples of this kind of coating are vacuum evaporated or sputtered metal films, usually gold or aluminum, and indium doped tin oxide films, either sputtered or chemically deposited on the glass sheet. The coating may be applied in a uniform fashion or may be applied as a pattern. Suitable coatings have resistivities on the order 0.1 to 100 ohms/square, are thermally stable at sealing temperatures and are generally scratch and chemically resistant. Etching the coating into patterns for use in defining the illumination zone of the panel may be done by the use of silkscreened, painted or stencilled patterns of resist followed by coating removal with chemical (acid or basic) solutions with local or general application, i.e. bath, spray or wipe, or by mechanical means such as abrasion or scraping.
Reflective conductive coatings reflect light, or reflects some percentage of the light falling on it, and are generally partially transparent and partially reflective. Examples are aluminum, chromium, silver or gold coatings with a reflectivity over 10%. The coatings are applied by sputtering, evaporation, chemical deposition or mechanical means, i.e. embossing, and may be applied as patterns or may be uniform and continuous. The resistivity varies from 0.01 to 10 ohms/square for the coatings, and they are generally capable of withstanding sealing temperatures and processing. The coating may be patterned for use as a sign or indicator a described above.
Opaque conductive coatings do not allow the penetration of light to any significant extent. Such coatings allow the view of the gas discharge from one direction only, and give it a higher contrast background. The coating is generally of a paint or ink type consisting of a vehicle, a binder and a conductive component in suspension such as nickel oxide, nickel metal powder, graphite, or mixes of these materials. It may be applied by spraying, rolling, brushing or any of a host of mechanical or chemical means, either as a uniform and continuous coating or as a pattern.
In the embodiment of FIG. 1, front surface 12a of sheet member 12 is adapted to receive the first (indicia-shaped) conductive coating 26. The back surface 14b of coating 14 supports the second conductive coating 28. Electrical contact to the coatings 26, 28 may be made directly, for example, by wiper arms (not shown) or conductive epoxy (not shown), in a manner permitting an applied drive voltage to be applied across those coatings. The various coatings 26, 28 may each be of the transparent, reflective or opaque type, depending upon the desired luminous image characteristics.
By way of example, in the illustrated configuration, the film coating 28 is a transparent 100 ohms per square deposited indium doped tin oxide film coating 28. As shown in FIG. 1, the front surface 12a has received, by silkscreening, a nickel-graphite colloidal suspension coating 26 (e.g. Type 401 conductive paint, manufactured by Acheson Colloids, Inc.). With this configuration, a 30 kHz, 900 volt sinusoidal signal applied across coatings 26 and 28 provides a yellow-orange-colored "A"-shaped display. The configuration illustrated in FIG. 1 is particularly well adapted to receive coating 26 by conventional processes such as silkscreening and the like, due to the overall planar structure of device 10, where the filling stem 22 lies substantially in the same principal plane as the device 10.
FIG. 1B shows another embodiment 10A in which the sheet member 14 is a wire reinforced safety glass sheet Wire or a wire grid may either be on the glass sheet surface, or embedded into the glass sheet 14 by means of lamination or suspension. Several versions of wire reinforced safety glazing are commercially available. Customary use of such safety glass is for added strength to the glass sheet, as well as the prevention of excessive fragmentation of the sheet in case of breakage. Some available safety glazing products use continuous individual wires which are laid parallel to each other and spaced at even intervals, while others use a woven wire mesh or wire grid. The use of reinforced safety glass sheets in this embodiment provides a strong surface, which reduces the chance of breakage. The high ratio of open area to wire area provides transparency as well as low resistance electrical contact between the wires in the glass and an external source of current.
The safety glass test panel 10A using a wire electrode was constructed using a normal sheet of glass as the back sheet 12 of the panel, to which was applied a conductive pattern (test pattern) 26 and a sheet of wire reinforced safety glass 14 as the front of the panel. The two glass sheets were sealed at their periphery so that there was a 1/4 inch separation between the sheets. The wire grid 28' of the safety glass had been placed interior to the sheet of glass at the time of manufacture by means of suspending it in the glass while it was still molten. The wire grid defined cells approximately 0.5 inch on a side and was made from an iron alloy wire. The grid had been placed approximately one third of the way into a one quarter inch thick plate of window glass. Electrical contact was made to one of the short pieces of wire that normally extend from the cut edge of wire reinforced plate glass (an artifact of the cutting process). The wire-to-wire contact resistance across the grid averaged less than 0.4 ohms per contact in a test of contact resistance made between 20 wires around a one foot square sample. The region 20 between the sheets 12 and 14 was filled with a gas mixture of Neon (99+%) and Xenon (trace), at 160 torr. Other trace gases could be used, such as Nitrogen or Argon, and other pressures may be used, such as 5-250 torr. The equivalent sheet resistance of this embodiment is less than that for an indium doped tin oxide coating on glass. The average per square resistance is comparable to semi-transparent metallic coatings which are approximately 1000 ohms per square. This embodiment provides a low cost, rugged and efficient alternative to continuous conductive coatings.
In operation at low pressures (less than 160 torr), a 4-6 Kvolt peak-to-peak 18-82 kHertz excitation is applied across the pattern electrode and the wire grid. Under these conditions, the safety glass test panel provides an illumination pattern that is similar to a panel with a continuous conductive surface as the charging electrode. At higher pressures, the pattern made by the wires is more discernable in contrast to the test pattern, however, this effect may be reduced by lowering the frequency of the applied voltage.
FIG. 2 shows a display device 10' similar to that in FIG. 1 where corresponding elements are identified with the same reference designations as in FIG. 1. In FIG. 2, a conductive border strip 30 is disposed on the peripheral portion of the front surface 12a of sheet 12. The border strip 30 is connected to coating 26 by portions 30a and 30b. With this configuration permits a simple connection (at contact 44) for coupling to an externally applied signal.
The embodiment of FIG. 2 also includes a third non-conductive sheet 40 overlying the back surface 14b of sheet 14. Sheet 40 provides an electrical insulation layer for the embodiment of FIG. 2 to protect a user from contacting a drive voltage applied to coating 28, relative to the grounded coating 26. A connector 46 is positioned on sheet 40 and feeds through to coating 28 to provide a convenient means for coupling a drive signal to coating 28. Otherwise, the embodiment of FIG. 2 is similar to and operates in the same manner as the embodiment of FIG. 1.
Another form of the invention uses an electrode configuration with a charging electrode (coating 28) in some location other than in direct opposition to the pattern electrode (coating 26). Gas pressure, electric signal and panel geometry may be controlled to provide an even illumination of the region between sheets 12 and 14 adjacent to the pattern electrode as the charging electrode provides a current path for the discharge current in the panel, even though it is not located directly across from the pattern electrode.
Cathode glow phenomena are the primary source of the illumination energy in these cases, and accordingly, the location of the anode is not critical, but rather the anode must have the ability to transfer current to the external circuit (even though these devices generally utilize a high frequency A.C. drive, so that the distinction between anode and cathode becomes minor). These conditions have been found particularly effective at pressures below 400 torr in neon, or neon with the addition of small percentages of a second rare gas or nitrogen, although the design is effective with other gases and combinations of gases.
In such panels, the location, size and dimensions of the charging electrodes may vary considerably. Preferably, the charging electrode is in proximity to the pattern electrode. In various forms, the charging electrode may have a smaller area than the pattern electrode. The charging electrode may be a wire interior to the panel and making direct contact with the gas. It may alternatively be an appendage containing an electrode which communicates with the gas discharge in the panel through a tube or hole, or a perimeter spacer, or it may be a peripheral seal that is conductive between the edges of sheets 12 and 14. FIGS. 2A-2D show exemplary configurations of these types, wherein elements corresponding to elements in the embodiment of FIG. 1 are shown with the same reference designations. In all of these configurations, contact regions 71 and 73 respectively provide electrical contact to the pattern electrode and the charging electrode.
FIG. 2A shows a display panel 10a similar to that in FIG. 1 where the conductive coating (or charging electrode) 28 of sheet 14 is configured and located other than as a uniform conductive sheet opposing any part of the conductive coating 26 of sheet 12. As shown in FIG. 2A, the conductive coating 28 forms a closed geometric pattern near the periphery of the back (or outside) surface 14b. Depending on the particular geometry of the pattern electrode ("ABC" in FIGS. 2A-2D), the charging electrode may or may not underlie the pattern electrode.
FIG. 2B shows a display panel 10b in which the charging electrode is in the form of a wire 28" extending (in direct contact with the gas in region 20) across the region 20.
FIG. 2C shows a display panel 10c in which the charging electrode is in the form of a conductive element positioned within the filling stem 22, or a separate chamber coupled to the closed region.
A display panel 10d is shown in FIG. 2D, where the spacer element 16 comprises a conductive material. That seal 16 establishes the charging electrode so that the region of chamber 20 adjacent to the pattern electrode 28 is illuminated.
All of these configurations may provide an even illumination of the closed region 20 of the chamber and adjacent to the conductive pattern, for example the "ABC"-shaped pattern in FIGS. 2A-2D.
FIGS. 3 and 4 show a similar configuration to the embodiment shown in FIG. 2, but further including eight raised spacers 55-62 projecting from sheet 12 and extending to sheet 14, all within the enclosed volume 20. The spacers permit a relatively large area pair of sheet members to be used while still retaining a relatively high level of structural rigidity. The spacers also permit use of a relatively broad range of gas pressures in chamber 20. The spacers 55-62 as shown are cylindrical in shape. Alternative forms for those spacers are shown in section in FIGS. 5-9. The spacers might be used in any of the above-described embodiments.
In the preferred form of the invention, as shown in FIG. 4, the raised spacers extend only part way between the surfaces 12b and 14a when enclosed volume 20 is filled with electroluminescent gas. With this configuration, during assembly of near-atmospheric pressure (in enclosed volume 20) embodiments, volume 20 can be evacuated and the raised spacers will play a limit on the resultant displacement of the sheet members 12, 14, thereby permitting use of relatively thin sheet members 12, 14. Then, after backfilling with the electroluminescent gas, the raised spacers again extend only partially between surfaces 12b and 14a, permitting a substantially uniform luminescent display across the entire enclosed volume 20. The spacers may also be used in embodiments where the sheet members are flexible.
Another embodiment, device 10f, is shown in FIG. 10. Device 10f is similar to that shown in FIG. 1, except that the coating 28 is disposed on the front surface 14a of sheet 14. With this configuration, there is no need for the third sheet 40 since the drive electrode is fully within the enclosed volume 20. Electrical contact is made to coating 28 by a portion 28a which extends beyond the seal/spacer element 16.
Here, the coating 28 is in direct contact with the gas in chamber 20. While better electrical coupling is achieved between coating 28 and the gas, a lower drive voltage may be used and increased edge definition for the image is attained, compared with embodiments where coating 28 is on the back surface 14b. There is, however, a somewhat reduced lifetime of the device due to sputtering that occurs at the coating 28.
FIG. 11 shows a display device 10g which allows a display panel (for example, a sign) to be read from both sides without a reversal of the letters from either direction. In this embodiment, there are effectively two devices 10h, 10i having an adjoining opaque insulating sheet 80. The two devices 10h, 10i may be mechanically joined within a single frame, or joined with a bonding agent, such as laminating plastic or adhesive. In the case of laminating plastic or adhesive, this may be dyed or otherwise made colored or opaque to increase the viewing contrast of the illuminated pattern.
Each separate device 10h, 10i comprising device 10g may be any of the above embodiments of this invention. For example, the first device 10h may comprise a first sheet 14h having a transparent conductive coating (charging electrode) 28h on the surface 14hb, a spacer 16h, and a second sheet 12h having a conductive coating (pattern electrode) 26 on surface 12ha. The second device 10i comprises corresponding elements (denoted with designation "i") as the device 10h. A third component, insulating sheet 80, may be a non-conductive glass sheet, a laminating non-conductive material, or similar opaque material of sufficient thickness and dielectric strength so as to prevent the pattern intended to be read from one direction from illuminating areas in the panel facing the opposite direction. The insulating sheet is attached on one side to the pattern electrode-bearing (inner) surface 12ha of device 10h and on the other side to pattern electrode-bearing (inner) surface 12ia of device 10i.
In this embodiment, two separate patterns may be applied to the surfaces 12ha and 12ia of sheets 12h and 12i. The presence of opaque insulating sheet 80 would permit the display of two separate patterns, such as letters, to be read from either side.
Since the panels of the invention operate on alternating current at relatively high frequencies, it may be important to provide a means of preventing the escape of an excessive amount of RF radiation. This may be accomplished readily with the configuration of FIG. 11, where the conductive coatings 28h and 28i cover the entirety of surfaces 14hb and 14ib. These coatings may be grounded, so that they establish radio frequency interference (RFI) shielding for device 10g. Another method of minimizing RFI is to use the dual display device 10j shown in FIG. 12. That device is similar to device 10g, in that it has two separate display devices 10k and 101 (each similar to the device of FIG. 1). However, the charging electrodes for these devices 10k and 10l is a single, perimeter-extending conductive spacer element 90. The pattern electrodes 26k and 26l are on surfaces 12ka and 12la respectively and are both grounded to provide RFI shielding. The spacer element 90 is separately shielded, for example by a conductive shield 94 such as a grounded cover frame separated by insulator 96 and extending along the perimeter of the device 10j.
An opaque member (similar to element 80 in device 10g) may be used in the space between devices 10k and 10l, to permit two-sided viewing without interference. Alternatively, either or both of sheets 12h and 12i may be opaque to permit two-sided viewing. The device 10j has the advantage over device 10g that the pattern electrode may be applied after assembly of the composite dual device.
In the dual device configurations, such as shown in FIGS. 11 and 12, at least three of sheet members may all be transparent so that overlapping images (e.g. in regions 20h and 20i of device 10g) may be viewed from at least one side of the device. Depending upon the gas mixtures in the respective regions, different color images may be established in those regions. Moreover, the shapes of the respective regions may be controlled, for example by selecting the shape of spacers in those regions.
The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. | A gas discharge display apparatus in the form of an electroluminescent gas filled panel adapted for quickly and inexpensively making a durable and robust luminous sign using image patterns transferred to the panel by painting, silkscreening, stencilling, lithography, or the like. The apparatus generally includes a pair of substantially parallel spaced apart rigid plates, or sheets, enclosing an electroluminescent gas, and having variously located and kinds of conductive elements, such as surface coatings, used as electrodes for energizing the enclosed electroluminescent gas. | 6 |
RELATED APPLICATIONS
This application, U.S. patent application Ser. No. 13/732,294 filed on Dec. 31, 2012, is a continuation of U.S. patent application Ser. No. 12/776,958 filed May 10, 2010, now U.S. Pat. No. 8,341,930, which issued on Jan. 1, 2013.
U.S. patent application Ser. No. 12/776,958 is a continuation-in-part of U.S. patent application Ser. No. 11/522,236 filed Sep. 14, 2006, now U.S. Pat. No. 7,739,863, which issued on Jun. 22, 2010.
U.S. patent application Ser. No. 11/522,236 claims benefit of U.S. Provisional Patent Application Ser. No. 60/717,627 filed Sep. 15, 2005.
The subject matter of the foregoing related applications are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to rope systems and methods and, in particular, to ropes that are coated to improve the resistance of the rope to bending fatigue.
BACKGROUND
The characteristics of a given type of rope determine whether that type of rope is suitable for a specific intended use. Rope characteristics include breaking strength, elongation, flexibility, weight, bending fatigue resistance and surface characteristics such as abrasion resistance and coefficient of friction. The intended use of a rope will determine the acceptable range for each characteristic of the rope. The term “failure” as applied to rope will be used herein to refer to a rope being subjected to conditions beyond the acceptable range associated with at least one rope characteristic.
The present invention relates to ropes that are commonly referred to in the industry as “lift lines”. Lift lines are used to deploy (lower) or lift (raise) submersible equipment used for deep water exploration. Bending fatigue and abrasion resistance characteristics are highly important in the context of lift lines.
In particular, a length of lift line is connected at a first end to an on-board winch or capstan and at a second end to the submersible equipment. Between the winch and the submersible equipment, the lift line passes over or is wrapped around one or more intermediate structural members such as a closed chock, roller chock, bollard or bit, staple, bullnose, cleat, a heave compensating device, or a constant tensioning device.
When loads are applied to the lifting line, the lifting line wraps around such intermediate structural members and is thus subjected to bending fatigue and abrasion at the intermediate structural members. Abrasion and heat generated by friction at the point of contact between the lifting line and the intermediate structural members can create wear on the lifting line that can affect the performance of the lifting line and possibly lead to failure thereof.
The need thus exists for improved ropes for use as lifting lines that have improved bending fatigue and abrasion resistance characteristics.
SUMMARY
The present invention may be embodied as a rope structure adapted to engage an intermediate structure while loads are applied to ends of the rope structure comprising a primary strength component and a coating. The primary strength component comprises a plurality of fibers adapted to bear the loads applied to the ends of the rope structure. The coating comprises a mixture of a lubricant portion and a binder portion. The lubricant portion comprises particles having an average size of within approximately 0.01 microns to 2.00 microns. The binder portion is applied to the primary strength portion as a liquid and dries to support the lubricant portion relative to at least some of the fibers. The matrix supports the lubricant portion such that the lubricant portion reduces friction between at least some of the plurality of fibers and between at least some of the plurality of fibers and the intermediate structure.
The present invention may also be embodied as a method of forming a rope structure adapted to engage an intermediate structure while loads are applied to ends of the rope structure, comprising the following steps. A plurality of fibers is combined to form a primary strength component adapted to bear the loads applied to the ends of the rope structure. A coating material is provided in liquid form and comprises a lubricant portion and a binder portion. The coating material comprises substantially between 5% and 40% by weight of the lubricant portion. The coating material is applied in liquid form to the primary strength component. The coating material applied to the primary strength component is allowed to dry on the primary strength component such that the binder portion at least partly surrounds at least some of the fibers to support the lubricant portion relative to at least some of the fibers such that the lubricant portion reduces friction between adjacent fibers and between at least some of the plurality of fibers and the intermediate structure.
The present invention may also be embodied as a rope structure adapted to engage an intermediate structure while loads are applied to ends of the rope structure comprising a primary strength component and a coating. The primary strength component comprises a plurality of fibers adapted to bear the loads applied to the ends of the rope structure, where the plurality of fibers are combined to form a plurality of yarns, the plurality of yarns are combined to form a plurality of strands, and the plurality of strands are combined to form the primary strength component. The coating comprises particles suspended within a matrix formed of binder material such that the binder fixes the particles relative to at least some of the fibers such that the particles reduce friction between at least some of the plurality of fibers and between at least some of the plurality of fibers and the intermediate structure. An average size of the particles is within approximately 0.01 microns to 2.00 microns.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are schematic cut-away views of example ropes constructed in accordance with, and embodying, the principles of the present invention;
FIG. 2 is a side elevation view of a first example of a rope of the present invention;
FIG. 3 is a radial cross-section of the rope depicted in FIG. 2 ;
FIG. 4 is a close-up view of a portion of FIG. 3 ;
FIG. 5 is a side elevation view of a second example of a rope of the present invention;
FIG. 6 is a radial cross-section of the rope depicted in FIG. 5 ;
FIG. 7 is a close-up view of a portion of FIG. 6 ;
FIG. 8 is a side elevation view of a third example of a rope of the present invention;
FIG. 9 is a radial cross-section of the rope depicted in FIG. 8 ;
FIG. 10 is a close-up view of a portion of FIG. 9 ;
FIG. 11 is a side elevation view of a fourth example of a rope of the present invention;
FIG. 12 is a radial cross-section of the rope depicted in FIG. 8 ; and
FIG. 13 is a close-up view of a portion of FIG. 12 .
DETAILED DESCRIPTION
Referring initially to FIGS. 1A and 1B of the drawing, depicted in cross-section therein are rope structures 20 a and 20 b constructed in accordance with, and embodying, the principles of the present invention. The rope structures 20 a and 20 b are each formed by one or more plys or strands 22 . The plys or strands 22 are formed by one or more yarns 24 . The yarns 24 are formed by a plurality of fibers 26 . By way of example, the fibers 26 may be twisted together to form the yarns 24 , the yarns 24 twisted to form the plys or strands 22 , and the strands 22 braided or twisted to form the rope structure 20 a or 20 b.
In addition, the example rope structures 20 a and 20 b each comprises a coating 30 that is applied either to the entire rope structure ( FIG. 1A ) or to the individual strands ( FIG. 1B ). In the example rope structures 20 a and 20 b , coating material is applied in liquid form and then allowed to dry to form the coating 30 . The coating 30 comprises a binder portion 32 (solid matrix) and a lubricant portion 34 (e.g., suspended particles). The binder portion 32 adheres to or suspends the fibers 26 to hold the lubricant portion 34 in place adjacent to the fibers 26 . More specifically, the coating 30 forms a layer around at least some of the fibers 26 that arranges the lubricant portion 34 between at least some of the adjacent fibers 26 and between the fibers 26 and any external structural members in contact with the rope structure 20 a or 20 b.
The fibers 26 are combined to form the primary strength component of the rope structures 20 a and 20 b . The lubricant portion 34 of the coating 30 is supported by the binder portion 32 to reduce friction between adjacent fibers 26 as well as between the fibers 26 and any external structural members in contact with the rope structure 20 a or 20 b . The lubricant portion 34 of the coating 30 thus reduces fatigue on the fibers 26 when the rope structures 20 a or 20 b are bent around external structures. Without the lubricant portion 34 of the coating 30 , the fibers 26 would abrade each other, increasing bending fatigue on the entire rope structure 20 a or 20 b . The lubricant portion 34 of the coating 30 further reduces friction between the fibers 26 and any external structural members, thereby increasing abrasion resistance of the rope structures 20 a and 20 b.
With the foregoing understanding of the basic construction and characteristics of the rope structures 20 a and 20 b of the present invention in mind, the details of construction and composition of the rope structures 20 will now be described.
In the liquid form, the coating material comprises at least a carrier portion, the binder portion, and the lubricant portion. The carrier portion maintains the liquid form of the coating material in a flowable state. However, the carrier portion evaporates when the wet coating material is exposed to the air, leaving the binder portion 32 and the lubricant portion 34 to form the coating 30 . When the coating material has dried to form the coating 30 , the binder portion 32 adheres to the surfaces of at least some of the fibers 26 , and the lubricant portion 34 is held in place by the binder portion 32 . The coating material is solid but not rigid when dried as the coating 30 .
In the example rope structures 20 a and 20 b , the coating material is formed by a mixture comprising a base forming the carrier portion and binder portion and PolyTetraFluoroEthylene (PTFE) forming the lubricant portion. The base of the coating material is available from s.a. GOVI n.v. of Belgium under the tradename LAGO 45 and is commonly used as a coating material for rope structures. Alternative products that may be used as the base material include polyurethane dispersions; in any event, the base material should have the following properties: good adhesion to fiber, stickiness, soft, flexible. The base of the coating material is or may be conventional and will not be described herein in further detail.
The example lubricant portion 34 of the coating material is a solid material generically known as PTFE but is commonly referred to by the tradename Teflon. The PTFE used in the coating material of the example rope structures 20 a and 20 b is in powder form, although other forms may be used if available. The particle size of the PTFE should be within a first preferred range of approximately 0.10 to 0.50 microns on average but in any event should be within a second preferred range of 0.01 to 2.00 microns on average. The example rope structures 20 a and 20 b are formed by a PTFE available in the marketplace under the tradename PFTE30, which has an average particle size of approximately 0.22 microns.
The coating material used by the example rope structures 20 a and 20 b comprises PTFE within a first preferred range of approximately 32 to 37% by weight but in any event should be within a second preferred range of 5 to 40% by weight, with the balance being formed by the base. The example rope structures are formed by a coating material formed by approximately 35% by weight of the PTFE.
As an alternative to PTFE, the lubricant portion 34 may be formed by solids of other materials and/or by a liquid such as silicon oil. Other example materials that may form the lubricant portion 34 include graphite, silicon, molybdenum disulfide, tungsten disulfide, and other natural or synthetic oils. In any case, enough of the lubricant portion 34 should be used to yield an effect generally similar to that of the PTFE as described above.
The coating 30 is applied by dipping the entire rope structure 2 a and/or individual strands 22 into or spraying the structure 20 a and/or strands 22 with the liquid form of the coating material. The coating material is then allowed to dry on the strands 22 and/or rope structure 20 a . If the coating 30 is applied to the entire rope structure 20 a , the strands are braided or twisted before the coating material is applied. If the coating 30 is applied to the individual strands 22 , the strands are braided or twisted to form the rope structure 20 b after the coating material has dried.
In either case, one or more voids 36 in the coating 30 may be formed by absences of coating material. Both dipping and spraying are typically done in a relatively high speed, continuous process that does not allow complete penetration of the coating material into the rope structures 20 a and 20 b . In the example rope structure 20 a , a single void 36 is shown in FIG. 1A , although this void 36 may not be continuous along the entire length of the rope structure 20 a . In the example rope structure 20 b , a void 36 is formed in each of the strands 22 forming the rope structure 20 b . Again, the voids 36 formed in the strands 22 of the rope structure 20 b need not be continuous along the entire length of the rope structure 20 a.
In the example rope structures 20 a and 20 b , the matrix formed by the coating 30 does not extend through the entire volume defined by the rope structures 20 a or 20 b . In the example structures 20 a and 20 b , the coating 30 extends a first preferred range of approximately ¼ to ½ of the diameter of the rope structure 20 a or the strands of the rope structure 20 b but in any event should be within a second preferred range of approximately ⅛ to ¾ of the diameter of the rope structure 20 a or the strands 22 of the rope structure 20 b . In the example rope structures 20 a and 20 b , the coating matrix extends through approximately ⅓ of the diameter of the rope structure 20 a or the strands 22 of the rope structure 20 b.
In other embodiments, the matrix formed by the coating 30 may extend entirely through the entire diameter of rope structure 20 a or through the entire diameter of the strands 22 of the rope structure 20 b . In these cases, the rope structure 20 a or strands 22 of the rope structure 20 b may be soaked for a longer period of time in the liquid coating material. Alternatively, the liquid coating material may be forced into the rope structure 20 a or strands 22 of the rope structure 20 b by applying a mechanical or fluid pressure.
The following discussion will describe several particular example ropes constructed in accordance with the principles of the present invention as generally discussed above.
First Specific Rope Example
Referring now to FIGS. 2 , 3 , and 4 , those figures depict a first specific example of a rope 40 constructed in accordance with the principles of the present invention. As shown in FIG. 2 , the rope 40 comprises a rope core 42 and a rope jacket 44 . FIG. 2 also shows that the rope core 42 and rope jacket 44 comprise a plurality of strands 46 and 48 , respectively. FIG. 4 shows that the strands 46 and 48 comprise a plurality of yarns 50 and 52 and that the yarns 50 and 52 in turn each comprise a plurality of fibers 54 and 56 , respectively. FIGS. 3 and 4 also show that the rope 40 further comprises a coating material 58 that forms a matrix that at least partially surrounds at least some of the fibers 54 and 56 .
The exemplary rope core 42 and rope jacket 44 are formed from the strands 46 and 48 using a braiding process. The example rope 40 is thus the type of rope referred to in the industry as a double-braided rope. The strands 46 and 48 may be substantially identical in size and composition. Similarly, the yarns 50 and 52 may also be substantially identical in size and composition. However, strands and yarns of different sizes and compositions may be combined to form the rope core 42 and rope jacket 44 . Additionally, the fibers 54 and 56 forming at least one of the yarns 50 and 52 may be of different types.
Second Rope Example
Referring now to FIGS. 5 , 6 , and 7 , those figures depict a second example of a rope 60 constructed in accordance with the principles of the present invention. As perhaps best shown in FIG. 6 , the rope 60 comprises a plurality of strands 62 . FIG. 7 further illustrates that each of the strands 62 comprises a plurality of yarns 64 and that the yarns 64 in turn comprise a plurality of fibers 66 . FIGS. 6 and 7 also show that the rope 60 further comprises a coating material 68 that forms a matrix that at least partially surrounds at least some of the fibers 66 .
The strands 62 are formed by combining the yarns 64 using any one of a number of processes. The exemplary rope 60 is formed from the strands 62 using a braiding process. The example rope 60 is thus the type of rope referred to in the industry as a braided rope.
The strands 62 and yarns 64 forming the rope 60 may be substantially identical in size and composition. However, strands and yarns of different sizes and compositions may be combined to form the rope 60 . In the example rope 60 , the strands 62 (and thus the rope 60 ) may be 100% HMPE or a blend of 40-60% by weight of HMPE with the balance being Vectran.
Third Rope Example
Referring now to FIGS. 8 , 9 , and 10 , those figures depict a third example of a rope 70 constructed in accordance with the principles of the present invention. As perhaps best shown in FIG. 9 , the rope 70 comprises a plurality of strands 72 . FIG. 10 further illustrates that each of the strands 72 comprises a plurality of yarns 74 , respectively. The yarns 74 are in turn comprised of a plurality of fibers 76 . FIGS. 9 and 10 also show that the rope 70 further comprises a coating material 78 that forms a matrix that at least partially surrounds at least some of the fibers 76 .
The strands 72 are formed by combining the yarns 74 using any one of a number of processes. The exemplary rope 70 is formed from the strands 72 using a twisting process. The example rope 70 is thus the type of rope referred to in the industry as a twisted rope.
The strands 72 and yarns 74 forming the rope 70 may be substantially identical in size and composition. However, strands and yarns of different sizes and compositions may be combined to form the rope 70 .
Fourth Rope Example
Referring now to FIGS. 11 , 12 , and 13 , those figures depict a fourth example of a rope 80 constructed in accordance with the principles of the present invention. As perhaps best shown in FIG. 12 , the rope 80 comprises a plurality of strands 82 . FIG. 13 further illustrates that each of the strands 82 comprise a plurality of yarns 84 and that the yarns 84 in turn comprise a plurality of fibers 86 , respectively. FIGS. 12 and 13 also show that the rope 80 further comprises a coating material 88 that forms a matrix that at least partially surrounds at least some of the fibers 86 .
The strands 82 are formed by combining the yarns 84 using any one of a number of processes. The exemplary rope 80 is formed from the strands 82 using a braiding process. The example rope 80 is thus the type of rope commonly referred to in the industry as a braided rope.
The strands 82 and yarns 84 forming the rope 80 may be substantially identical in size and composition. However, strands and yarns of different sizes and compositions may be combined to form the rope 80 . The first and second types of fibers are combined to form at least some of the yarns 84 are different as described above with reference to the fibers 24 and 28 . In the example rope 80 , the strands 82 (and thus the rope 80 ) may be 100% HMPE or a blend of 40-60% by weight of HMPE with the balance being Vectran.
Given the foregoing, it should be clear to one of ordinary skill in the art that the present invention may be embodied in other forms that fall within the scope of the present invention. | A rope structure adapted to engage an intermediate structure while loads are applied to ends of the rope structure comprises a primary strength component and a coating. The primary strength component comprises a plurality of fibers adapted to bear the loads applied to the ends of the rope structure. The coating comprises a mixture of a lubricant portion and a binder portion. The lubricant portion comprises particles having an average size of within approximately 0.01 microns to 2.00 microns. The binder portion is applied to the primary strength portion as a liquid and dries to support the lubricant portion relative to at least some of the fibers. The matrix supports the lubricant portion such that the lubricant portion reduces friction between at least some of the plurality of fibers and between at least some of the plurality of fibers and the intermediate structure. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates to methods for the manufacture and use of compositions derived from aqueous dispersions of water-insoluble polymers, many of which are believed to be new compositions of matter. The products are found useful in the processing of aqueous mixtures and are particularly suited to crude oil production, oily water processing, waste water treatment and water purification.
PRIOR ART
[0002] Preparations of Aqueous Polymer Dispersions
[0003] There are numerous methods for the preparation of aqueous dispersions of nano- and micro-sized polymer particles. Dispersions may be formed in situ, for example in aqueous emulsion polymerization of latex. Alternatively, polymers may be dispersed in separate, post-polymerization steps, for example alkaline dispersion of copolymers of ethylene acrylic acid (EAA). Dispersed polymer characteristics such as particle size, stability to re-agglomeration, viscosity and other properties useful in the target applications may be varied by control of preparation conditions such as mixing shear and/or additives such as surfactants.
[0004] Uses of Aqueous Polymer Dispersions
[0005] Water-based formulations containing emulsified and/or dispersed water-insoluble polymers, waxes, oils and so forth have found broad application as lubricants, adhesives, coatings and in processes for production of polymer composites and filters.
[0006] It is generally known that such dispersed materials may be flocculated via addition of soluble salts of metals such as aluminum, iron etc. However, the flocs thus produced are often disadvantageously voluminous, fragile, incompletely flocculated and/or difficult to separate from the treated water. Further, metal residues may remain dissolved in the treated water, requiring subsequent treatment to remove them.
[0007] Water-soluble flocculating polymers may be used in flocculation processes but such polymers present difficulties in preparation and use due to their high polymer molecular weight (“MW”), low rate of dissolution and high solution viscosity. Further, soluble flocculants typically cannot be regenerated from the flocs, leading to waste disposal issues. Still further, many soluble flocculating polymers are toxic and special measures may be needed to ensure complete polymer removal prior to use or discharge of the treated aqueous phase.
[0008] In the case of metal removal using aqueous polymer dispersions, only certain limited types of dispersed polymer have been taught. Typical prior art references include U.S. Pat. Nos. 5,447,643, 4,747,954, 3,798,194, 3,790,521 and 3,801,551. As disclosed in one or more of these references, aqueous dispersions or suspensions of solid carboxylic acid polymers such as ethylene acrylic acid (EAA) are introduced into aqueous compositions in order to effect metal removal by ion exchange.
[0009] The referenced processes may consume undesirably large amounts of polymer per unit of metal removed. For example, removal of aluminum would require addition of 40 times its weight of an EAA polymer of equivalent weight=360. Further, significant metal and polymer residues may remain in the treated aqueous phase. The prior art does not contemplate the concepts and methodologies of the present invention as applied to metals removal, and which result in significant enhancements in polymer performance.
[0010] Further, the prior art fails to anticipate that aqueous dispersions of insoluble polymers could be generally useful as flocculants for processing of non-metallic dissolved, suspended and/or liquid aqueous contaminants or phases, including oils, suspended solids, dissolved toxic organic materials and the like.
SUMMARY OF THE PRESENT INVENTION
[0011] In accordance with the present invention, methods have been developed involving the use of aqueous polymer dispersions (“APD”) capable of undergoing phase inversion for the production of phase-inverted polymer compositions, which methods can be adapted for a wide variety of uses including treatment of contaminated water, crude oil fluids separation, etc. as discussed herein. Other applications include the manufacture of membranes and production of novel polymer compositions and structures. These aspects are detailed in a co-pending patent application.
[0012] The term “phase inversion” as used herein is defined as spontaneous or induced nano- and/or micro-polymer phase inversion, flocculation, catenation, gellation, sorption, complexation, precipitation and/or coalescence from a dispersed aqueous first form into a second form. The term “nanopolymer” as used herein refers to a dispersed polymer-water-additive aggregate, or catenated forms thereof.
[0013] Obviously, not all APD compositions will be phase invertible to yield a readily separated polymer phase and/or purified liquid phases(s). It has been found possible to modify such compositions via methods disclosed herein to form more readily phase inverted compositions and/or more readily separable polymer and treated liquid phase(s). Moreover, it will be clearly understood by those skilled in the art that “readily phase inverted” and “readily separable” are relative to the context of the specific process objectives and separation method desired. For example, formation of a neutral-buoyancy polymer-contaminant microfloc may be acceptable where membrane filtration systems are installed but unacceptable where flotation and/or screening is the separation method of choice.
[0014] In contrast to the homogeneous nature of conventional aqueous flocculating polymers, phase invertible APD polymers are substantially insoluble in the aqueous carrier and are present as finely divided particles containing hundreds or thousands of polymer chains forming a particulate structure. APDs do not exhibit the high bulk viscosity and other undesirable characteristics associated with a conventional aqueous polymer solution (“APS”) of similar concentration, and mobile liquid APD containing 20 to 60 wt. % polymer can be readily prepared. Colloidal dispersions of water-soluble polyacrylamides are also known, but these are distinguished from the phase invertible APD in that the polyacrylamide particles form an APS upon dilution while APDs retain their particulate characteristics even at low aqueous concentrations.
[0015] The structure and physicochemical behaviour of phase invertible APD is influenced by numerous variables including pH, temperature, salinity, added particulates, polymer concentration, particle size, zeta potential, concentration of surfactant(s), concentration of co-reagents, concentration of dispersed non-aqueous fluid phases, mixing shear and so forth.
[0016] It is a further highly significant feature of the present invention that polymer-contaminant materials may often be readily separated, the concentrated contaminant recovered or disposed and the polymer re-dispersed, thus reducing polymer consumption and minimizing waste volumes generated. In contrast, APS/contaminant precipitates typically are not conveniently separated.
[0017] In accordance with one aspect of the invention, there is provided an improved method for removing a contaminant from an aqueous mixture containing the contaminant comprising the steps of: providing or forming an aqueous mixture containing a contaminant and an aqueous polymer dispersion, the polymer being a substantially water insoluble polymer and being capable of undergoing phase inversion or coalescence; forming an aqueous composition of the aqueous polymer dispersion and the aqueous mixture containing the contaminant; and effecting phase inversion or coalescence of the polymer in the aqueous composition to thereby form at least one contaminant precipitated phase and a treated aqueous phase.
[0018] In the above method, a preferred aspect further comprises the step of adding a precipitation agent to initiate phase inversion. Another preferred embodiment of this aspect includes the step of separating the precipitated phase from treated aqueous phase.
[0019] In a still further aspect of the present invention there is provided a method for, removing oil from an aqueous mixture containing oil comprising the steps of: providing an aqueous mixture containing oil; providing an aqueous polymer dispersion, the polymer being a substantially water insoluble polymer and being capable of undergoing phase inversion or coalescence; forming an admixture of the aqueous polymer dispersion and a weak base; and forming an aqueous composition of (a) the admixture of the polymer dispersion and the weak base and (b) the aqueous mixture containing the oil to thereby induce release of dispersed polymer from the paste into the aqueous phase followed by spontaneous or induced phase inversion of the polymer and form a solid floating oil precipitate on the surface of the aqueous composition.
[0020] In another aspect of the present invention there is provided a method of separating a fluid mixture comprising the steps of: providing a fluid mixture; providing an aqueous polymer dispersion, the polymer being a substantially water insoluble polymer and the polymer being capable of undergoing a phase inversion; mixing the dispersion with the fluid mixture; effecting the phase inversion to yield solidified, coalesced or gelled polymer phase and one or more coalesced fluid phase(s); and separating the phase(s).
[0021] In the preceding method, a preferred embodiment is where the precipitation agent is added to the aqueous polymer dispersion to form an intermediate composition prior to addition of the intermediate composition to the aqueous mixture.
[0022] In various of the above methods there is preferably included the step of separating a precipitated phase by a process selected from one or more of magnetic separation, sedimentation, flotation, centrifugation, hydrocyclone treatment, screening, filtration, skimming, distillation, drying, differential pressure press-filtration and membrane permeation processes. Another aspect of this embodiment preferably comprises the step of selectively heating or electromagnetically treating the precipitated phase prior to or simultaneous with the separation step.
[0023] In the above and subsequently described methods, the invention may be used for treatment of aqueous mixtures containing a wide range of contaminants such as colloidal solid or liquid, emulsified oil, free-phase oil or hydrocarbon, dissolved gas, dispersed gas, edible or essential oil, tar, bitumen, fat, dissolved metal, chelated metal, precipitated metal, dissolved organic substance, surfactant, soluble polymer, paint, carbon, clay, colour, protein, pharmaceutical agent, biocide, biological fluid fraction, fermentation fraction, blood, fertilizer, food residue, alkyl amine, ethoxylated alkyl amine, phenol or derivative thereof, aromatic hydrocarbon, halogenated hydrocarbon, sulfonated hydrocarbon, carboxylic acid, soap, micelle, natural product, radionuclide; latex; and ore particles.
[0024] In the preceding methods, preferred embodiments are where at least one process condition selected from pH, temperature, shear, mixing rate, residence time, addition rate, ionic type and concentration, soluble polymer type and concentration, oil type and concentration, dispersed gas concentration, dispersed solid concentration, microwave intensity, is controlled during the method.
[0025] If desired, following the various methods of the present invention described hereinabove or hereinafter, the polymer can be recovered and used again. Suitable recovery techniques include e.g. filtration, flotation, sedimentation, centrifugation, etc. Conveniently, undesirable levels of contaminants can be removed prior to re-use.
[0026] In the embodiment of the present invention where a gas generating composition is employed, any suitable agent compatible with the aqueous composition or admixture may be employed. Such agents may be added in solid or liquid forms. Typical agents can be various carbonates and bicarbonates such as ammonium carbonate, sodium carbonate, etc. The amount of agent added will vary depending on the intensity and amount of gas generation desired.
[0027] In carrying out phase inversion, any suitable treatment or additive may be employed including: addition of acid, soluble metal salt, soluble flocculant, dispersed oil, colloidal organic solid, colloidal inorganic solid, fibrous material, porous material, dissolved and/or dispersed gas phase; heating; cooling; dilution; exposure to electromagnetic radiation or ultrasonic treatment, varying mixing shear, turbulence or any combination of the foregoing, simultaneously or sequentially. The selection of the treatment or additive will depend on the nature of the dispersed polymer and aqueous phase as well as process conditions and desired solid-liquid separation method. The initiating agent may be added to the aqueous solutions prior to the addition of the polymer in certain cases. The amount of initiating agent will vary depending on several factors—e.g. the amount and nature of the polymer used, the amount and nature of contaminant, pH and temperature conditions, etc.
[0028] In some cases, addition of a precipitating agent or agent which initiates phase inversion may not be required where the mixture flocculates spontaneously after addition of the polymer dispersion.
[0029] In a still further aspect of the present invention, there is provided a method of enhancing a flotation process comprising the step of adding an aqueous polymer dispersion to the mixture during the process, the polymer of the dispersion being a substantially water insoluble polymer and being capable of undergoing phase inversion.
[0030] Another embodiment of the present invention relates to a method of enhancing a sedimentation process comprising the step of adding an aqueous polymer dispersion to the mixture during the process, the polymer of the dispersion being a substantially water insoluble polymer and being capable of undergoing phase inversion.
[0031] In a different embodiment of the present invention, there is provided a method of enhancing a phase coalescence process comprising the step of adding an aqueous polymer dispersion to the mixture during the process, the polymer of the dispersion being a substantially water insoluble polymer and being capable of undergoing phase inversion.
[0032] In various embodiments of the present invention, the polymer dispersions can be mixed by suitable means or process steps with the aqueous mixture to form a composition, with separation of a solid precipitate from the resulting treated phase. Typical mixing methods include mechanical agitation, ultra-sonic mixing, magnetic stirring, static mixers, etc. The intensity of mixing will depend on the nature of the admixture and whether or not high or low shear is employed will likewise depend on several factors, such as the nature of the contaminants, the characteristic properties of the resulting floc as to whether it is of a fragile or a robust nature. Suitable techniques are well known in the flocculating art for handling such floc types.
[0033] Another aspect of the present invention involves a method of removing a contaminant from an aqueous contaminant spill comprising the steps of: locating an aqueous spill at a site containing the contaminant; providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being a substantially water insoluble polymer; applying the aqueous polymer dispersion to the aqueous spill and permitting the polymer dispersion to undergo a phase inversion to effect solidification and immobilization of the contaminant with the polymer and form a solid precipitate; and removing the solid precipitate from the spill. In this method, preferably there is included the step of adding a precipitation agent to initiate the phase inversion.
[0034] The invention also provides, in another embodiment, a method of in-situ leak reparation comprising the steps of: providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being a substantially. water insoluble polymer; injecting the aqueous polymer dispersion to a subsurface source having an aqueous contaminant leak, and in which the contaminant is contained within the aqueous mixture; effecting polymer phase inversion to form a solid precipitate of contaminant with the polymer; and permitting the solid precipitate to seal the leak. In this method, preferably there is included the further step of adding a precipitation agent to initiate phase inversion.
[0035] In another aspect of the present invention, there is also provided a method of removing a contaminant from soil comprising the steps of: providing a soil containing oil or other contaminant leachable therefrom; providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being a substantially water insoluble polymer; mixing together, under conditions which substantially inhibit deposition of polymer onto the soil surfaces, the aqueous polymer dispersion, the soil containing the contaminant, water and a surfactant to cause the contaminant to enter the aqueous phase; and separating soil from the resulting aqueous phase.
[0036] In preferred embodiments of the above described method, phase inversion is utilized to solidify the contaminants with the polymer and separating water from the solidified contaminants. In some cases, it may be desirable to add a solvent to increase extraction rate and or efficiency of the extraction.
[0037] In related aspects of the present invention, there is also provided a method of preparing an aqueous polymer dispersion with improved characteristics comprising the steps of: providing a first aqueous polymer dispersion in which the polymer is substantially water insoluble; adding a substance at a controlled pH and temperature sufficient to form a second aqueous polymer dispersion having improved properties over the first aqueous polymer dispersion. Desirably, the added substance is selected from the group consisting of acid, multivalent metal, cellulose, bitumen, rubber, oil, colloidal organic or inorganic solid.
[0038] In a still further development, there) is also provided a method for the solvent extraction of metals from an aqueous mixture comprising the steps of: providing an aqueous mixture containing metals and emulsified solvent-chelant; providing an aqueous polymer dispersion, the polymer being substantially water insoluble and being capable of undergoing phase inversion; mixing the dispersion with the aqueous mixture; creating a polymer phase inversion; and separating the resulting polymer solid from the extracted solution.
[0039] There is also provided a method of enhancing dewatering of a hydrous floc comprising: providing a hydrous floc; providing an aqueous polymer dispersion, the polymer being a substantially water insoluble polymer and being capable of undergoing phase inversion or-coalescence; forming an aqueous composition of the aqueous polymer dispersion and the hydrous floc; and effecting phase inversion or coalescence of the polymer in the aqueous composition to thereby form a second floc with improved dewatering properties.
[0040] Moreover, the present invention also provides a method for the selective extraction of metals from aqueous solution comprising the steps of: providing an aqueous metal solution containing at least two different metals dissolved therein; providing an aqueous polymer dispersion of a substantially water insoluble polymer, the polymer being capable of phase inversion; mixing the dispersion with the metal solution; inducing polymer phase inversion under conditions to preferentially incorporate one of the metals into polymer solids resulting from phase inversion while the other metal remains substantially in dissolved form; and separating the polymer solids from the selectively extracted solution.
[0041] Another aspect of the present invention provides a method for enhancing a solvent extraction process comprising: providing an aqueous solvent mixture; providing an aqueous polymer dispersion, the polymer being capable of undergoing phase inversion and being substantially water insoluble; mixing the aqueous solvent mixture and the polymer dispersion to effect a polymer phase inversion and form a polymer solvent extract solid and extracted water phase substantially free of solvent.
[0042] Still further, the present invention teaches a method for the extraction of a soluble substance from water comprising the steps of: providing an aqueous polymer dispersion, the polymer being substantially water insoluble and being capable of phase inversion; providing an aqueous solution containing a substance to be extracted; mixing the dispersion and solution such that polymer phase inversion occurs; and producing a solid phase containing the substance and extracted water phase.
[0043] Moreover, there is also disclosed herein a method of purifying a dispersable polymer comprising the steps of: providing a dispersable polymer to be purified, the polymer being substantially water insoluble and being capable of undergoing phase inversion; preparing a dilute aqueous dispersion of the polymer; inducing a phase inversion in the dispersion; and separating purified polymer. Desirably, the preceding method includes the step of preparing an aqueous dispersion from the purified dispersable polymer.
[0044] The invention also provides for a new method for producing polymer-additive solids with improved dispersibility comprising the steps of: providing an aqueous polymer dispersion-additive mixture, the polymer being substantially water insoluble and being capable of undergoing phase inversion; inducing a phase inversion under conditions to form a polymer-additive solid intermediate; separating the intermediate solid; re-dispersing the intermediate solid; removing undispersed material; inducing a phase inversion; and isolating the refined solid, the refined solid exhibiting improved dispersibility characteristics.
[0045] In general terms, the invention also provides a method of inducing a phase inversion in a mixture containing an aqueous polymer dispersion or flocculated slurry comprising: providing an aqueous polymer dispersion or flocculated slurry derived therefrom, the polymer being substantially water insoluble and being capable of undergoing phase inversion, and adjusting the pH of the slurry to thereby form a polymer product having enhanced contaminant removal capability. In particular, such enhanced capabilities include properties such as increased contaminant removal, increased separation efficiency, increased selectivity for target contaminants. Thus, for example, selective removal of copper is enhanced by addition of calcium ions, metal removal capacity can be increased by addition of e.g. hydroxide ions.
[0046] Another embodiment of the present invention provides a method of particulate flocculation comprising: providing an aqueous mixture containing particulates, providing an aqueous polymer dispersion and mixing the polymer dispersion with the aqueous mixture.
[0047] Still further, there is also disclosed a method of forming a metastable or activated form of an aqueous polymer dispersion or slurry comprising: providing an aqueous polymer dispersion, providing an aqueous mixture containing one or more from the group comprising acid and multivalent metal and mixing the aqueous mixture into the dispersion. Such metastable dispersions may have lifetimes long enough to permit manufacture at a first site and transportation to a second site for use.
[0048] Certain embodiments of the present invention can involve or can be based on one or more of (a) direct contaminant sorption by the phase-inverted polymer surfaces and/or permeation into the polymer structure, (b) coalescence and/or flocculation induced by very high surface area polymer structures; (c) solid or liquid contaminant-polymer catenation, and/or (d) liquid and particulate entrapment, sorption and/or microencapsulation within the flocculated polymer macrostructure.
[0049] Clear distinctions exist between aqueous polymer solution (“APS”) and APD structures and properties. Unlike the solvated monomeric polymer chains in APS, the colloidal structures of APD may contain several hundreds to several thousands of individual polymer chains, with this assembly having some of the characteristics of polymers of very high MW (up to tens of millions). However, APD structures do not exhibit the high bulk viscosity and other undesirable characteristics associated with an APS of similar effective MW. APS do not contain colloidal structures in sufficient concentration for utility in the processes hereinafter discussed. However, it is noted that APSs may react with suitable materials to form an APD-like structure in-situ.
[0050] The structure and physicochemical behaviour of APDs is strongly influenced by numerous variables including pH, temperature, salinity, zeta potential, multivalent cations, concentration of polymer, co-reagents and/or non-aqueous phases and so forth. Control of suitable variables allows APDs of various nanopolymer structures to be prepared; these have been found to be of utility in removing contaminants from aqueous mixtures via phase inversion of the APD to form polymer solids containing the contaminants.
[0051] Utility
[0052] The present invention finds wide utility for numerous uses. One prominent use is the application of the method to remove contaminants from aqueous mixtures for various purposes, such as plant stream clean up, purification of aqueous mixtures containing contaminants to recover the contaminants and provide a potential feed stream for re-use in various processes or industries, etc. Other applications of the present invention relate to oil spill clean-ups, use of the methods of the present invention also finds application for land-based spills involving e.g. oil, which will provide a solidified oil fraction, which is then easily removed from a spill site.
[0053] In the case of contaminant spills such as oil spills into a body of water, utilization of the methods of the present invention will result in a polymer-contaminant solid which floats on the water body and thus may be removed by well-known surface skimming/screening techniques. In the case of oil spills in water bodies, the present invention also finds use where it has been determined that the oil-water mixtures resulting from such a spill can be gelled using relatively small amounts of the polymers described herein, in combination with high shear mixing. In other words, a polymer is added to the oil-water mixture and after phase inversion together with high shear mixing gelled emulsions will result which will have the consistency of a stiff whipped cream. Such compositions can be stable for up to several days which would permit cleanup operations to be employed (e.g. using boom deployments). This particular technique has the advantage that many times the weight of the polymer in terms of contaminant, can be- immobilized.
[0054] Other uses of the methods of the present invention include metal removal from aqueous compositions as well as use in providing in-situ leak repairs. The invention can also be used to prepare aqueous polymers dispersions having improved chemical and/or physical characteristics. Selective extraction of metals is also possible using the present invention as well as purification of dispersible polymer. The methods of the present invention provide significant improvements over the prior art, particularly as to the efficiency of the present methods in removing contaminants from aqueous mixtures.
[0055] Polymers
[0056] In the present invention, the polymers which can be employed are those which are substantially insoluble in water and are dispersible therein and which are capable of undergoing phase inversion. Such polymers can be chosen from a very wide range of known polymers, preferred classes of which are identified hereinafter.
[0057] Alternatively, the substantially water insoluble polymer can be one which is capable of coalescing once mixed in an aqueous solution containing a contaminant to undergo transformation to a non-dispersed-form. As used herein, the term “dispersible polymer” refers to a polymer which in an aqueous mixture, forms with the aqueous mixture, a two phase system in which one phase is water with the other phase being composed of very small particles of polymer, either in a solid, liquid or gel state.
[0058] It has been found that a wide variety of physical forms and compositions of polymers derived from colloidal aqueous dispersion may be employed in the present invention, e.g. micro-emulsion; micro- or macro-fibrous, membranous or particulate slurry or suspension; porous solid or gel. As such, the polymer compositions which can be used in the present invention may include liquid polymers such as paraffins, oils, silicones, polyglycols, latexes, and so forth, and solid polymers which are fibrous or resinous polymers as well as a wide range of thermoplastic polymers. With respect to solid polymers, preferably they are used in the present invention in highly porous, permeable, swellable and/or finely divided particulate form; more desirably such polymers are micronized polymers having a particle size which can range, desirably, to between about 1 to about 50 microns.
[0059] A most preferred embodiment of the present invention utilizes dispersed nano sized particles for more desirable results—such particles may range from about 1 to 50,000 nanometers, desirably 2 to 20,000 nanometers, with the most preferred range being 3 to 2000 nanometers.
[0060] In general terms, the polymers which may be employed in the present invention can be various types of water-insoluble polyamides, polyolefins, and particularly polyethylene or co-polymers of ethylene with one or more other monomers or polymers; in addition, oxidized polyolefins and in particular, highly oxidized polyethylenes; teflon polymers such as tetrafluoroethylene polymers and co-polymers, vinylacetate polymers such as polyvinyl acetate, or co-polymers of vinylacetate polymer; urethane polymers, e.g. polymers of isocyanate/polyol; styrene polymers and co-polymers and particularly carboxylated styrenes; acrylic acid polymers or co-polymers such as methacrylic acid co-polymers; polymers and co-polymers containing diene groups such as polystyrene-butadiene, polychlorobutadiene, polyvinylpyridines.
[0061] Clearly, the optimal polymer composition and/or form to be used may be tailored for specific feeds, as illustrated by the examples disclosed herein. Thus, certain polymer compositions and forms will be more suitable than others for different processes, e.g. oil-water separation vs. dissolved metals removal.
[0062] By way of example, the present invention can utilize solid, water-insoluble thermoplastic organic acid addition polymers which can be of a wide ranging chemical structure, provided that they have the physical properties and characteristics described above. Such typical polymers which may be acid polymers which are addition polymers of ethylenically unsaturated monomers where the starting monomers include one having an acid group of the kind specified. For example, suitable polymers are the random copolymer products of copolymerization of mixtures of one or more polymerizable ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and anhydride, itaconic acid, fumaric acid, citraconic acid and anhydride, methyl hydrogen maleate, and the like, and one or more non-acid polymerizable monomers, such as ethylene, propylene, butene-1,1,3-butadiene, and other aliphatic olefins; styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and other aromatic olefins; ethyl acrylate, methyl methacrylate, vinyl acetate and other unsaturated esters; vinyl and vinylidene chloride; vinyl ethers, acrylamide; acrylonitrile; and the like.
[0063] One class of suitable copolymers for use in the present invention includes: co-polymers of ethylene and from at least about 1 % to about 25% by weight of one or more ethylenically unsaturated acids, such as acrylic acid, methacrylic acid, methyl hydrogen maleate, etc. as above recited; co-polymers of ethylene, from about 1 to about 25% by weight of one or more ethylenically unsaturated acids, and up to about 50% by weight of one or more other monomers such as ethyl acrylate, vinyl acetate, etc., as above recited; and co-polymers of styrene (and/or other ar-vinylaromatic compounds) and from about 3.5 to about 11% by weight of one or more ethylenically unsaturated acids such acrylic acid, maleic anhydride, etc., as above recited.
[0064] In addition, other polymers which-can be used include preformed and non-acid polymers by subsequent chemical reaction carried out thereon. For example, the carboxylic acid group may be supplied by providing carboxylic anhydride, ester, amide, acyl halide, and nitrile groups which are then hydrolyzed to carboxylic acid groups.
[0065] Within the above defined groups of known polymers and co-polymers, reference may be made specifically to ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, ethylene/itaconic acid copolymers, ethylene/methyl hydrogen maleate copolymers, ethylene/maleic acid copolymers, ethylene/acrylic acid/methyl methacrylate (ternary) copolymers, ethylene/acrylic acid/ethyl acrylate copolymers, ethylene/methacrylic acid/ethyl acrylate copolyrners, ethylene/itaconic acide/methyl methacrylate copolymers, ethylene/methyl hydrogen maleate/ethyl acrylate copolymers, ethylene/acrylic acid/vinyl acetate copolymers, ethylene/methacrylic acid/vinyl acetate copolymers, ethylene/acrylic acid/vinyl alcohol copolymers, ethylene/propylene/acrylic acid copolymers, ethylene/acrylamidelacrylic acid copolymers, ethylene/styrene/acrylic acid copolymers, ethylene/methacrylic acid/acrylonitrile copolymers, ethylene/fumaric acid/vinyl methyl ether copolymers, ethylene/vinyl chloride/acrylic acid copolymers, ethylene/vinylidene chloride/acrylic acid copolymers, styrene/acrylic acid copolymers, styrene/methacrylic acid copolymers, styrene/itaconic acid copolymers, styrene/methyl methacrylate/acarylic acid copolymers, styrene/maleic anhydride copolymers, styrene/citraconic anhydride copolymers, archlorostyrene/acrylic acid-copolymers, ar-t-butylstyrene/acrylic acid copolymers, methyl methacrylate/isobutyl acrylate/acrylic acid copolymers.
[0066] In general terms, the amount and type of polymer(s) used will depend on numerous factors including feed type and contaminant concentration, feed conditions, desired rate, separation method to be employed, desired floc particle size and so forth. Generally speaking, since the nature of the feed may vary considerably, it will be understood that the optimal amount, form and composition of nanopolymer for processing of a specific feed will be readily determined and optimized by techniques well known in the art.
[0067] Oil-Polymer Dispersions:
[0068] It is known that addition of oil can facilitate preparation and/or increase stability of APDs. It has been found that oil-polymer dispersions have utility in certain processes discussed herein. It is therefore a feature of one embodiment of the present invention to prepare oil-polymer dispersions, slurries and solids with improved properties over commercially available dispersions for the processes described herein.
[0069] Other Applications:
[0070] In further embodiments of the present invention, the aqueous polymer dispersion, together with a precipitation initiator agent if required, may be applied onto spills to solidify and immobilize the contaminants, which may then be more easily recovered from a spill site. The aqueous polymer dispersion may also be injected with a precipitation initiator agent into subsurface sources of contamination including leaking landfills, underground fuel storage tanks or the like. Optionally, the polymer is injected at elevated temperature to form molten polymer which solidifies to a relatively impermeable mass on cooling. The polymer after flocculation and/or solidification acts to immobilize and solidify contaminants, while at the same time, forms a barrier to further leakage. In a preferred embodiment of the invention a water-soluble non-toxic acid and/or multivalent metal salt such as calcium chloride may be used as precipitation agent.
[0071] Advantages
[0072] The present invention provides advantages compared to prior art techniques. Specifically, the present invention provides compositions and methods for the convenient on-site or in-situ manufacture, optimization and use of nanopolymer dispersions and derivatives. Contaminated polymer flocs may be processed to separate potentially valuable ‘contaminant’ in concentrated form and to regenerate a dispersed nanopolymer for recycle. The simplicity of the processes of the present invention is another significant advantage over the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0073] Having thus generally described the invention, reference will now be made to the accompanying drawings illustrating preferred embodiments, and in which:
[0074] FIG. 1 is a schematic view of a nanopolymer—oil aqueous mixture;
[0075] FIG. 2 is a schematic view of a portion of FIG. 1 enlarged;
[0076] FIG. 3 is a schematic view of nanopolymer-oil floc agglomeration;
[0077] FIG. 4 is a schematic view of the condensed solid nanopolymer-oil matrix; and
[0078] FIG. 5 is a schematic view of other flocculation mechanisms.
DETAILED DESCRIPTION OF THE INVENTION
[0079] Liquid Processing Using Nanopolymers
[0080] Polymer dispersions can be prepared separately from solid dispersable polymer(s) plus additive(s) prior to addition to the feed to be processed. Additive(s) were selected to optimize phase inversion characteristics for the feed to be processed. Alternatively, commercially available or prior art dispersions were used and modified with additive(s) prior to or during addition to the process stream.
[0081] Mixing and Separation Steps:
[0082] The dispersion can be injected into the feed with sufficient mixing to ensure good nanopolymer distribution prior to phase inversion. Alternatively, the method involves contacting or mixing pre-formed phase inversion solids or catenated nanopolymer slurry with the feed. Mixing is continued for the desired period at selected operating conditions, producing one or more polymer/contaminant phase(s) and purified water. The produced solid/gel/liquid phase(s) may then be removed from the aqueous solution by filtration, flotation or any other convenient process.
[0083] The separation step can be preceded by a residence time. Preferred residence times will vary according to the feed composition, polymer type, process conditions, separation method, etc. In cases where several different contaminants and/or phases are present, some components may more rapidly form separable phases than others, in which case it is possible to perform sequential selective separations. Further, the mixture may be treated during the residence time by methods of the present invention to optimize the microstructure of the nanopolymer solids for the desired separation method.
[0084] Contaminant Recovery and Regeneration of Polymer:
[0085] The contaminant and the polymer can be separated from each other by, eg. aqueous leaching, solvent extraction, re-dispersion followed by removal of non-dispersed solids, etc. Liquid oils may be recovered by squeezing the polymer-oil solids. The dispersion may then be regenerated from the purified solids.
[0086] EAA-Metal flocs may be acid-leached to yield a metal solution and extracted polymer. Alternatively, reaction with aqueous base gave dispersed polymer and hydrous metal oxide/hydroxide which was separated by settling/decantation. Acid leaching of aged metal-EAA solids of over ˜95% EAA content was not efficient.
[0087] It was found that addition of an oil to the mixture prior to phase inversion facilitated some metal/polymer leaching and regeneration processes presumably by preventing or slowing the condensation of the polymer-metal structures into non-porous, non-leachable solids.
[0088] Polishing of Effluents:
[0089] Effluent water, brine or other treated fluid can be further purified or polished via additional treatment with APD according to the methods of the present invention and/or via application of known materials and techniques such as activated carbon treatment, vapour stripping, ion exchange, distillation, membrane technologies and the like.
[0090] Nanopolymer Flocculation Mechanisms
[0091] The interaction between dispersed polymers and emulsified or dispersed oil contaminant is illustrated in FIGS. 1 to 4 . FIG. 1 represents dispersed polymer particles (represented by numeral 2 ) and oil droplets, one of which is represented by numeral 4 . FIG. 2 represents an enlarged view of the surface of the oil droplet (numeral 4 in FIG. 1 ) during the phase inversion step. The initiation of phase inversion enables catenated polymer particulates (numeral 8 ; structure illustrated in the insert) penetration of the electric double layer surrounding the oil droplet surface (numeral 9 ), presumably via polar, charged and/or ionic surface species formed and/or adsorbed during phase inversion. Alternatively, the oil droplets when in relative abundance as compared to amount of nanopolymer present may coalesce with other oil droplets via destabilized polymer particles, similar to the particulate flocculation illustrated in FIG. 5 discussed hereinafter. Either initial step may be followed by further flocculation to more extended structures ( FIG. 3 ) followed by subsequent contraction to a denser, less porous polymer-oil-water gel/solid ( FIG. 4 ), releasing water and coalesced oil phases (not shown). Obviously, whether coalesced liquid oil is released will depend on oil: polymer ratio, polymer oil capacity at the operating temperature and many other variables.
[0092] FIG. 5 illustrates possible mechanisms for particulate flocculation by soluble polymers vs APD. Structure 14 illustrates dissolved polymer chain 13 bridging through electric double layers 11 between particles 12 , binding the particles together, while 14 ′ depicts an equivalent arrangement to 14 , with insoluble polymer structure 15 acting to bridge between the particles. Alternatively, it is obvious that flocculation could proceed via interaction of the particles with a catenated polymer structure as illustrated in FIG. 2 .
[0093] The polymer surface 16 is depicted in close-up in 16 A and 16 B for PFC and EAA, respectively. 16 A shows the heterogeneous nature with an insoluble, non-porous fluorocarbon surface (shaded portion) coated with adsorbed surfactant molecules. 16 B depicts an EAA polymer cluster comprising a porous, water-swelled structure with both hydrophilic and oleophilic characteristics.
[0094] Different APD compositions possess different physicochemical properties. For example, the preferred upper limit of operating temperature in the case of acid-induced EAA flocculation is about 50° C. In contrast, acid-induced PFC flocculation can be effective at temperatures exceeding 100° C. Thus, the polymer composition will be selected to operate efficiently under the desired process conditions.
[0095] Interaction of APD Derivatives with Liquid Phases:
[0096] APD derivatives show strong interactions with liquid phases, such as variation in floc volume vs oil concentration and time (see Table 5a) and floc volume vs pH (see Table 5b).
EXAMPLES
[0097] All filtrations were done at a low pressure differential (about 4″ H2O maximum) using a coarse cellulose No2 cone-type coffee filter, unless specified otherwise.
Example 1
Processing of Oily Mixtures
[0098] General Summary: Typically, dispersed polymer and desired additive(s) were added to the oil-water mixture and mixed for the desired retention time, yielding de-oiled water phase and polymer-oil condensed phase(s). Tests were run in batch and continuous flow-through modes. Depending on oil type, oil viscosity, operating conditions and nanopolymer composition, different oil: polymer ratios were found necessary to incorporate substantially all of the oil into a filterable oil-polymer gel/solid. Higher oil: polymer ratios gave mixtures of oil-polymer gel/solid and coalesced liquid oil phase.
[0099] Addition of soluble flocculants, viscosity modifiers, particulates and/or fibrous materials could increase clarification rates and/or reduce overall polymer consumption depending on feed type, desired flocculation rate, etc. Addition of dispersed gas phase caused enhanced flotation of the coalesced oil-polymer phase(s).
[0100] Various separation methods well-known to the art, e.g. screening, filtration, membrane filtration, flotation and so forth were used as appropriate to separate the polymer-oil phase(s) from the treated water. Typically, oily suspended solids, if present, were also incorporated into the polymer phase.
[0101] Free-phase oil treatment: Pre-flocculated porous nanopolymer solids derived from EAA were found effective in absorbing non-emulsified oil droplets and bulk oils floating on water surfaces.
[0102] Using hydro-philic/phobic control of the activated floc solids, remediation efficiencies can be maximized for oil spill clean-up and other bulk oil removal applications including absorbtion and membrane phase processing. Generating ‘freshly hydrophobic’ polymer macrosolids at the instant of application to non-dispersed/floating oils increased the effective oil solidification rate and polymer oil solidification capacity. A spill clean up vessel may generate these solids either on-board for slurry application to a spill, or at the tips of mixing nozzles injecting directly into the spill surface.
[0103] It is clear that various methods of spill cleanup may be practiced according to the present invention. In-situ versus ex-situ polymer application and pre-treatment selected for the polymer dispersion, slurry or porous solid will depend on a variety of factors.
[0104] Emulsified oil treatment: Numerous qualitative tests were performed to test phase inversion as a general emulsified oil removal procedure. Water phase clarification was observed for treated aqueous mixtures containing every oil or oily contaminant type tested including crude oil/produced water mixtures, bilge water, waste oil, oil from groundwater remediation operations, refined oil, solvent extraction reagent-carrier mixture, vegetable oil, mineral oil, edible oil, fish oil, essential oil, plant oil, non-dairy coffee creamer, milk, peanut oil, peanut butter, food residues, engine oil, lubricating oil, hydraulic oil, soluble cutting oil, silicone oil, bitumen, tar, drilling mud, coal tar, tar sand extract, animal oils and fats, soap, grease, butter, dairy product, paraffin, oil-based paint, linseed oil, DEET toluamide mixture, epoxy resin, alkyl amine, ethoxylated alkyl amine, ethoxylated alkyl phenol and so forth.
[0105] Further details for treatment of specific mixtures are described in Examples 1a-1g and Tables 1a-1h.
[0106] 1a: Oil Solidification Via In-Situ Acid-Induced EAA Phase Inversion:
[0107] 2.3 g of emulsified [waste-crude-kerosene (1-1-1)] in 450 ml water+20 ppm Ca, 2.3 g dispersed EAA (20% acrylic acid, ˜6000 MW), HCl to pH<4, >5 min stir @ RT, coarse cellulose filter=clarified water plus oil-polymer solid.
[0108] 1b: Oil Coalescence Via In-Situ Metal-Induced EAA Phase Inversion:
[0109] 1,000 ml of 4,000 ppm 1:1 kerosene: bitumen emulsion, 20 ppm Ca, 2 ppm Al, 30 ppm EAA, ˜10 min stir, ˜5 min settle=clarified water+floating polymer-oil solid/liquid layer.
[0110] 1c: Non-emulsified oil removal using EAA phase inversion solids:
[0111] EAA phase inversion solids and slurries and were found to coalesce, absorb and/or solidify “free-phase” oil droplets or floating oil from water and liquid oils from surfaces. Capacities and rates varied with, e.g. porosity, pore size, oleophilicity, particle size, formulation, phase inversion additive, etc. Some of the solids had capacities of up to 5 or more times polymer weight in oil, which was recoverable from the solids by pressing.
[0112] 1d: Shear-induced EAA/oil gel formation: Mixtures of EAA/oil/water exposed to appropriate levels of mixing shear were found to produce very stiff gels with lifetimes of several days to several weeks at low polymer doses relative to amounts needed for complete oil solidification. Air could also be incorporated into the gels. This property could be useful in e.g. immobilization of oil spills on water and where APD supply is limited.
[0113] 1e: (i) EAA Recycle from Oily Flocs
[0114] (A) 20.95 g of Teresso 32 TM lubricating oil in 2000 ml H 2 O;+10 g EAA; +HCl to pH<4; filter=clarified filtrate+solid A (pressed wt=38.8 g)
[0115] (B) 30.35 g of solid A+50 ml hexane; press-filtration=18.21 g solid B.
[0116] (C) Solid B+NaOH ; 95° C.=dispersion C
[0117] (D) Dispersion C+10 g Teresso 32; 2400 ml H2O; filter=clear filtrate+solid D.
[0118] (E) Steps (B) to (D) were repeated on solid D=clear filtrate+solid E (17.8 g).
[0119] (F) 7 dispersion-precipitation cycles were completed; in all cases, re-dispersed solids had good oil flocculation activity.
[0120] 1e(ii) Re-dispersion of mixed APD polymer to yield new APDs: Re-dispersed products in some cases had superior phase inversion performance and re-dispersibility characteristics relative to the original non-phase inverted polymer admixture (see Table 1h, 7d vs 7e). It was also found possible to partially phase invert. APD mixtures prior to use with beneficial results (see Table 1 h, 9a-b).
[0121] 1f: Removal of Water from Oil Via EAA-Cellulose ‘Reverse Phase Inversion’:
[0122] Composition: kerosene (250 ml)—water (7 g) emulsion; +NaOH (1 meq); +AP820 (1 mg); high shear mix 25C=milky kerosene; +7.2 g EAA-cellulose powder, 15 min stir 25 C=cloudy kerosene; heat to 60 C, ˜1 min stir=powder agglomerated, water absorbed into polymer solids, clear kerosene phase.
[0123] 1g: Treatment of Surfactants
[0124] 1g(i) Soap (1.14 g); 650 ml water, 20 ppm Ca, 1.39 g EAA; 11 ml 1 N HCl, 5 m stir=clarified water+2.51 g dried solids. Wt calculated=2.53 g for 100% removal
[0125] 1g(ii) Ethoxylated alkyl phenol: 440 ml water, 20 ppm Ca, 0.2% TritonX45 (TM), ˜5 ppm phenol red, 0.55 g powdered carbon; 0.5 g EAA6000; 19 ppm Fe(III); 5 m stir, filter=Clear, colorless filtrate. COD's (Chemical Oxygen Demand, ppm): Feed=1120; Coarse filtrate=46, Fine (0.45 um) filtrate=17.
[0126] Tables 1a-h summarize data on samples obtained from various sources.
TABLE 1a CRUDE OIL - PRODUCED WATER SEPARATIONS ppm crude; additive source P*; ppm aq. oil; ppm Other 1: 4,000 oil; 1-3 Al oil = site1, 10-50* <10 (turb.) Settled 5-15 min aq = lab 2: 100,000 oil; 3-30Fe oil = lab, 20-50* <1 ppm TPH floc screenable from 200 ml/m bench aq = site 2 clear oil, aq phases pilot 3: ˜10,000 heavy o/w = site 3 4,000* <1 ppm TPH oil solidified, filtered oil 4: ˜2500 light oil, 2-20 o/w = site 2 30-200* <10 (turb) Metals also removed; Al phenol = C polished 5: 2,000-10,000 o/w = site 2 30-70* <10 (turb.) 200 ml/m bench pilot oil, 2-10 Al *Dose ranges are for NaHEAA Polymer types tested include: 1, 5 = EAA, EAA-CBD; EAA-cellulose; EAA-SBDVP-trioctyl amine; EAA-AP820-Fe; PE; PE-EAA; EAA-Carbon. 2-4: EAA, EAA-AP820-Fe
[0127]
TABLE 1b
TREATMENT OF OILY H 2 O/D 2 O MIXTURES
Sample type
Polymer:
TOC in
TOC out
1
(a) 0.3:1
5500;
2000*;
titration
(b) 0.7:1
2000
547**
1
1.1:1
5500
1320*
batch run A
1
0.9:1
5500
1210*
batch run B
2
(a) 0.5:1
4030;
1360*;
titration
(b) 1:1
1360
482**
2
1:1
4030
652*
batch run
“TOC” means total organic carbon;
*no visible oil in filtrate; and
**gas chromatography-mass spectrometry (“gc/ms”) detection limit estimated at ˜100 ppm.
[0128] Thus, oil and soluble TOC were removed via acid-induced phase inversion of EM
TABLE 1c TREATMENT OF OILY GROUNDWATER EMULSION (Stage 1 = EAA-oil solidification; Stage 2 = 250 ppm Paraffin oil-EAA extraction of Stage 1 filtrate) Influent Effluent Removal Compound (ppb) (ppb) (%) Stage 1 TPH* 42700 1200 97 Total BTX* 180 48 73 Total PAH* 175.6 1.8 99 Stage 2 TPH* 1200 590 50 Total BTX* 48 20 58 Total PAH* 1.8 1.2 34 *TPH = total petroleum hydrocarbons; BTX = benzene toluene ethylbenzenes xylene; PAH = polynuclear aromatic hydrocarbons
[0129] Table 1b data illustrate oil solidification (Stage 1) and solvent extraction (stage 2). Obviously, higher stage 2 removals may be achieved via replacement of oil/EM by a solvent/polymer combination with a greater affinity for aromatics.
TABLE 1d CONTINUOUS TREATMENT OF OILY WATER Acid-induced EAA phase inversion Oil in (ppm) Oil out (ppm) Polymer:oil Removal (%) 85 1 1.1:1 >99 814 4 1:1 99 1786 2 1:1 >99 101 3 0.9:1 97 126 4 0.7:1 97 189 3 0.5:1 98 378 2 0.2:1 99
[0130]
TABLE 1e
EAA polishing of APD-oil-aluminum phase inversion mixtures
NTU
APD1
HCl
APD2
Turb1*
Turb2
reduction, %
Observations
AF4530
0
EAA6000
>500
7.01
>98.6
W830/256
0
EAA6000
23.8
5.10
79
W830/256
0
EAA8000
23.8
12.1
49
W830/140
2
EAA6000
15.4
0.47
97
W830/177
2
EAA6000
31.1
0.13
99.6
W830/397
2
EAA6000
91.4
0.48
99.5
AirFlex 325
2
EAA8000
911
0.55
>99.9
NTU pre-HCl
ME68725
2
EAA8000
14.01
0.40
97
33 NTU pre-HCl
ME68725
2
MP4983
14.01
0.68
95
50 NTU pre-
HCl
ME68725
2
EAA-Rubber
14.01
0.67
95
55 NTU pre-
HCl
*measured for APD1 + oil aqueous mixture
For polymer identification, see list in Example 3
***Test 22-31 base sol'n = 100 ppm Crude Oil Emulsion + 20 ppm Al + 500 ppm APD1 + 233 ppm APD2
[0131]
TABLE 1f
Oil and iron removal from API separator effluent
Sample
Ca
EAA
Turbidity
Oil
Fe
ID
(ppm)
(ppm)
(NTU)
(ppm)
(ppm)
Sample 1
—
—
˜2,500
18.2
Trial1
10
50
12.51
7.0
0.26
Trial 2
10
100
19.38
20
0.38
Trial 3
10
25
44.2
68
1.14
Sample 2
—
—
n.a.
10.36
Trial 1a
0
50
14.1 (5 m mix;
10
0.02
screen-decant)
Trial 1b
0
0
3.95 (1a decantate,
0.2
0.03
15 m stir, filter)
[0132]
TABLE 1g
Some EAA-oil removal variables
Feed = ˜800 ppm crude/waste/kerosene
APD
time
test
Ca
Al
(100 ppm)
(m)
Filtrate oil, ppm
1
20
0
none
3
525
2
20
9
none
3
120
3
20
0
cel-EAA
3, 20
45, 18
4
40
0
cel-EAA
3, 10
18, 12
5
20
1
cel-EAA
4
˜1
6
20
0
EAA1&2
3, 10
18, 12
7
20
5
EAA2
3
<1
EAA1 = Dow Primacor 5990,
EAA2 = Dow Primacor 5980
[0133] Table 1g 3-7 shows that 1-5 ppm Al removes oil turbidity faster and more efficiently than 20 ppm Ca when used with 100 ppm EM or cellulose-EM. Further, EM and cellulose-EAA both removed circa 8 times their weight in oil There was no difference in performance of Dow EAA polymers of MW 6,000 or 8,000 in this test.
TABLE 1h Oil removal: Effect of soluble polymer and APD formulation size Al sol. plmr/ Filtrate; ‘oil’ removal Test APD/ppm nm ppm ppm ppm ‘oil’* % 1a none — 3 AP820/3 48 94 1b bentonite/100 <35,000 2 AP820/3 <1 99.9 1c ben/100; EAA/10 — 2 0 ˜60 93 2a EAA/3 ˜25 2 0 54 94 2b EAA/3 ˜25 2 AP820/1 <1 99.9 2c EAA/2 ˜25 2 AP820/0.67 ˜1 99.9 2d EAA/10 ˜25 1 0 ˜30 97 2e EAA/10 ˜25 2 mucilage/10 ˜2 99.8 3a PTFE/400 12,000 5 0 4 99.5 3b PTFE/400 12,000 5 AP820/2 <1 99.9 4 Sty-Acr/100 30 5 0 3 99.6 5a amide/100** 500 7 AP820/2 ˜15 98.3** 5b am-EA-Fe/200*** — 9 0 <1 99.9 6a Paraffin-PE/10 60 3 AP820/1 <1 99.9 6b Paraffin-PE/3 60 3 AP820/1 <1 99.9 6c Paraffin-PE/100 60 5 0 ˜1 99.9 7a CBD/50 60 5 0 ˜180 79 7b CBD/50 — 5 AP820/2 <1 99.9 7c CBD/50; EAA10 — 5 0 ˜120 86 7d CBD/50; EAA/50 — 7 0 100 88.5 7e 1:1 CBD-EAA-Fe — 7 0 3 99.7 8a PE ‘phob’/200 12,000 3 0 30 96.6 8b PE ‘phob’/200 12,000 3 AP820/1 <1 99.9 8c PE ‘phil’/200 12,000 3 0 3 99.6 9a*** EAA-AP820-Fe/3 — 2 — ˜4 99.5 9b EAA-AP820-Fe/6 — 3 — ˜1 99.9 ALL: kerosene = 870 ppm; Ca = 20 ppm, 5 m stir, filter. APD = 1 aliquot except 2c, 9b = two aliquots separated by 30 s. 1a-c, 1aliquot AP820, 2-9; AP820 = 2 aliquots spaced by 30 s, 30 s after Al (time 0). *estimated from turbidity; other sources of turbidity will analyse as oil. **results were highly variable due to fragility of flocs ***am-EA-Fe = 1% {1:1 EAA:amide + [⅔HCl + ⅓Fe]/stir} + NaOH/90 deg C.; EAA-AP820-Fe = ([1% EAA − 1/16% AP820] + 27 ppm Fe)
[0134] The results summarized in Table 1h have several features worthy of note. Test 1a shows that 3 ppm soluble flocculant leaves significant oil in the filtrate while test 1b and lc show that provision of suspended inorganic bentonite solids improves performance of soluble polymer but not EAA(cf 2d). Further, addition of small amounts of EAA without soluble polymer (2a, 2d) leaves significant oil residues in the filtrate. However, tests 2b,c and e show that addition of soluble polymer results in substantially complete oil removal even at low EAA doses.
[0135] The results for tests 2 discussed for EAA are reflected in tests 3 and 5-8 for other polymers, i.e. addition of soluble polymer enhances oil removal by APD.
[0136] Also illustrated in Table 1h are the effects of particle size: larger APD particles require larger doses for similar oil removal performance. Further, comparison of EAA/CBD admixture performance (7d) to that of a 1:1 EAA-CBD phase inversion-redispersion product (7e) shows that the formulation derived via phase inversion methods was superior to that of a non-inverted APD mixture.
[0137] Of particular interest in Table 1h is the comparison of performance between “hydrophobic” (“phob” in Table 1h) PE and “hydrophilic” (“phil” in Table 1h) PE. The “hydrophobic” form was created by wetting dry PE powder with isopropanol, then diluting with 9 volumes of water. The “hydrophilic” form was created by wetting the dry PE powder with isopropanol and adding directly to the stirred oil-water mixture. The data indicate that the process of in-situ phase inversion of the dispersed polymer from more to less hydrophilic states is an important factor in APD performance.
[0138] Of further interest in Table 1h are tests 9a and 9b, indicating that a combination product from the partial phase inversion of soluble flocculating polymer—APD mixture is useful as a de-oiling agent.
[0139] It will be obvious to those skilled in the art that the methods of the present invention may be combined with each other and/or with any other suitable method(s) to optimize performance.
[0140] Such techniques include gravity settling, absorption, adsorption, precipitation, electrostatic precipitation, heating, cooling, chemical addition, filtration, hydrocyclone treatment, centrifuging, flotation, gas flotation, hollow fibre phase separation, coalescence, ultrasonic treatment, exposure to electromagnetic radiation, microfiltration, nanofiltration, distillation, freezing, drying, solvent extraction, etc.
Example 2
Metal Processing
[0141] In addition to the aforementioned novel aspects, the processes of the present invention as applied to metal processing will be further discussed and compared with prior art methods in Examples 2a-2d.
[0142] 2a: Titration of EAA with Mixed Metals:
[0143] 500 ml sulfide ore leachate. Sequential EM addition; 20° C./stir 5 m/filter/isolate solids, repeat.
[0144] EM additions: Stage A=3.2 meq; Stages B to F=0.83 meq; Stage G=3.1 meq; Stage H=2.1 meq. Selected polymer-metal precipitates were analysed for metals content. The results are summarised in Table 2a.
TABLE 2a ANALYSES OF EAA-MIXED METAL SOLIDS FROM MULTISTAGE TITRATION* Stage H Metal Feed** Stage A solid Stage B solid Stage F solid solid Al 102.1 1650 5480 9390 54 Sb 0.153 2.8 17.5 1.2 <0.3 As 1.013 25 13 7 3 Ba 0.0012 <0.3 <0.3 <0.3 7 Be 0.009 <0.3 0.6 2.1 <0.3 Bi 0.001 12 1.1 <0.3 <0.3 B 0.088 11 <0.3 <0.3 <0.3 Cd 0.206 3.1 3.2 7.1 3.4 Ca 29.32 1120 1420 2180 14600 Cr 0.0036 6 5 10 <3 Co 0.463 4.1 4.3 6.9 85.9 Cu 98.74 992 1570 3760 205 Fe 113.4 19000 9290 200 <60 Pb 0.138 8.6 4.4 9.5 0.9 Mg 53.9 190 230 330 430 Mn 30.53 296 293 631 6650 Mo 0.0002 0.8 0.9 0.4 <0.3 Ni 0.25 <3 4 4 43 Se 0.002 49 39 23 12 Ag <0.0001 <0.3 <0.3 <0.3 <0.3 Sr 0.023 5 5 8 43 Te 0.0001 1.3 0.6 <0.3 <0.3 Tl <0.0001 1.2 0.5 <0.3 0.4 Sn 0.0008 1.2 1.1 0.5 0.5 U 0.026 1.4 7.9 2.1 <0.3 V 0.007 <0.3 <0.3 <0.3 <0.3 Zn 13 1320 1350 2550 11400 *All values are in ppm. **Calculated from concentrate analysis divided by dilution factor of 19.85
[0145] 2b: Reaction of Dispersed Latex with Copper and Iron Solutions:
[0146] 2b(i) 600 ml of 1,000 ppm siliconized acrylic latex; ˜320 ppm Cu; pH=8.5. 2 m stir, ˜30 m settle=blue sinking floc+clear colourless supernatant. Decantate-Filtrate=<1 ppm Cu or >99.7% Cu removal. The blue solids released copper at pH ˜5.5.
[0147] 2b(ii) Similar results were obtained with Fe(III)- and Fe(III)/Cu(II)-latex mixtures. The metal-latex solids also absorbed kerosene from a water/kerosene mixture.
[0148] 2c: Metal Oxide-Hydroxide Flocculation, Dispersion Regeneration and Metal Oxide-Hydroxide Concentrate Recovery:
[0149] Mixed metal oxide/hydroxide floc was produced from (Fe,Zn,Cu) sulfide ore leachate plus NaOH. Treatment of a first ore leachate aliquot with EAA at 15 C followed by warming to ˜40° C. gave compact metal-polymer floc.
[0150] The mixed metal floc was re-dispersed (100C aq. NaOH) and added to a second aliquot of ore leachate resulting in formation of a brown polymer-metal floc and blue solution, indicative of flocculative selectivity for iron over copper. This re-dispersion/re-precipitation cycle was repeated five times and resulted in increasingly brown precipitate and filtrates containing copper, i.e. copper-iron separation.
[0151] In similar experiments, iron oxide/hydroxide concentrate was separated from the re-dispersed phase via settling/decantation, thus providing an improvement to procedure 2a for the selective separation and production of purified metal concentrates and purified aqueous phase at much lower polymer consumption than anticipated by the prior art.
[0152] 2d: Comparison of Present Invention and Prior Art for Copper Removal:
[0153] 2d(i) Prior art method: Similar to that described in Vaughn et al, U.S. Pat. No. 4,747,954: 1,000 ml of DI water containing 3.6 ppm Cu(II) was stirred at 25° C. for 5 minutes with 0.042 g of EAA6000 (˜7% excess). The filtered solution contained substantial unremoved copper-EAA dispersion and rapid filter fouling was observed. Similar results were obtained when a cellulose-EM polymer dispersion was used.
[0154] 2d(ii) Comparative example: In a comparison of copper removal capacity, 0.13 g Cu(II) in 1000 ml of DI water was mixed with 4 meq NaOH then 0.022 g of EM6000 polymer, giving blue solids and colourless filtrate. In a comparative test of the method according to Vaughn, addition-of 0.022 g a EM6000 polymer to 0.13 g Cu/1 000 ml produced only a trace of blue solid and the filtrate was blue, indicating the presence of substantial unremoved copper.
[0155] 2d(iii) EAA/emulsified solvent extraction, 1100 ml of 3.6 ppm Cu(lI) in DI water was emulsified with 0.48 g of 1:1 w/w tri-n-octyl amine in kerosene. 0.4 g of EAA6000 was added as a 10% dispersion; a voluminous pale blue floc formed; addition of 1.44 g of 1 N HCl resulted in a less voluminous floc. Filtrate was substantially copper-free.
[0156] 2d (iv) In a typical example of copper removal by acid-promoted polymer phase inversion, 4 ppm Cu(II) in 1,000 ml DI water and 0.08 g of EAA6000 (77% excess) were stirred 1 min at 25° C., then adjusted to pH ˜4 using 1 ml 1 N HCl. Pale blue floc and a filtrate substantially free of copper were obtained.
[0157] 2d(v) This example illustrates copper removal by metal ion-promoted phase inversion: 1 ppm Cu(II) in 10,000 ml of water containing 21 ppm Ca was stirred at 22° C. with 20 ppm of EM6000 for 10 min. A green (copper-containing) floc was obtained. A similar preparation without addition of Cu(II) yielded colourless solids.
[0158] 2d(vi) Selective removal and recovery of copper. 2,000 ml vol; 20 ppm Cu(II), 21 ppm Ca, 20 ppm Fe(III); +NaOH (2.5 meq);+EAA (25 ppm); 2 m stir; 20 m settle=circa 55 ml green floc; +0.5 meq acid=Cu leachate+solids; filter=˜53 ml pale blue filtrate and 1.45 g pressed filter cake containing iron.
[0159] 2d(vii) Removal of Cu was also achieved via flocculation with the non-EAA type polymer styrene-butadiene-vinyl pyridine(SBDVP) at approximately 0.6:1 Cu: polymer weight ratio.
[0160] Example 2d(i) shows that 3.6 ppm copper is not removed by 40 ppm EAA polymer dispersions when processed by the method of Vaughn. In contrast to this observation, 2d(iii to v) show that addition of appropriate amounts of co-additive and/or co-reagent including oil-chelant mixture, acid, and/or suitable non-target metal ion to dispersed EAA resulted in substantial removal of similar copper levels. Therefore, the results exemplify the significant differences of the present invention as compared to Vaughn.
[0161] Example 2b describes the use of a commercial latex of unknown formulation to treat copper and iron solutions. 99% metals removal was achieved. Example 2d(vii) illustrates use of a non-EAA derived polymer for copper removal. Thus, a variety of nanopolymer phase inversion-based processes are of utility in the treatment and processing of aqueous metal mixtures.
Example 3
Treatment of Suspended Solids
[0162] Nanopolymer floc processing of certain feeds containing solids in mixtures with oil and/or metals is described in preceding Examples 1 and 2. Additionally, a wide variety of other aqueous suspensions were successfully clarified via nanopolymer flocculation, including in a non-limiting sense suspensions of tar sand tailings, ore tailings, municipal sludge, industrial sludge, clay, carbon, yeast, protein, talc, blood, food residue, precipitated compound, etc. The procedures of the present invention may also be adapted to processing “non-phase invertible” APD mixtures as exemplified previously e.g. for oil-APD1 mixtures (Table 1e).
[0163] “Non-phase invertible” APD will refer to APD polymers and/or APD mixtures in which phase inversion and/or floc separation is difficult or inconvenient to achieve under the process conditions, as opposed to, e.g. the readily separated EAA-oil phases of Examples 1a and 1b. It has been found that separating such mixtures may be facilitated by addition of a readily phase invertible polymer such as EAA or a soluble flocculant e.g. AP820. This procedure may be useful for example in the treatment of mixtures in which the desired contaminant is optimally sorbed by a non-phase invertible APD, with the resulting APD-contaminant particles being removed via treatment using a phase invertible APD and/or a soluble flocculating agent.
[0164] Examples 3(a-e) and Tables 3(a-f) summarize data from typical experiments.
[0165] 3a: Flocculation and De-watering of Yeast:
[0166] 3a(i) 1.0 g yeast; 1 meq NaOH; 1,000 ml water; 20 ppm Ca; 0.08 g EAA; 2 m stir, 3 m settle, decant-filter=clarified water+pressed solids (2.57 g; ˜31% solids).
[0167] 3a(ii): Time:settled floc volumes: 5 m: 40 ml, 15 m: 20 ml, 30 m: 20 ml.
[0168] 3b: Inorganic coagulant/hydroxide co-flocculation: 4 ml 0.6N Al(III); 1.00 g yeast; 900 ml DI water; 2 m stir; 3 meq NaOH, 1 m stir, 0.005 g EAA, 15 m mix; 30 m settle=clarified supernatant+20 ml floc.
[0169] 3c: Tables 3a-3f Summarize Other Results
TABLE 3a EAA-LATEX RATIO VS FILTRATION RATE Latex:EAA Filtrate/2 min (ml) Turbidity, NTU 13.3:1 92 — 50:1 40 — 100:1 32 0-25 ml = 7.8; 95-120 ml = 0.34 200:1 29 — 500:1 28 (hazy) —
[0170]
TABLE 3b
EAA - CELLULOSE AND EAA - YEAST FLOC DATA
X:Plm/meq/l NaOH
Filter cake % solids
Recovery, %
Cel:EAA = 10:1/1
48
87
Yeast:EAA/meq/l NaOH
5:1/1
34
91
10:1/1
28
80
20:1/2
45
72
[0171] 3(d) EAA Sludge Dewatering
[0172] 14.73 g Fe/EM/H2O sludge (˜15% solids); water (50 ml); 0.2 g EAA(16% dispersion); 30 s stir; +HCl to pH<4; 1 m stir; +250 ml 100C water=press-dewatered sludge (10.6 g; solids content=30%, for a 100% increase in solids % over starting Fe/EM sludge.) summarizes data from similar tests except 100 C water was not added prior to pressing.
[0173] 3(e) Preparation of phase invertible APD mixtures in-situ: The data in Table 3c illustrate that EM-APD mixtures may be co-flocculated resulting in substantial removal of both-APD types.
TABLE 3c APD1/APD2 FORMULATION SCREENING 500 ppm APD1; 20 ppm Ca; 20 ppm Al; EAA MW = 6000; 15 m stir; filter; +acid (opt) APD 1 ml HCl EAAppm *NTU in **NTU out % removal 1 CBD 0 116 733 0.41 >99.9 2 ML156 0 233 375 2.71 99.3 3 ML110 0 233 150 1.02 99.3 4 SBA 0 233 468 0.31 99.9 5 ME27720 0 233 1174 0.24 >99.9 6 BSVP 0 233 193.5 0.50 99.7 7 BSAA 0 233 209 1.36 99.3 8 EAA1410 0 233 755 1.6 99.8 9 AF 315 0 233 1057 5.0 99.5 10 Flbond325 1 233 842 0.2 >99.9 13.2 NTU pre-HCl 11 AF 4500 1 233 347 6.24 98.2 14 NTU pre-HCl 12 AF 4530 2 233 423 0.83 99.8 14 NTU pre-HCl 13 430Em 2 233 576 0.50 99.9 14 MP4983R 2 233 S/F 0.47 >99 19NTU pre-HCl 15 ME68725 2 233 N/A 2.04 >98 17.45 NTU pre- HCl 16 Mic05940 2 233 128 1.16 99.1 17 Fstr 2774 2 233 678 0.67 99.9 18 EAA/AP820 0 233 S/F 0.17 >99.9 19 EAA-Rubber 0 233 S/F 0.50 >99.5 20 urethane 2 233 91.7 0.39 99.6 21 Soap 0 233 S/F 0.15 — *Denotes nephelometric turbidity units **Denotes reduction in nephelometric turbidity units SF denotes self flocculating
[0174]
APD Polymer compositions
Trade Name
Polymer Type
PrimacorTM series (Dow
EAA, pH˜9; 25-90 nm; NS
Chemical Co)
EAA derivatives
Various
BAYPREN-LATEX T 58%
Chlorobutadiene (“CBD”), NS
BAYSTAL S X 8678 50%
Styrene - Butadiene; NS
ACRALEN BS 40%
Butadiene-Styrene-acrylamide-acrylonitrile-methacrylic acid;
NS
LIPATON AE 4620 50%
Styrene-n-butyl acrylate; NS
PYRATEX 241
Styrene-butadiene-Vinyl pyridine; NS
ABK: - AS 6800VP50%
Styrene-mod Acrylic-methacrylic acid ester; Anionic 30 nm
ABK: - H 595 30%
Styrene-mod Acrylic-methacrylic acid ester; Anionic 30 nm
ABK: - AC548 50%
Acrylic-Methacrylic acid ester; Anionic 60 nm
ML110, 25%
#1 Carnauba wax, PE, anionic; 60 nm, pH ˜9
ML180, 25%
#1 carnauba wax, paraffin; 180 nm; anionic
MG15, 40%
PTFE, 12,000 nm; anionic surfactant; pH8.5
ME05940, 40%
Paraffin; 90 nm; nonionic
ME27720, 20%
Polyamide; 500 nm; nonionic
ME68725, 25%
PE type AC(TM)629, nonionic, 45 nm; pH˜10
ME39235, 35%
AC(TM)392 high density oxidized polyethylene; 35 nm,
nonionic
ML156, 25%
#3 Carnauba wax; 130 nm; nonionic; pH˜5
AP: 4500
Poly Ethylene-Vinyl Chloride
4530
Poly Ethylene-Vinyl Chloride
315
Poly Vinyl acetate
325
Poly Vinyl acetate
430
Poly Ethylene-VinylAcetate-VinylChloride
INCOREZ W830/140
Polyurethane; Polycarbonate backbone; 7.3% co-solvent
INCOREZ W830/177
Polyurethane; Polyester backbone
INCOREZ W830/256
Polyurethane; Polycarbonate backbone; 8.4% co-solvent
INCOREZ W830/397
Polyurethane; Polyether backbone
(NS = no surfactant; “anionic” = anionic surfactant; “nonionic” = nonionic surfactant)
(ML = Michem Lube; ME = Michem Emulsion; MP = Michem Prime; MG = Michem Glide; ABK = ALBERDINGK; AP = Air Products)
[0175] Soluble polymers: Mucilage (LePage) and AP820 (Cherokee Chemical Co Inc) were diluted in water prior to use.
TABLE 3d APD-CARBON FLOCCULATION Mixture composition: 500 ml pre-settled carbon suspension/approximately 200 ppm APD/0.8 meq Fe Filt. NTU* % removal APD composition Visual observations control vs none (control) black suspension 14.6 — EAA6000 fine fragile floc 0.53 96 Chlorobutadiene fine fragile floc 0.75 95 Styrene-butadiene-vinyl large robust floc 0.34 98 pyridine *20 min settle, filter 2 × 100 ml, measure turbidity of second 100 ml aliquot; **settle 30 m; decant top 100 ml
[0176]
TABLE 3e
CARBON-APD FLOCCULATION VS APD TYPE
1,000 ppm C; 20 ppm Ca; Feed turbidity = ˜152 NTU
APD type
Polymer, ppm
% turbidity removal
none
0
0
S-BD-vinyl pyridine(SBDVP)
5
92
Chlorobutadiene (CBD)
5
90
EAA MP4983R
10
99
[0177]
TABLE 3f
FLOC DEWATERING
X: Polymer Type and dry wt Ratio
Pressed Filter cake; %
Recovery, %
Cellulose:EAA = 10:1
48
87
Yeast(Y):EAA = 5:1
34
91
Y:EAA = 10:1
28
80
Y:EAA = 20:1
45
72
Y:SBDVP:EAA = 60:5:1;
48
—
+0.4Fe/1.2Cu
Cu:SBDVP = 0.6:1*
36
—
0.3 Fe(III):11.6 CBD*
71
95
1 Fe(III):39 EAA
25
—
1 Fe (III):39 (1:1 EAA:CBD)
26
—
1 Fe (III):39 CBD*
71
95
carbon:EAA = 10:1
40
—
carbon:SBDVP = 10:1
45
—
carbon:CBD = 10:1
42
—
municipal sludge:EAA = 15:1
62 (60 C.)
—
*no metal observed in filtrate
SBDVP denotes a styrene-butadiene-vinyl pyridine copolymer
[0178]
TABLE 3g
Effect of EAA formulation
20 ppm Al
EAA derivative
filtrate turbidity, NTU
MP4183 (as supplied)
1.22
NaPE/EAA8000
0.22
Cellulose/EAA6000
0.23, 0.15
Rubber-EAA6000
0.18
EAA6000/AP820
0.20
PEVC/EAA6000
0.30
Cu/EAA6000
0.18
5C/EAA6000
0.20
3C/EAA6000
1.00
[0179] The above examples clearly illustrate that the methods of the present invention can be used to flocculate and/or dewater a variety of aqueous suspensions, sludges, flocs and non-phase invertible polymer dispersions. Clearly, APD type(s) and process conditions will be chosen to maximize flocculation, clarification and de-watering characteristics for specific feeds.
Example 4
Processing of Soluble Non-Metallic Compounds
[0180] 4a: Colour removal from commercial effluent: 500 ml blue fabric dye plant effluent+5.5 meq Fe(III); 1 m stir; 500 ppm EAA; 2 m stir; 1.1 meq Fe(III); 5 m stir=blue solid+colourless filtrate.
[0181] 4b: Separation of dye components: (0.1 g blue+0.1 g yellow) food colour liquids+125 ml water=green solution; +1.0 g of EAA; +1.7 g 10 N HCl=blue solid+yellow filtrate, thus the yellow and blue dyes were separated by the treatment.
[0182] 4c: EAA and pH-indicating dyes: A number of qualitative tests were performed on acidification of EAA-dye mixtures in water. Dyes included bromocresol purple, chlorophenol red, metacresol purple, dimethyl yellow, bromophenol blue and methyl violet. Phase inversion resulted in the formation of coloured polymer solids and partial colour removal from the aqueous phase, depending on factors such as EAA: dye ratio, pH, metal concentration, etc. The polymer solids underwent colour changes upon exposure to different pH's, all released dye when mixed with water at pH>˜8.
[0183] 4d: Non-EAA polymers: Similar results to 4c were obtained using non-EAA APD's including styrene-butadiene-vinyl pyridine, chlorobutadiene, styrene-acrylic, carboxylated styrene-butadiene and other formulations.
[0184] In combination with colloidal carbon, superior decolorization results were achieved. It is noted that functional groups including substituted aromatic hydrocarbon, phenol, cresol, halogen, sulfur-oxygen, carboxylic acid are contained in one or more of the dyes evaluated. Therefore, soluble organics having a variety of substituent types may be processed by the methods of the present invention.
Example 4e
[0185] Egg yolk (5 ml); 200 ml water; +0.5 g EAA; +10 ml 5% acetic acid; 5 min stir; filter=clear colorless filtrate+yellow solids. The presence of residual colorless organic compound(s) was inferred by the slight foaming tendency of the filtrate on shaking. Example 4e shows separation of egg yolk into components via nanopolymer phase inversion.
[0186] In addition to Examples 4a-e, soluble TOC removal is illustrated in Tables 1a and 1b, thus it is demonstrated that the present invention has utility in the processing of a wide variety of water-soluble organic materials.
Example 5
Effect of Selected Variables
[0187] 5a: Filterability vs. Mixing Time:
[0188] 21 ppm Ca plus 100 ppm EAA were stirred (medium speed magnetic stirrer setting) without aeration for the desired interval at 20° C. and filtered (coffee filter) until ˜90% of filter flux was lost, yielding the following data:
[0189] Mix time (min: sec) 0:05 0:15 0:30 0:45 1:00 2:00 5:00 10:00 15:00 30:00
[0190] Filtrate volume (ml) 45 52 68 89 115 240 490 960 1,310>2,000
[0191] 5b: Thermal and Aging Effect on Floc Volumes
[0192] 5b(i): 1.5 g EM, 500 ml H2O; +10 meq HCl; stir, settle; measure floc vol vs time
[0193] 5b(ii): Procedure (i) was repeated using EAA MW 6000 polymer.
[0194] 5b(iii): Procedure (i) was repeated using 1:1 EAA:PE mixture
[0195] 5b(iv): Procedure (i) was repeated except 3 ml corn oil was also added to the mixture.
[0196] 5b(v): Procedure (ii) was repeated except 3 ml corn oil was also added to the mixture.
[0197] 5b(vi): Procedure (iii) was repeated except 3 ml corn oil was also added to the mixture.
[0198] 5b(vii): Procedure (i) was repeated using 1.9 g EAA8000, 0.1 g Fe(III).
[0199] 5b(viii) Procedure (vii) was repeated except equivalent amount of Cu was added
[0200] 5b(ix) Procedure (vii) was repeated except equivalent amount of Al was added
[0201] Results are summarized in Table 5a.
TABLE 5a THERMAL STABILITY OF NANOPOLYMER FLOCS Relative floc volumes (ml/g) vs time, polymer type and additives 43(i) 43(ii) 43(iii) 43(iv) 43(v) 43(vi) 43(vii) 43(viii) 43(ix) Time(m); T˜15 C. 1 50 74 74 6 6 10 100 100 95 10 — — — — — — 100 88 88 30 33 67 60 2.7 5 3.3 — 25 — 60 27 50 47 2.7 3.3 2.7 — — — 240 10 17 14 2.7 3.3 2.7 — — — Temperature 50° C. 2.7 4 3.3 2.7 3.3 2.7 50 17 65 100° C. — — — — — — ˜6 6 —
[0202] 5c: Ca-EAA Floc Interactions:
[0203] A voluminous floc was prepared by extended shaking/aeration (about 10 min.) of 0.36 g EAA8000 polymer (added as a 13% dispersion) in 1 liter of water containing about 21 ppm of Ca. Floc volumes were monitored after ˜15 min. settling as temperature and NaOH concentration were varied. A similar trial was run with PE dispersion. Results are summarized in Table 5b.
[0204] 5d: Floc—pH Interactions
[0205] 38(vii): A voluminous floc was prepared by extended shaking/aeration (circa 10 min.) of 0.36 g EAA in 1 l of 20 ppm Ca followed by treatment as summarized in Table 5c.
TABLE 5b floc volumes vs NaOH concentration, T and dispersion type floc volume (ml) Temperature(deg C.) ml 1 N NaOH EAA PE 20 0 200 ˜45 33 0 400 ˜45 40 0 300 ˜45 45 0 200 ˜45 50 0 100 ˜45 50 1 150 floc disintegration 50 2 200 —
Example 6
Soil Extraction Process Enhancement
[0206] General Procedure: A sandy soil containing 5 wt. % (heavy crude: train yard waste: used lubricating oil=1:1:1 (wt.)) was used as “soil” feed. Aliquots were extracted by stirring (5 m); compositions and extractions are presented in Table 9.
TABLE 9 EAA soil extraction Run # soil, g Surf., g gasoline, g EAA, g % extraction 1 16 1 0.1 0** 30 2(i) 16.1 1.5 0.1 1.0** 88; 2(ii) 16.4 2.7 0.1 0.88 68 3(i) 16.5 2.0 0.1 0.35** to stage 2 3(ii) Stage 2 4.6 0.1 0.46** 108 150 ml aqueous phase; 15 C unless otherwise noted *= ethoxylated nonyl phenol surfactant, 2.75% in water **= plus 0.1 g NaOH
[0207] The data in Table 9, 2(i) vs 1; indicate significantly improved performance of prior art surfactant-solvent mixtures upon addition of EAA to the composition. It is noted that for 2(ii), EAA nanopolymer without NaOH, the degree of performance enhancement is reduced, inferring a less optimized aqueous nanopolymer structure for the leaching process relative to 2(i). 3(i-ii) illustrate data from a two-stage leach/drain/leach process. | The present invention provides for a method of producing a composition containing a polymer having undergone phase inversion, the method comprising the step of: effecting phase inversion of a phase invertible water insoluble polymer in an aqueous composition and the composition comprises a mixture of at least two different substances, one of which is a water insoluble dispersible polymer having undergone phase inversion while the other is optionally a contaminant. | 8 |
This is a Rule 60 Continuation of parent application Ser. No. 127,205, now abandoned.
BACKGROUND OF THE INVENTION
The invention relates to an apparatus for pulling monocrystals out of a melt situated in a crucible under vacuum. The apparatus has a vacuum chamber in which the crucible is disposed, a means for heating the melt, a pulling means above the melt, and a cover having an opening and situated above the melt through which the monocrystal can be pulled upwardly from the surface of the melt.
When monocrystals are pulled from a melt under vacuum conditions it is very important to keep the temperature ratios at the crucible margin as low as possible and prevent flows from forming in the melt.
To counteract disadvantageous effects in the pulling of monocrystals in a known apparatus for pulling monocrystals (U.S. Pat. No. 3,359,077 to Arst) a cover has already been used over the melt to reduce the thermal gradient at the surface of the melt.
It is furthermore known (EU-0 170 856) to make the crucible for the melt bipartite and provide it with a cylindrical insert and arrange the charging funnel of a recharging apparatus such that the recharging material can be poured into a marginal portion remaining between the margin of the inner shell of the crucible and the insert. This known apparatus is equipped with two heaters of which one has a flat, discoidal configuration and is held underneath the crucible, and the other is in the form of a hollow cylindrical body surrounding the crucible.
Lastly, an apparatus (U.S. Pat. No. 3,511,610) is already known which serves to reduce any excessively great temperature difference between the end of the seed crystal and the melt, the part bearing the seed crystal being provided with a heating means by which the heat can be transferred to the seed crystal with the aid of the carrier of the latter. This purpose is served by a plate on the element that pulls up the crystal holder.
SUMMARY OF THE INVENTION
The present invention has the object of improving the melting of the continuously fed charge material, to prevent any great agitation of the bath by the charging during the pulling, and to prevent increases in the temperature of the crucible wall caused by the passage through it of energy for melting the added charge material.
This object is achieved by an approximately annular, flat first heater body extending in a plane parallel to the bottom surface of the crucible, and a substantially cylindrical second heater body at least partially surrounding the crucible and disposed so as to be perpendicular to the plane of the first heater body, which merges at its upper end with an approximately plate-like heater body parallel to the first heater body, which is disposed in a plane between the upper margin of the crucible and the bottom of the annular covering.
The plate-like portion of the second heating body which is constructed in the manner of a flange and at least partially covers the melt, permits direct heating of the added material without exposing the crucible as a whole to heating.
Instead of a cylindrical second heater equipped with an annular, flat portion, a substantially discoidal, flat second heater can also be provided whose thin annular portion is disposed in a plane between the upper margin of the crucible and the bottom of the annular cover, the thin annular portion having one or more heater feet extending perpendicularly downward, which engage in recesses which are provided on the clamping jaws, the heater feet being clamped, wedged or screwed into the recesses.
The power supply both of the first heater body (the one heating or temperature-controlling the crucible) and of the second heater body (the one acting directly on the charge material) is best separate for each, since the heating power of the second heater body depends directly on the amount of additional charge put in per unit time.
Preferably the plate-like first heater body is held by at least two rod-like power feeders disposed parallel to the crucible supporting column, the power feeders being on the one hand brought through the bottom plate of the pot with insulation, and on the other hand being fastened to the feet of the first heater body.
The feet of the first heater body, which are affixed to the power feeders, are bound together through two substantially semicircular portions. These portions, which include a central opening, are formed of serpentinely configured heater coils.
To advantage, the annular, flat portion of the cylinder-shaped second heater body is provided with a plurality of slots distributed on its circumference, which extend all the way into the area of the cylindrical wall. Alternatively or additionally the wall of the substantially cylindrical second heater body is equipped with a plurality of slots distributed on the circumference of the wall, which extend inwardly from the bottom edge of the heater body into the area of the annular flat portion extending radially inward.
The wall of the second heater body is best provided with downwardly extending feet which are engaged in recesses which are provided on radially inwardly extending clamping jaws held by the power feeders, the foot portions of the second heater body being wedged in the more or less rectangular recesses with the aid of wedges, or being screwed or riveted therein.
To assure the continuous feeding of the charge material, the annular, flat portion of the cylindrical second heater body has openings or holes through which the filler funnel of a filler tube of the charging apparatus reaches, which is provided outside of the pot.
Preferably the crucible and the two heater bodies are at least partially surrounded by a substantially cylindrical guard tube which rests with its bottom margin, provided with openings, on a molten material catching pan which in turn is held on the bottom plate of the pot by a tube, the molten material catching pan extending in a plane parallel to the plane of the bottom surface of the crucible and having a central bore through which the vertical crucible holding column is passed.
To assure a uniform distribution of heat with low heat losses, both the pan for catching the molten material in the event of crucible breakage, and the guard tube, and the cover plate disposed over the crucible and borne by the guard tube is clad with insulating material mats, preferably of graphite felt.
To prevent agitation of the melt, a hollow cylindrical ring concentrically placed i the melting crucible and provided with openings or break-throughs for the passage of the melt, and made from a material that does not react with the melt, is provided, the filler funnel bringing in the charge material emptying in an area which is defined by the outside surface of the ring and the margin of the crucible.
Contamination of the melt is also prevented by the fact that the inner wall of the crucible is provided with a dish or an insert of a material which does not react with the melt, and that at least the annular, flat portion of the second heater body disposed above the crucible is coated.
The invention admits of a great variety of embodiments, one of them being shown in the appended drawings, wherein
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal cross section through part of an apparatus for pulling monocrystals
FIGS. 2 and 3 are a plan view of the bottom heater according to FIG. 1, and a cross section through the latter along lines A--A
FIG. 4 shows the radiation guard tube laterally surrounding the melting crucible and the heater
FIGS. 5 and 6 are a top view of the cylindrical heater according to FIG. 1 and a longitudinal section taken along lines B--B
FIGS. 7-9 are different views of an alternative annular, flat heater.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The apparatus depicted in FIG. 1 of the drawing includes double-walled pot 4 which is placed on the also double-walled pot bottom 3 of the frame of the apparatus and forms a vacuum chamber 52. A supporting tube 5 is disposed in the pot 4 and mounted on the pot bottom 3 has a thermal insulation 6 enveloping the tube. An annular pan 7 held by the supporting tube 5 has graphite felt plates 8 mounted in the pan. Two power feeders 9 and 9a held on the pot bottom 3 feed a bottom heater 10 held above the pan 7, and two additional power feeders 11 and 11a on which clamps 12 and 12a are screwed feed a top end or cylindrical heater 13 borne by the clamps. A radiation guard tube 15 is supported on the pan 7 and provided with thermal side insulation 16, and a cover plate 17 borne by the radiation guard tube 15 has an upper end thermal insulation 18 and feed-throughs 19 and 20 with protective glasses 21 and 22. A tube 23 feeds charge material to crucible 14 through a filler funnel 24 brought through the cover plate 17 and 17a. The crucible column 25 which is rotatable and movable upward and downward for holding the crucible supporting column 26.
The bottom heater 10 held by the two electric power feeders 9 and 9a is represented in FIGS. 2 and 3 and consists of the two lateral heater feet 31 and 32 situated opposite one another, and the two serpentine heating coils 33 and 34. The heating coils 33 and 34 together form in the center of the bottom heater 10 an opening 35 through which the crucible supporting column 26 extends, which is affixed at its upper end to the melting crucible and by which the melting crucible 14 can be both moved up and down and made to rotate. The top end heater 13 represented in greater detail in FIGS. 5 and 6 is formed by an annular, flat part 38 provided with radially disposed slots 36, 36', . . . and 37, 37', . . . and a hollow cylindrical lateral wall 39. The hollow cylindrical portion 39 is provided on two portions lying opposite one another with downwardly extending heater feet 40, 40a, which are engaged in recesses 41 and 41a, respectively, which are provided in the two clamps 12, 12a, held by the current feeders 11 and 11a. In order to assure a reliable passage of current to the top end heater 13 in the two recesses 41 and 41a of the clamps 12 and 12a, additional wedges 42 and 42a are driven into the trapezoidal recesses 41 and 41a.
The radiation guard tube 15 represented in FIG. 4 has four rectangular openings 43, 43', . . . which are uniformly distributed on the circumference of the radiation guard tube 15, and disposed on its bottom margin 57. The clamps 12 and 12a on the one hand and the heater feed 31, 32, of the bottom heater 10 on the other, are brought out through these openings 43, 43', . . . Furthermore, the radiation guard tube 15 is provided with a sloping bore 45 which is aligned with the protective glass 21 of the cover plate 17 and 17a and the protective glass 46 of the pipe nipple 47 fastened in the wall of the pot 4. Additional openings 48, 48', 48", . . . in the side wall of the radiation guard tube 15 permit an unhampered passage of gas from the upper section of the interior of the pot 4 into the bottom section. The pot 4 is furthermore provided in the area of its cover 4' with a collar 48 which permits the entry of the puller 49. It is also to be noted that an additional pipe nipple 50 with a viewing glass 51 is also present in the cover 4' of the pot.
The bottom heater 10, which is slotted to give it a serpentine pattern, is screwed by two graphite nuts 27 and 27a to the two feeders 9 and 9a. The bottom heater 10 has the purpose of heating the crucible and the melt therein from the bottom. A second heater 13, which is constructed as a top heater, is fastened by clamps 12 and 12a to two additional power feeders 11 and 11a, the top surface heating improves the melting of the continuously fed charge material. The top surface heater 13 can, in the case of a silicon melt, be coated or shielded with silicon carbide to prevent graphite particles from dropping into the melt resulting in carbon contamination. Any reaction of SiO with graphite (2C+SiO→SiC+CO) is also prevented. The irregular broken lines indicate an argon gas stream which flows downwardly through the collar 48 through the central opening 53, and over the melt and around the crucible 14 through the holes 48, 48', . . . , and is finally withdrawn through the pipe nipple 70.
In the center of the heating system is a graphite crucible 14 into which is inserted a crucible 28 which is formed from a material that does not react with the melt. To assure quieting of the bath when it is charged during the pulling process, an additional ring 29, which is also formed from a material that does not react with the melt, is inserted into the crucible 28. At the bottom end of the ring 29 are openings or break-throughs 30 through which the molten material can flow into the center of the crucible insert 28. A thermal barrier 8, 16, 18 is placed around both heaters 10 and 13, and consists of the pan 7, additional graphite felt plates 8, a lateral thermal barrier 16 in the form of a cylinder fitted over the radiation guard tube 15, and a top end thermal barrier 18. The top plates 17 and 17a rest, together with the thermal barrier 18, on the inside surface of the pot 4.
In FIGS. 7 to 9 there is represented a heater 59 which can be used as an alternative to the second heater. This heater 59 consists essentially of an annular, flat, serpentinely slotted piece 60 having two heater feet 61 and 62 disposed at right angles to the piece. FIG. 8 depicts a top view of heater 59 showing the flat portion 60 of the second heater body 59, has a plurality of radially extending slots (63, 63', 62", 64', 64") and, as is shown in FIG. 9, is provided with at least one heater foot 61 and/or 62 (extending perpendicularly downward from the margin of the flat portion 60. The second heater body 59 has openings or holes 65, 66 through which the filler funnel 24, as shown in FIG. 1, of a feed tube 23 (shown in FIG. 1) of a charging apparatus extends. The temperature of the heater 59 can be established individually, and for this purpose the temperature of the melt in the crucible 14/28 can be measured through the nipple 67 in the cover of the pot 4. When unmelted material is fed through the filling funnel 24 into the melt in the crucible 14/28, an immediate and rapid melting of this added material can be produced by the two heaters alone (FIGS. 4 to 6 and FIGS. 7 to 9), and this can be done with a comparatively minimal agitation of the melt, and also without more greatly heating the crucible 14/28 itself. | Apparatus includes a crucible, a cover with an opening over the crucible, a pulling element for pulling monocrystal from melt in the crucible, and first and second heating elements. The first element is a substantially flat radiaent heat source below the crucible and the second element is a pot shaped, comprising a flat heat source above the melt and a cylindrical heat source about the crucible. A ring having holes therethrough is inserted in the crucible to quiet the melt, a filler funnel emptying material to be molten outside of the ring while the monocrystal is pulled from inside the ring. | 2 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates generally to a hypodermic syringe and more particularly to a syringe device having at least one ridge within the barrel portion of the syringe or along the plunger stem of the syringe device.
[0002] Syringe devices may be designed or intended for single or repeated use and may be operated manually or all or a portion of their operation may be mechanized. In general, a syringe device is comprised of three basic components: a barrel, which is typically cylindrical, a plunger, and a gasket which is affixed to the plunger so as to move in conjunction with the plunger. The gasket is typically designed to substantially seal within the barrel such that during operation the units function as a displacement piston. As such, this piston configuration provides for two directions of axial movement which may generally be termed an aspiration cycle and a dispensing cycle. Needles, filters, drive mechanism, locks, and protectors, as well as other components, are often used to augment the basic syringe device. Commonly, the barrel portion is translucent to allow visualization of the contents such as medicinal fluids, body aspirates or glue. Accordingly, aspiration draws matter, such as fluids, into the syringe, or the negative pressure developed by the aspiration stroke may be used for other purposes, for example, to suction and hold parts being manipulated on an assembly line. Similarly, the opposite stroke provides an outward force that may be used, for example, to inject fluids, or to provide a puff of air to blow dust off of optics. Combining piston movements with valves allows syringe devices to function in other ways, such as a pump. Precise movements and operation can be accomplished in a number of ways, for example by driving the syringe plunger with a computer-controlled stepper motor. Due to low cost, ease of manufacture, and established use, when appropriate, syringe devices can be further innovated to provide novel functionality.
[0003] U.S. Pat. No. 2,549,417 to Brown entitled “Syringe ampoule” discusses temporary compartments for use within a hypodermic syringe. Accordingly, to provide for temporary compartments, by-pass ribs (the length of the by-pass ribs being greater than the width of the stopper) are projected into the barrel of the syringe. In such a manner, a valve of sorts is created by projecting ribs to establish communication between potentially a plurality of compartments. One use described provides for dry chemicals in one compartment that may be measured and transported in the device. Subsequently, providing a fluid passage (using the ribs as a valve) allows these chemicals to be mixed with a diluent and dispensed.
[0004] U.S. Pat. No. 2,591,046 to Brown entitled “Hypodermic syringe assembly” further discusses syringe configurations and among other things, provides for multiple ribs so that the liquid vehicle may pass through these passages.
[0005] U.S. Pat. No. 5,000,735 to Whelan entitled “Single use syringe” discusses general use of syringes and more particularly a means of preventing reuse, for example, by breaking off or otherwise separating the plunger or plunger gasket after downward movement.
[0006] U.S. Pat. No. 4,469,482 to Lissenburg entitled “Disposable hypodermic syringe” discusses various aspects of syringes, their composition and use.
[0007] U.S. Pat. No. 6,379,328 to Mac Clay entitled “Disposable syringe” discloses a novel piston design used generally for dispensing fluids, such as drugs.
[0008] U.S. Pat. No. 5,389,070 to Morell entitled “Syringe apparatus with a fluid reservoir for injecting and aspiration of fluids” discusses advantages of connecting more than one syringe via a three-way stopcock, for example.
[0009] Among other things, U.S. Pat. No. 6,171,285 to Johnson entitled “Retractable syringe” discusses plunger locks and needle retraction into the syringe barrel.
[0010] Another form of plunger lock or plunger inhibitor is discussed in U.S. Pat. No. 6,368,305 to Dutton entitled “Syringe plunger immobilizing device”.
[0011] U.S. Pat. No. 5,480,064 to Yan entitled “Dispensing syringe for a fluid glue” discusses additional aspect of operating a syringe for dispensing fluids.
[0012] U.S. Pat. No. 4,430,079 to Thill entitled “Fluid dispensing device” among other things discusses coupling a syringe with a hose and providing for the application of a uniform force to the plunger to prove steady flow over a period of time.
[0013] For some applications it is useful to know the position of the plunger, as in a belt-driven infusion pump as discussed in U.S. Pat. No. 5,259,732 to Stern entitled “Syringe pump with syringe barrel position detector”. Stern also discusses use of a pressure detector to detect occlusions. Other aspects of syringe use in infusion pumps may be found in U.S. Pat. No. 5,295,966 to Stern. Various aspects of driving syringes is also discussed within.
[0014] U.S. Pat. No. 6,287,282 to Bonaldo entitled “Syringe safety sleeve and adaptor” discusses attachment of a protective sleeve. Other attachments within or external to syringes, such as filters are discussed in U.S. Pat. No. 4,137,917 to Cohen entitled “Syringe filter unit”.
[0015] U.S. Pat. No. 6,419,656 to Vetter entitled “Medical syringe with braked step-advance plunger” discusses plunger projections as well as a bypass passage forward of the piston. In certain positions the configuration may act with the by-pass groove and operation allows stop bumps to engage an elastically deformable brake element. At least two axially space projecting stop bumps are provided for on the stem or plunger rod. Vetter provides for a bypass passage forward of the plunger which may for example, hold a soluble medicament, but provides no mechanism to ensure that such a medicament is substantially dissolved and dispensed. The present invention discusses internal ridges formed from soluble components such as medicaments and provides a means in the form of resistive changes to assess when any such components have been substantially dispensed. In addition, Vetter discusses pairs of stop bumps on the plunger stem that act as brake elements to prevent the plunger from advancing too rapidly requiring that the user twist the piston to align for further advance. In some embodiments, the present invention seeks to simplify syringe operation providing the user with feedback regarding syringe speed or plunger position, such tactile feedback allowing operation of the syringe in stressful, poor lighting or other unfavorable conditions. Accordingly, Vetter does not contemplate rings or single bumps formed on the syringe stem so as to provide tactile feedback and does not suffer as a consequence. While the present invention primarily discusses ridges formed on the inner barrel of a syringe, some of this novel functionality may be derived by forming ridge structures on the plunger stem.
[0016] Accordingly, because of their simplicity, ease of manufacturing, low cost, varied materials, availability, adaptability and other aspects, it would be advantageous to further exploit the use of syringes. The present invention provides for a novel syringe device which provides a ridge in the form of a partial or tactile stop within the barrel of a syringe. Such innovation provides for new functionality and uses as will be further discussed herein.
SUMMARY
[0017] The present invention is a syringe in which one or more ridges are formed within the barrel of the syringe or along the plunger stem of the syringe device to provide tactile or sensory feedback in the form of resistive changes. The tactile feedback is useful to humans who are, for example, visually impaired, rushed, or in low lighting situations. The sensory feedback is also useful to machinery in automated operations.
[0018] “Ridge” as used herein means a protrusion or indentation formed within the barrel of a syringe or along the plunger stem of a syringe device. A ridge as used herein may be of desired size, shape, dimension, elasticity, and number so as to provide tactile or sensory feedback, typically in the form of a resistive change to axial movement of the gasket within the barrel. Tactile feedback may be sensed by a user or via a machine interface and provide indication of gasket position and/or speed and/or displacement, for example. Accordingly, a ridge may be substantially tactile, provide strong resistance to provide a stopping or holding action, provide substantially the same or different amounts of resistance depending on the direction of axial movement, be designed for one time use, be formed in a pattern to provide additional indication of position or speed, or otherwise be exploited to advantage.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] [0019]FIG. 1 shows a syringe device of the present operation with novel tactile ridge.
[0020] [0020]FIG. 2 a shows a syringe device of the present operation with novel impeding ridge with plunger gasket in a forward position (prior to aspiration stroke).
[0021] [0021]FIG. 2 b shows a syringe device of the present invention with novel impeding ridge in retracted position (subsequent to an aspiration stroke).
[0022] [0022]FIG. 3 shows a syringe device of the present invention in retracted position with two impeding ridges in the syringe barrel.
[0023] [0023]FIG. 4 shows a variety of ridge configurations.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] [0024]FIG. 1 shows syringe device 100 of the present invention having a cylindrical tube or barrel 110 with plunger 120 and ribbed gasket 115 attached to the plunger 120 . A novel, tactile ridge 125 has been implemented within the barrel 110 . (Please note that the ridge 125 is illustrated in FIG. 1, as are all of the ridges illustrated in subsequent figures, in exaggerated size for clarity. The actual size and shape of a particular ridge depends on the use of the device.) The tactile ridge 125 is further shown in expanded cross-section as a protruding ring within the barrel 110 . The tactile ridge 125 is implemented so as to provide a slight, incremental resistance that may be physically sensed as the gasket 110 is caused to move over the tactile ridge. As shown in expanded view in FIG. 1, the tactile ridge 125 in this instance is formed as an internal ring. As will be described further, protrusions such as bumps or indentations formed within the syringe barrel may also be used to provide such a tactile feedback.
[0025] For many applications such tactile ridges are preferably implemented in a manner that does not break the seal within the syringe to a degree that undermines or otherwise impedes intended use. The tactile ridge 125 provides feedback that may be useful to human users or may be sensed in various ways when machine interfaced thus providing information regarding position or movement of the syringe plunger. In the illustrated embodiments, the tactile ridge 125 ( 225 and 331 through 335 in subsequent drawings) is a rounded protrusion or nub projecting axially from the interior wall of the barrel 210 . But any shape, such as square, rectangular, wedged, polygonal, etc., can be used, depending on the materials used, the manufacturing process, and the degree of tactile feedback desired.
[0026] The use of tactile feedback is advantageous in a variety of circumstances, for example, it may facilitate usage of a syringe for the visually impaired. Accordingly a series or coded (patterned) series of such tactile ridges could extend such functionality. Accordingly the present invention may be used to provide tactile feedback at volume intervals, such as each 1 cc, may be used in conditions 160 with restricted lighting, or may be used under conditions when it may be advantageous to free some attention, for example, during emergency medical situations encountered by the military or in trauma centers. Tactile ridges may be incorporated to work in conjunction with various syringes innovations such as compartments as previously described
[0027] [0027]FIG. 2 a shows a syringe device 200 of the present invention having a cylindrical tube or barrel 210 with ribbed gasket 215 attached to plunger rod 220 . A more substantial tactile ridge in the form of an impeding ridge 225 has been implemented as a temporary impediment to movement. As diagramed, the impeding ridge 225 provides sufficient resistance so as to keep the plunger 220 from returning past the impeding ridge 225 when the open end 240 of the syringe is substantially occluded during the aspiration stoke (plunger retraction). As the plunger 220 is retracted with the inlet occluded, a negative pressure (vacuum) is developed. Such vacuum may be exploited in a variety of ways, which will be further discussed in association with FIG. 2 b.
[0028] [0028]FIG. 2 b shows a syringe device 200 having a cylindrical tube 205 with ribbed gasket 215 attached to the interior end plunger 220 . A novel tactile ridge, in the form of an impeding ridge 225 has been implemented in the barrel of the syringe as described in association with FIG. 2 a , so as to provide sufficient resistant to keep the plunger from returning to its forward position of FIG. 2 a , during intended use. In this instance, to better describe use of the syringe 200 as a vacuum device, the syringe tip 240 is shown attached to a filter apparatus 245 . The filter apparatus 245 is submerged in a vessel containing a particle suspension 250 . When submerged, the plunger is retracted from its forward position of FIG. 2 a , which is accomplished by retracting the syringe plunger, thereby forcibly drawing the gasket 215 over to the top side of the impeding ridge 225 . Such movement initiates the aspiration of particle suspension and will continue, typically until the vacuum is depleted or other factors effect the system. Material captured by the filter apparatus could be examined microscopically, for example. Other advantages of such a configuration are discussed in co-pending United States patent application entitled Method of Depositing Material and Density Gradients of Material from Sample Suspensions and Filter Devices for Same, filed on Aug. 26, 2002.
[0029] As an example of another configuration ridge for tactile feedback, an indentation 235 is shown in the barrel 210 in FIGS. 2 a and 2 b . This indentation 235 is preferably of less width than the width of the gasket 215 , or the gasket 215 is selected of material of sufficient elasticity, in order to prevent leakage around the gasket 215 . As the plunger 220 moves the gasket 215 axially within the barrel 210 , the user will feel different sensations as the gasket 215 moves over a protruding ridge 225 than when the gasket 215 moves over an indentation 235 . The indentation 235 therefore provides the user with more detailed feedback as to the location of the plunger 220 within the barrel 210 . As discussed above with respect to different shapes of the protruding ridge 225 , this difference is sensation may be exploited for different applications.
[0030] [0030]FIG. 3 shows another configuration and use of syringe device 300 of the present invention. As diagramed the syringe device has five ridges identified as 331 , 332 , 333 , 334 , and 335 . The uppermost ridge 331 has been designed as a wedge to facilitate assembly of the syringe device (insertion of the plunger gasket assembly into the barrel 310 ) and inhibit separation of these components. For some applications, or to prevent spillage, for example, it may be desirable to provide such an impeding ridge 331 in the vicinity of the upper barrel of the syringe 300 . Typically such impediment should be implemented so as not to inadvertently dislodge the gasket if disassembly is required or desired.
[0031] Beginning with the plunger 320 down (not shown) and the tip portion of the syringe 300 submerged in fluid 350 as shown, fluid 350 may be aspirated into the syringe 300 by retracting the plunger 320 , drawing attached gasket 315 to ridge 332 , a position in this instance intended to aspirate slightly more fluid 350 than is required for use, in the form of a priming volume to purge trapped air, for example. Typically, the syringe 300 is then inverted to facilitate priming which is accomplished by advancing the plunger 320 from ridge 332 , to, in this instance, tactile ridge 333 . Then the plunger 320 may be further advanced from tactile ridge 333 to another, in this instance tactile ridge 334 . As illustrated, the ridges are formed on the interior wall of the barrel 310 as a series of round shaped protrusions or nubs, but can be of a different shape or size, or even of varying shapes and sizes, in order to provide more detailed tactile feedback. As described, this movement displaces the fluid volume 361 that exists between the two ridge positions 333 and 334 . To provide additional indication of position or volume, accompanying markings striations 341 and 342 have been formed externally on barrel 310 . In such a manner, the syringe device 300 provides a means to dispense preset fluid volumes with ease, and relative accuracy while providing indication of the position of the gasket 315 during operation.
[0032] Advancement of the plunger 320 may continue from ridge 334 (for example after waiting ten seconds) as required or desired, to tactile ridge 335 , therefore in this instance providing a level of control over the dispensing of two fluid volumes, over a desired time interval.
[0033] The dimensions and sizes of the ridges 331 through 335 and the materials of the syringe barrel 310 should be considered for use. For example, gaskets with relatively elastic properties (e.g. rubber like compounds) will understandably perform different than firmer Teflon coated plastics or other materials. A small striation, scribe or bump encountered by a Teflon gasket may provide sufficient tactile feedback whereas a more substantial ridge may be required to achieve the same ends, employing a more elastic material. As describe, ridges of various types may be formed or distributed over an effective area to provide sufficient tactile resistance. Rounded contact surfaces, to minimize abrasion to the gasket 315 are preferable but not required by the scope and intent of the present invention. Similarly, extended ridges in the form of narrowings or widenings of the syringe body are also considered within the scope of intended functionality of the present invention.
[0034] [0034]FIG. 4 a shows an alternative embodiment. In this embodiment, the ridge is formed by a tapering of the barrel of the syringe, along some portion or even substantially all of the syringe barrel. When the sealing gasket 401 , with appropriate elastic properties, is inserted into the hollow cylindrical syringe barrel 402 and moved from approximate position 403 , in the direction of the arrow 405 , towards approximate position 404 , an increase in resistance is generated due to frictional forces. This increase may be sensed, by a human user or machine-sensors interfaced to the plunger (not shown) and exploited to provide information as to the position of the sealing gasket 401 within the barrel 402 . The syringe device is so formed and materials selected so that the seal between the sealing gasket 401 and the barrel 402 is substantially maintained during operation. If required or desired, however, the resistance, for example in approximate area 404 , could be substantial enough to act as a mechanical stop, for intended use.
[0035] [0035]FIG. 4 b shows a embodiment in which different resistances are generated in different sections of the barrel of the syringe. In this embodiment, sealing gasket 411 is advanced, typically by pushing or pull it via the attached plunger (not shown), through approximate regions 412 , 413 , and 414 . During passage through region 412 , the sealing gasket 411 encounters constant resistance. During passage through region 413 , an increase in resistance is generated, and sensed. The resistance then remain relatively constant over some other a region of the syringe barrel, such as that designated as 414 . Various forms of tapering may be implemented as required or desired to provide feedback to the human user or machine-interfaced sensors.
[0036] [0036]FIG. 4 c shows other embodiments of ridges in the form of deformable tabs projecting into the interior wall of the syringe barrel 422 . Ridges 423 are designed and intended in this instance to provide a certain resistance to movement as the sealing gasket 421 is pushed over them in the direction of movement indicated by arrow 425 . Similarly, when the sealing gasket 421 is moved over these ridges 423 in the opposite direction, the design and implementation provides slightly less resistance than was generated in direction 425 . Further along syringe barrel 422 , ridges 413 have been implemented as distributed tabs around the interior of the barrel 422 , providing a resistance increase that is lower in direction 425 and higher in the opposite direction. Alternatively, these ridges may take the form of a ring 424 , projecting circumferentially around the interior of the barrel 422 , instead of as tabs.
[0037] [0037]FIG. 4 d shows sealing gasket 431 for insertion into syringe barrel 432 having ridges 433 formed on the interior wall of barrel 432 in the form of coded bumps. The number and interval of resistive pulses generated and sensed as the sealing gasket 431 is advanced over them, provides information such as position, movement, speed, or displaced volume. Such information may be useful as sensed by the visually impaired, in poor lighting conditions, etc. Also, machine-interfaced sensors could employ this information to advantage, for example, to simplify position detection or otherwise provide feedback for robotic operation. Alternatively, for the same stroke distance, using larger syringe barrels may simplify the mechanics or electronics necessary to accomplish a desired task. Similarly, in certain situations, such as isolating electronics from fluids may favor such implementation. An alternate series of ridges in the form of nubs 434 are designed to provide information in the form of resistive pulses that change in magnitude as gasket 431 is caused to pass over them. Both ridges 433 and numbs 434 can project as tabs from the interior of the barrel 432 or as circumferential rings projecting from the interior of the barrel 432 , as described above with respect to FIG. 4 c . The number, size, position, sequence, and resistance of the ridges 433 or numbs 433 can be designed as needed to provide feedback to the human user or the machine-interfaced sensor.
[0038] [0038]FIG. 4 e shows additional embodiments with ridges of various types formed as indentations in the interior wall of the syringe barrel 442 so as to provide resistive changes as the sealing gasket 441 passes over them, is delayed by them, or its motion is substantially halted, as desired or required. The sealing gasket 441 has been designed and in this instance customized to operate in this barrel 442 . Additionally, ridge 448 has been formed as a protruding ridge in the form of a collapsible bubble, designed to be sensed once, thereafter providing no further resistive change, if subsequently encountered. Alternatively, such a single sense element could be reversed in curvature and sprung into an adjacent indentation, or alternatively a single sense element could be a break-off or otherwise separating component, as required or desired.
[0039] Another useful form of ridge could be provided by chemicals formed, for example, as rings within the barrel 442 . In this instance the ridge resistance may provide information regarding mixing, quantity of dissolved chemical dispensed, etc.
[0040] While preferred embodiments of the present invention are shown and described, it is envisioned that those skilled in the art may devise various modifications of the present invention without departing from the spirit and scope of the appended claims. | A syringe device incorporating ridges that cause resistive changes to the movement of the syringe gasket or plunger, thereby providing user feedback as to the position and speed of plunger movement. Such user feedback may be useful in stressful situations, under poor lighting conditions or in other unfavorable circumstances. Additionally, in certain embodiments these ridges may aid in accurate dispension or allow the syringe to derive additional functionality, such as performing as a vacuum source. Ridges can be protrusions such as tabs, bubbles or continuous rings for single or repeated use or these ridges may be formed as indentations. Ridges may be formed in patterns, in various sizes and shapes or these ridges may be mixed and matched as required or desired. Ridges may also be formed from a soluble material and the resistive change may itself provide indication that the material has been substantially dissolved and dispensed. In some embodiments these ridges are formed primarily within the barrel portion of the syringe. In other embodiments these ridges may be formed on the plunger stem of the syringe. Ridges may be constructed to provide one type of resistive change during the aspiration stroke and a different resistive change to motion in the opposite direction. | 0 |
TECHNICAL FIELD
This invention relates generally to the fabrication of glass fiber, nonwoven mats, composed of strands of highly dispersed, continuous glass strands arranged in interengaging swirled relationship. More particularly, the invention relates to an improved method and apparatus for directing continuous glass strands onto a moving conveyer while simultaneously oscillating the strand impingement point laterally across the width of the conveyer at an essentially constant velocity.
BACKGROUND ART
Glass fiber mat has long been manufactured by directing continuous strands of glass fiber down onto a moving conveyer as the fiber trajectory and point of impingement is oscillated back and forth across the width of the conveyor. This builds up a random, homogeneous layer of interengaging strands in a swirled, overlapping arrangement. A variety of methods and apparatus for directing the glass fiber onto the moving conveyer have been attempted in the past several decades.
For example, U.S. Pat. No. 2,855,634 illustrates a plurality of continuous glass fiber strands directed onto a conveyer from a plurality of different pulling wheels distributed above the conveyer.
Others have suggested the deflection of a continuous glass fiber which is impinged upon a reflecting surface. Such patents include U.S. Pat. Nos. 2,736,676 and 4,345,927.
A more practical system for oscillating the trajectory of the glass strands utilizes a pulling wheel, having lateral slots through which the fingers of a finger wheel project. The finger wheel rotates about an axis of rotation which is offset from the axis of rotation of the pulling wheel. The fingers move out to release the strand from the pulling wheel so that it is projected along a substantially tangential path from the wheel to the moving conveyer. Structures of this type include those shown in U.S. Pat. Nos. 4,368,232 and 3,485,610.
Another system utilizes air blasts in place of the fingers, such as is illustrated in U.S. Pat. No. 2,450,916. The linear feed of a continuous multi-filament strand is illustrated in U.S. Pat. No. 2,935,179.
Finally, more recently, oscillating air current systems have been used for guiding a glass fiber along its trajectory and to cause the trajectory to oscillate back and forth laterally across the conveyer. Such systems are illustrated in U.S. Pat. Nos. 2,859,506; 2,875,503; 3,738,894; and 4,601,741.
One of the principal goals of a system for producing glass fiber mat is to fabricate a product exhibiting a uniform distribution of fibers randomly across the conveyer within the limits of the width of the finished glass fiber mat. Ideally, such a mat has a uniform density laterally from one edge, through the center, to the other edge of the mat and would terminate with relatively sharp lateral edges.
One difficulty with the air current systems is that the fibers flutter uncontrollably, providing little control of the curl and providing relatively ragged edges of nonhomogeneous density. Thus, the mat product is not sufficiently uniform near its edges. This necessitates that the mat be manufactured with an oversized width so that a strip of material can be removed from the opposite, lateral Substantial trim loss scrap is therefore produced.
A difficulty with the finger wheel systems is that the fingers create a small kink in each fiber and no control of the curl is permitted.
It is therefore an object and feature of the present invention to provide an apparatus and method which permits more accurate control of the glass fiber which is projected onto the conveyer without the inaccuracies caused by turbulent air currents or the deformities caused by the finger wheels.
A further object and feature of the present invention is to provide improved uniformity and density across the width of the glass fiber mat and also provide for control of the curl.
BRIEF DISCLOSURE OF INVENTION
In the present invention a glass fiber is directed onto a rotating pulling wheel which is rotating at an orientation in which tangents to the wheel intersect a support surface, such as a travelling conveyer. The fibers follow around the pulling wheel and are stripped from it by the edge of a stripping body which extends across the periphery of the pulling wheel and is reciprocating along a circular path adjacent to the periphery of the wheel. The stripping body, such as a tight wire, oscillates within an angular range at which tangents to the pulling wheel intersect the support surface so that glass fiber is stripped from the rotating pulling wheel and projected toward the support surface, substantially tangentially to the pulling wheel. Oscillation of the stripping body or wire causes oscillation of the fiber trajectory and therefore of the impingement point of the fiber upon the support surface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic top plan view of the preferred embodiment of the invention.
FIG. 2 is a view in side elevation of the embodiment of FIG. 1.
FIG. 3 is a side view in detail illustrating the principal components of the preferred embodiment of the invention.
FIG. 4 is an end view of the embodiment illustrated in FIG. 3.
In describing the preferred embodiment of the invention which is illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is to be understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose. For example, the word connected or terms similar thereto are often used. They are not limited to direct connection but include connection through other circuit elements where such connection is recognized as being equivalent by those skilled in the art.
DETAILED DESCRIPTION
Referring to FIGS. 1 and 2, a plurality of molten glass fibers are drawn by a pulling wheel 12 from a plurality of orificed projections 10 which are conventionally formed on the bottom of a glass melting furnace. The fibers are pulled through shoes or rotating sheaves 14 and gathered into strands in the conventional manner. For example, in the preferred embodiment of the invention, 300 filaments are gathered into 6 multifiber strands, each composed of 50 filaments per strand. The filaments 8 and the sheaves 14 are actually oriented in a plane which is parallel to the axis of rotation of the pulling wheel 12, but are diagrammatically illustrated otherwise for clarity.
The fibers are carried along the lower periphery of the rotating pulling wheel 12 until they are stripped in the conventional manner from the pulling wheel 12 by means of a wire 16 stretched tightly across the outer circular periphery of the pulling wheel 12. This causes the fibers 18 to be projected along a trajectory, substantially tangentially of the pulling wheel 12 and impinge upon a second pulling wheel 20.
The glass strands are carried around the second pulling wheel 20 and in accordance with the present invention are stripped from the pulling wheel 20 in a manner which causes them to be projected onto a conventional, foraminous, linked chain conveyer 22, positioned below the pulling wheel 20. They are projected in a manner which causes the strands to repetitively loop back and forth across the width of the conveyer 22 and build up a layer of stacked, intertwined strands to form the glass fiber mat. As the strands are built up, the conveyer 22 advances transversely to the lateral path of impingement of the fibers on the conveyer support surface 22.
Referring now additionally to FIGS. 3 and 4 for detail, the pulling wheel 20 is rotatably driven by rotating drive means not illustrated, and has an outer, circular, peripheral surface 30. The pulling wheel 20 is oriented in a position so that tangents to the surface 30 of the pulling wheel 20 intersect the support surface 22 of the conveyer. This is illustrated in FIG. 2 for tangents 32, 34, 36, 38, and 40.
The rotating axle 42 of the pulling wheel 20 is journalled in a bearing 44. A bearing is also provided on a support frame 46 so that the support frame 46 is pivotable about the axis of rotation of the pulling wheel 20. The support frame 46 provides a stripping body support means which movably supports a wire 48, or other stripping body. This stripping body 48 is supported tightly across the peripheral surface of the pulling wheel 20, transverse to the fiber travel direction on the peripheral surface 30 and preferably parallel to the axis of rotation of the pulling wheel 20. The stripping body support frame 46 is pivotable so that it can reciprocate the stripping wire 48 along an arcuate path adjacent to the peripheral surface 30 of the pulling wheel 20. The wire 48, or other stripping body with a suitably thin edge which can function equivalently, reciprocates within an arc from which tangents to the wheel 20 intersect the support surface of the conveyer 22.
A drive means is linked to the stripping body support frame 46 for driving the stripping body wire 48 in its arcuate reciprocation. The drive means includes a rotating drum 76 around which there is a thick band 78 forming a cam. The band 78 encircles the drum 76 in a diagonal manner, directed one way in the first 180° of rotation and the opposite way in the remaining 180° of rotation, to form a closed loop. A follower 72 is attached to a reciprocating drive bar 74 and follows the reciprocating left and right apparent linear displacement of the band 78. A bolt 80 is attached to the reciprocating drive bar 74 and extends slidably through a slot 66 formed at the end of a second drive bar 56. This allows the drive bar 74 to drive the reciprocating drive bar 56 in linear reciprocation transverse to a radial of the axis of reciprocation of the stripping body support frame 46. The reciprocating drive bar 56 is mounted in a slide arrangement which includes a mounting plate 60 and bearings 62.
The stripping means support frame 46 also includes a radial bar 64 that extends into a pivoting sleeve 61 which pivots about a transverse axis to remain parallel to the radial bar 64, while allowing free coaxial movement. The series of slots 66 and 68 and sleeve 61 allow for repositioning and vertical adjustment of the mounting plate 60 and the reciprocating drive bar 56. The adjustment changes the distance between the reciprocating drive bar 56 and the center of rotation of the stripping means support frame 46, thus effectively changing the angular range of the arc in which the stripping body 48 travels along the peripheral surface 30.
Preferably, the radial bar 64 and the reciprocating drive bar 56 are relatively aligned so that the reciprocation path of the drive bar 56 is perpendicular to the radial bar 64 when the stripping body or wire 48 is intermediate the bounds of its arcuate reciprocation.
The rotating drum 76 and follower 72 are arranged to reciprocate the drive bars 74 and 56 at a substantially constant velocity. This occurs when the drum 76 rotates and the follower 72 follows the reciprocating left and right apparent linear displacement of the band 78. For every half revolution of the rotating drum 76 the follower 72 will travel from one extreme end of the band 78 to the opposite end. Thus, as the rotating drum 76 rotates, for example clockwise as viewed from the left end in the drawing, the follower 72 will move first to the left, then, as the band's 78 direction reverses, to the right. Similarly, when the follower 72 reaches the extreme right end of the band 78, where the band's 78 direction reverses again, the follower 72 will begin it's leftward motion, thus initiating repetition of the reciprocation of the drive bar 56.
In the operation of the preferred embodiment illustrated in the drawings, the glass fibers travel around the peripheral surface of the pulling wheel 20 until they strike the stripping body 48. Upon striking the stripping body they are stripped from the outer peripheral surface of the pulling wheel 20 and their momentum carries them along a trajectory which is substantially tangential to the peripheral surface of the pulling wheel 20 at the point they separated or restrict from that surface. Thus, as the stripping wire 48 reciprocates arcuately within an angle, the tangential trajectory of the fiber oscillates back and forth across the conveyer within the range illustrated in FIG. 2.
With the reciprocating drive bar 56 driven at a constant velocity, the stripping body is reciprocated at an angular velocity which is an increasing function of the angle between the support surface and the substantially tangential fiber trajectory along which the fiber travels to impinge upon the support surface. To accomplish this, the angular velocity of the stripping wire 48 is greatest where the fiber trajectory is making the maximum angle with the conveyer. For example, if the stripping wire 48 is centered directly above the support surface of the conveyor 22, the angular velocity is greatest when fiber is being directed straight down upon the support surface. The stripping wire moves at a slower angular velocity at a lesser angle between the trajectory and the support surface of the conveyer 22, that is, in the above example, when fiber is being directed toward the edges of the support surface.
The structural relationships of the illustrated embodiment cause a constant velocity traverse of the point of impingement of the fiber on the support surface back and forth across the conveyer to deliver the fiber at a uniform, homogeneous density laterally across the support surface.
There can be for example an angular reciprocation of + and -30 degrees. At +30° and at -30° the tangents intersect point B. Intermediate those positions the tangent intersects point A. If the approximation is made, that all tangents between plus and minus 30 degrees fall at the identical point between points A and B, then it can be shown from conventional geometry and trigonometry that the relationship of the velocity of the reciprocating bar 56 to the velocity of the impingement point of the fibers laterally along the support surface or conveyer is given by the following equation:
V.sub.1 =[d.sub.o /r.sub.o ]V.sub.2
where
d o equals the perpendicular distance from the stripping wire 48 to the conveyer support surface 22;
r o equals the radius from the axis of rotation of the support frame 46 to the center of the pin 66 at the center of the arc of reciprocation of the support frame 46;
V 2 equals the linear velocity of the reciprocating drive bar 56; and
the V 1 equals the linear velocity of the point of impingement of the tangential trajectory of the glass fibers upon the conveyer.
If the above approximating assumption is not made, then the relationship is as follows:
V.sub.1 =[d.sub.o /r.sub.o ]V.sub.2 -Y.sub.o [sinα/cos.sup.2 α]
where alpha is the angle of reciprocation from the center of the arc of reciprocation to the boundaries.
Mathematical analysis of these equations makes it apparent that the velocity of the tangential trajectory of the impingement of the glass fiber on the mat is approximately proportional to the velocity of the reciprocating drive bar 56. The approximation becomes more accurate as the angle of reciprocation becomes less.
Other linkages may also be developed for similarly causing the impingement point of the fibers on the conveyer to traverse laterally across the conveyer at a constant velocity.
One advantage of the invention is that the cycle rate or frequency of the oscillating fiber trajectory can be controlled and varied. This allows control of the curl size and along with conveyer speed, control of the density.
While certain preferred embodiments of the present invention have been disclosed in detail, it is to be understood that various modifications may be adopted without departing from the spirit of the invention or scope of the following claims. | Glass fibers are projected along an oscillating trajectory onto a travelling conveyer to form a glass fiber mat. The trajectory is made to oscillate by stripping glass fibers from a pulling wheel by means of a stripping edge, such as a tight wire, which is oscillated arcuately immediately adjacent the surface of the pulling wheel. The stripping means is oscillated at a greater angular velocity where the trajectory makes a greater angle with the conveye=r in order that the impingement point of the trajectory upon the conveyer travel at a substantially uniform velocity across the conveyer so that a mat of uniform density is fabricated. | 3 |
BACKGROUND OF INVENTION
This invention relates to an internal combustion engine and more particularly to an improved, compact and low cost oil pump arrangement for such engines.
Generally four-cycle internal combustion engines are lubricated by an oil pump that is generally positioned within the body of the engine and which is generally driven off of the crankshaft at one end thereof. Such constructions have some disadvantages, particularly when considering that it is also a conventional practice to embody the pressure relief system for the oil pump within the oil pump body. By positioning this part of the engine within the engine body, it tends to elongate the engine, particularly when the accommodation for the relief valve is considered.
With the modern space constraints placed upon internal combustion engines, particularly those for automotive applications, such increases in engine length are unacceptable or undesirable.
It is, therefore, a principal object to this invention to provide an improved, compact and simplified oil pump for an internal combustion engine.
It is a further object to this invention to provide an improved oil pump and relief arrangement for an engine that permits the engine to be compactly constructed.
SUMMARY OF INVENTION
This invention is adapted to be embodied in an internal combustion engine that comprises an engine body, which defines at least one combustion chamber in which a piston reciprocates. A shaft is driven by the reciprocation of the piston. The shaft has an end portion that extends beyond an outer wall of the engine body. A pulley is affixed to the shaft end portion for driving an engine accessory. An oil pump housing is affixed to the outer wall in surrounding relationship to the shaft end portion and containing a pumping element driven by the shaft end portion for pumping a lubricant for the engine.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a cross sectional view of an engine constructed in accordance with an embodiment of the invention taken along a transverse plane to the crankshaft axis.
FIG. 2 is a perspective, front view of the front or timing cover of the engine.
FIG. 3 is an enlarged front elevational view of the engine front cover in the area of the oil pump.
FIG. 4 is a cross sectional view taken along the line 4 — 4 of FIG. 3 .
FIG. 5 is a cross sectional view taken along the line 5 — 5 of FIG. 3 .
FIG. 6 is a cross sectional view taken along the line 6 — 6 of FIG. 3 .
DETAILED DESCRIPTION
Referring now in detail to the drawings and initially primarily to FIG. 1, an internal combustion engine constructed in accordance with an embodiment of the invention is indicated generally by the reference numeral 11 . Although the invention deals primarily with the construction and operation of its oil pump, which is shown in more detail in the remaining figures, the overall construction of the engine 11 will be described generally so as to permit those skilled in the art to understand an environment in which the invention can be practiced. Of course, the description of the basic engine components is for illustration only and those skilled in the art will readily understand how the invention can be utilized with a wide variety of types of engine constructions and engine configurations.
The engine 11 , in the illustrated embodiment, is of the V-type and accordingly is embodied in an engine having a cylinder block 12 having a pair of angularly related cylinder banks in which cylinder bores 1 3 are formed. In the specific embodiment illustrated, the engine 11 is of the V8 type and there are four cylinder bores 13 in each cylinder bank.
One end of each cylinder bank and specifically the cylinder bores 13 formed therein is closed by a respective cylinder head assembly 14 . These cylinder head assemblies 14 have recesses 15 formed in their lower surfaces that cooperate with the cylinder bores 13 and pistons 16 reciprocating therein to form the combustion chambers of the engine.
The pistons 16 are connected by piston pins to the upper or small ends of respective connecting rods 17 . The connecting rods 17 are, in turn, journalled on the throws of a crankshaft 18 .
The crankshaft 18 is rotatably journalled in a crankcase assembly 19 which is comprised of the skirt of the cylinder block 12 , an oil pan and bearing forming member 21 and an oil pan 22 that is affixed to the underside thereof and which defines an oil reservoir in which lubricant for the engine is contained.
The engine 11 is preferably, but not necessarily, liquid cooled and to this end, the cylinder block 12 is provided with a cooling jacket 23 and the cylinder head assemblies 14 are provided with cooling jackets 24 . Coolant is circulated through these cooling jackets 23 and 24 by a coolant pump of a known type in any suitable manner.
An induction system is provided for supplying at least an air charge to the combustion chambers of the engine. This induction system includes a plenum chamber device 25 which is disposed above one of the cylinder banks and specifically the cylinder head assembly 14 thereof and which has a suitable atmospheric air inlet. This atmospheric air inlet may include a filtering and silencing device as well as a throttle body for controlling engine speed.
The plenum chamber device 25 serves an intake manifold, indicated generally by the reference numeral 26 , that has discharge ends which communicate with intake passages 27 formed in the valley side of the cylinder head assemblies 14 . These intake passages 27 are valved by intake valves 28 that are slidably mounted in the cylinder head assemblies 14 . These intake valves 28 are urged to their closed position by means of coil compression spring assemblies 29 . The intake valves 28 are opened by the lobes 31 of respective intake camshafts 32 that are journalled in the cylinder head assembly 14 in an appropriate manner. These camshafts 32 are covered by cam covers 33 that are affixed to the respective cylinder heads.
The cam lobes 31 cooperate with thimble tappets 34 that are interposed between the cam lobes 31 and the stems of the intake valves 28 in a manner well known in this art. The intake camshafts 32 are driven at one half the rotational speed of the crankshaft 18 by any suitable cam shaft driving arrangement.
Fuel injectors 35 are mounted in the cylinder head assemblies 14 for injecting fuel into the intake passages 27 for delivery to the engine combustion chambers. The admitted fuel charge is ignited by means of spark plugs 36 that are mounted centrally in the engine combustion chambers by the cylinder head assemblies 14 .
The charge which is admitted to the combustion chambers and ignited by the spark plugs 36 will expand and then be discharged through exhaust passages 37 formed in the cylinder head assemblies 14 on the sides away from the valley and opposite to the intake passages 27 . These exhaust passages 37 communicate with exhaust manifolds 38 fixed to the outer surface of the cylinder head assemblies 14 . These exhaust manifolds 38 communicate with any suitable type of exhaust system.
The flow through the exhaust passages 37 is controlled by exhaust valves 39 that are mounted in the cylinder head assemblies 14 and which like the intake valves 28 are urged to their closed position by coil spring assemblies 41 . The exhaust valves 39 are opened by means of lobes 42 of exhaust camshafts 43 that are also journalled by the cylinder head assemblies 14 and enclosed within the cam chambers defined by the valve covers 33 .
The lobes 42 act upon thimble tappets 44 for opening the exhaust valves 39 in a well known manner. Like the intake camshafts 32 , the exhaust camshafts 43 are driven at one half-crankshaft speed by a suitable cam timing drive.
The construction of the engine 11 as thus far described may be considered to be conventional and, for the reasons already noted, further discussion of its detailed construction except for the oil pump, which will be described shortly, is not believed to be necessary to permit those skilled in the art to practice the invention.
The invention deals with the oil pump, which is shown, in most detail in FIGS. 2-6 but before referring these figures, it should be noted that the oil pump draws oil from the oil pan 22 through a strainer 45 and pick up tube 46 . The pick up tube 46 delivers oil to the oil pump in a manner, which will be described shortly.
Referring now to FIGS. 2-6, it has been mentioned that the camshafts 32 and 43 are driven by a suitable timing drive and that drive is positioned at the front end of the engine as seen in FIG. 6 and which may include a timing chain 47 that is driven by a sprocket mounted on the crankshaft 18 . This timing chain 47 is disposed outwardly of a front end wall 48 formed in the main engine body and primarily the cylinder block 12 and which is closed by a timing case cover 49 which forms the outer peripheral edge at one end of the engine body. This timing case cover 49 is affixed to the cylinder block 12 in a suitable manner and is shown in more detail in FIG. 2 .
Referring specifically to FIGS. 2, 4 and 6 , the timing case cover 49 is provided with an opening 51 through which one end of the crankshaft 18 extends. A pulley 52 is affixed to this extending crankshaft end portion for driving one or more engine accessories and other pulleys. This is conventional practice. However, and in accordance in accordance with the invention, an oil pump assembly, indicated generally by the reference numeral 53 , is positioned within the hollow interior of the drive pulley 52 and on the outer front face of the timing cover 49 or front end wall of the engine 11 .
The oil pump assembly 53 is formed in part by a circumferentially extending flange 54 of the timing cover 49 which flange receives a pump cover 55 . An O-ring seal 56 is provided around the flange 54 for providing an oil tight seal in this area. The pump cover 55 has an end wall 57 , which receives a seal 58 around the crankshaft end and inwardly from the point where the pulley 52 is affixed.
The oil pump 53 is of the trochoidal type, although other types can be utilized, and has a driving member 59 . This driving member 59 is suitably coupled to the portion of the end of the crankshaft 18 that extends into the pump cover 55 and cooperates with the pump cover 55 to draw oil from the tube 46 through a passageway 61 formed in the cylinder block 12 and a corresponding passageway 62 (FIG. 6) formed in the timing cover 49 . This oil then enters the oil pump 53 through an opening 63 formed in the timing cover 49 radially outwardly of the opening 51 that passes the crankshaft 18 .
The oil pumped by the oil pump 53 is then delivered through a supply passageway 64 (FIGS. 3-5) formed in the timing cover 49 and from there to an arcuate passageway 65 that is also formed in the rear side of the timing cover 49 . The outer side of this passageway 65 is closed by a closure plate 66 that is affixed in a suitable manner to the timing cover 49 in overlying relationship to the passageway 65 . The passageway 65 is intersected by a drilled passageway 67 which is, in turn, communicates with the supply passageway 64 of the timing cover 49 . The outer end of the supply passageway 64 is closed by a sealing ball 68 .
The passageway 65 delivers the pumped lubricant to a further drilled passageway 69 formed in the timing cover 49 which communicates with a pressure relief valve 71 that is slidably supported in a drilled passageway 72 also formed in the timing cover 49 . The outer end of this passageway 72 is closed by a closure member 73 . A coil compression spring 74 normally urges the relief valve 71 to a closed position wherein communication with a small bypass port 75 is precluded. The bypass port 75 is also formed in the timing cover 49 . This bypass port 75 communicates back with the inlet side of the pump 53 or with the oil pan 22 , depending upon the preference of the designer.
The passageway 69 also communicates with a main oil gallery 76 that is formed in the cylinder block 12 and which serves to distribute lubricant to the engine 11 for its lubrication in any well known manner.
Thus, from the foregoing description, it should be readily apparent that the oil pump 53 is positioned externally of the main engine body and specifically the cylinder block 12 and oil pan 22 and thus, permits shortening of the internal portion of the engine. Because the oil pump 53 is nested within the drive pulley 52 it also does not add to the overall length of the engine. Furthermore, a simpler construction is possible and thus the engine can be made more compact and yet the lubrication system very easily manufactured. Of course, the foregoing description is that of a preferred embodiment of the invention and various changes and modifications may be made without department from the spirit and scope of the invention, as defined by the appended claims. | An improved oil pump drive arrangement and pressure relief valve therefore for an internal combustion engine. The oil pump is disposed externally of the engine around a shaft that extends through the body of the engine. This extending portion of the shaft drives at least one engine accessory through a pulley which axially overlaps and circumferentially surrounds the oil pump housing to provide a compact engine construction. | 5 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This patent application is related to and claims priority from U.S. Provisional Patent Application Ser. No. 60/570,530, entitled: Rocking Infant Carrier, filed, May 12, 2004. U.S. Provisional Patent Application Ser. No. 60/570,530 is incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The present invention is directed to infant carriers or seats. In particular, the present invention is directed to a rocking infant carrier.
BACKGROUND OF THE INVENTION
[0003] Infant safety car seats or infant carriers are designed to be portable, to and from a vehicle such as an automobile or the like. A contemporary exemplary infant safety car seat or infant carrier is shown in FIG. 1 . This infant carrier 20 is formed of a body 22 , that in a typical orientation includes a seat portion 24 , whose front side 26 , is configured for holding an infant. The body 22 also includes a ground contacting portion 28 , for contacting the ground.
[0004] The body 22 is such that in a typical orientation, the infant's head and upper body are positioned in the seat portion 24 , at an elevation above the feet. The body 22 is designed to receive a seat belt, such that the infant can be in the infant carrier while in a car or other moving vehicle. The seat portion 24 is typically of a shape that conforms to the shape of an infant or baby, and the infant typically fits snugly therein.
[0005] The infant carrier 20 typically includes a handle 30 , from which the infant carrier 20 is carried. The body 22 , at its ground contacting portion 28 , typically includes rails or side members 32 , 33 , with an open area or cavity 36 , between the rear 38 of the seat portion 24 , and the rails 32 , 33 . The rails 32 , 33 , are continuous with the sides of the ground contacting portion 28 , and as such typically define a curvature, extending along both sides of the carrier 20 . A cover typically is fitted over the seat portion 24 of the body 22 of the infant carrier 20 .
[0006] The infant carrier 20 is designed to be removed from the vehicle, by being disconnected from the seat belt, base and/or other retaining structure. As a result, the infant is carried to the new location in the same infant carrier. This is advantageous, for the infant, who may be sleeping, is not disrupted by being transferred to a different seat or carrier upon leaving the vehicle. Moreover, while the infant is in the carrier in the vehicle, the motion of the vehicle as it travels typically lulls the infant to sleep.
[0007] However, when the infant carrier 20 , with the infant therein, is removed from the vehicle, the infant may wake up. Upon waking up, the infant can sense that they are no longer in motion, and they typically become agitated. To calm the infant, a parent or other person attending to the infant typically rocks the infant carrier manually, to typically lull the infant to sleep.
[0008] Rocking infants (babies) to sleep with rhythmic motion relaxes them. Infants crave movement after birth, because motion is the norm to them. Being still disconcerts infants, as they are very sensitive to outside stimulus, and easily awaken when still.
[0009] Once the infant (baby) falls asleep, they enter an active sleep state (also called light sleep or Rapid Eye Movement sleep). After about 20 - 30 minutes of active sleep, the infant enters a deep sleep state. Rocking the infant typically lulls the infant to sleep, such that they reach the deep sleep state.
SUMMARY OF THE INVENTION
[0010] The present invention improves on the contemporary art by providing an apparatus for automatically rocking an infant. The apparatus is typically portable. The apparatus includes an infant carrier, with a seat portion for holding an infant, the carrier including oppositely disposed curved rails, that contact the ground surface. A panel is movably mounted to the carrier between the oppositely disposed rails. A mechanism for moving the panel, for rocking the carrier, is in the space between the rails and the panel. Rocking occurs as the panel is moved between retracted and extended positions, while the carrier remains in its initial location (position) during the entire time of rocking. Additionally, the rocking is such that it will normally lull an infant to a relaxed state, whereby they fall asleep.
[0011] An embodiment of the invention is directed to an infant carrier. The carrier includes a body, including a portion configured for holding an infant, and a curved portion for contacting a surface, and a panel. The panel is movably mounted to the body, and the panel is positioned proximate to the curved portion of the body. There is also a movement mechanism at least partially within the body, the movement mechanism operatively connected with the panel for moving the panel between a retracted position with respect to the body, and an extended position with respect to the body, for rocking the body on the surface.
[0012] Another embodiment of the invention is directed to a rocking apparatus for placement at least partially into a partially open space in an infant carrier. The infant carrier includes at least one ground contacting portion. The rocking apparatus includes, a panel movably mounted to the infant carrier, the panel positioned proximate to ground contacting portion of the infant carrier; and, a movement mechanism. The movement mechanism is operatively connected to the panel for moving the panel between a retracted position with respect to the open space in the infant carrier, and an extended position with respect to the open space in the infant carrier, for rocking the infant carrier along the at least one ground contacting portion.
[0013] Another embodiment of the invention is directed to a rocking apparatus for placement at least partially into a partially open space in an infant carrier, the infant carrier including at least one ground contacting portion. The rocking apparatus includes, a movement mechanism, and, a ground contacting member coupled to the movement mechanism, such that movement of the ground contacting member by the movement member causes the infant carrier to rock along the at least one ground contacting portion.
[0014] Another embodiment of the invention is directed to an infant carrier. The infant carrier includes, a body including a portion for holding an infant, and a curved portion for contacting a surface, a movement mechanism, and, a ground contacting member. The ground contacting member is coupled to the movement mechanism, such that movement of the ground contacting member by the movement member causes the body to rock along the curved portion.
[0015] Another embodiment of the invention is directed to a method for rocking an infant. The method includes providing an infant carrier. The infant carrier includes, a body including a portion configured for holding an infant, and a curved portion for contacting a surface, a panel movably mounted to the body, the panel positioned proximate to the curved portion of the body, and, a movement mechanism at least partially within the body, the movement mechanism for moving the panel between a retracted position with respect to the body, and an extended position with respect to the body, for rocking the body on the surface. An infant is provided to the carrier, typically by placing an infant, into the portion of the body configured for holding an infant, movement mechanism is activated, for rocking the body on the surface.
[0016] Another embodiment of the invention is also directed to a method for rocking an infant. The method includes providing an infant carrier. The infant carrier includes, a body including a portion configured for holding an infant, and a curved portion for contacting a surface, a movement mechanism, and, a ground contacting member coupled to the movement mechanism, such that movement of the ground contacting member by the movement member causes the body to rock along the curved portion. An infant is provided to the carrier, typically by placing an infant, into the portion of the body configured for holding an infant, movement mechanism is activated, for rocking the body on the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Attention is now directed to the drawing figures, where like numerals or characters indicate corresponding or like components. In the drawings:
[0018] FIG. 1 is a perspective view of a conventional infant carrier;
[0019] FIG. 2 is a rear perspective view of the apparatus in accordance with an embodiment of the invention;
[0020] FIG. 3 is a perspective view of a portion of the rotation mechanism of the apparatus of FIG. 2 ;
[0021] FIGS. 4A-4D are side views of the apparatus detailing an exemplary operation;
[0022] FIGS. 5A and 5B are partially broken-away side views of an apparatus in accordance with a second embodiment of the invention;
[0023] FIGS. 6A and 6B are rear perspective views of the apparatus in the positions of FIGS. 5A and 5B , respectively, showing the rocking mechanisms and the positions of the components therein;
[0024] FIG. 7 is a partial broken-away side view of an apparatus in accordance with a third embodiment of the invention;
[0025] FIGS. 8A and 8B are partially broken-away side views of an apparatus in accordance with a fourth embodiment of the invention; and
[0026] FIG. 8C is a rear perspective view of the apparatus, in the position of FIG. 8A , in accordance with a fourth embodiment of the invention.
DETAILED DESCRIPTION
[0027] FIGS. 2 and 3 show an apparatus 100 in accordance with an embodiment of the invention. The apparatus 100 includes an infant carrier 20 , for example, infant carrier 20 , as detailed above and shown in FIG. 1 , with identical and/or similar components having the same numbers as those on the infant carrier 20 .
[0028] Throughout this document, references are made to the directions, up, down, upward, downward, front, rear, frontward, rearward, and other directional references are made. These directional references are made for exemplary purposes, to describe the embodiments of the invention in typical orientations, and the embodiments of the invention are not limited by these directional references.
[0029] The infant carrier 20 , as stated above, typically includes a seat portion 24 , within the body 22 of the infant carrier 20 . The seat portion 24 is typically covered by a cover 102 ( FIG. 4A ), elastically fitted over the edges of the body 22 of the apparatus 100 . A rocking mechanism 110 , for rocking the infant carrier 20 , is housed, at least partially within the cavity 36 of the body 22 .
[0030] The apparatus 100 includes a carrying handle 30 ( FIGS. 4A-4D ), that is moveable in a rotating manner. The body 22 includes curved rails 32 , 33 for contacting the ground surface GS ( FIGS. 4A-4D ), that are continuous along the sides of the body 22 , to define a curvature extending from the front end 40 of the carrier 20 of the apparatus 100 to the rear end 41 of the carrier 20 of the apparatus 100 . The curvature allows the infant carrier 20 to rock back and forth, along the ground surface GS ( FIGS. 4A-4D ).
[0031] The rocking mechanism 110 includes a motor 112 , that is coupled to a shaft 114 , that is in turn coupled to a panel 116 . The panel 116 is typically movably mounted to the body 22 of the carrier 20 , and is shaped to typically cover at least a portion of the cavity 36 .
[0032] The motor 112 moves the shaft 114 , that moves the panel 116 , between positions where the panel 116 extends beyond the arc defined by the curvature of the rails 32 , 33 (an extended position), and retracts to a point at least coincident to, and typically within the arc (a retracted position), in order to cause the carrier 20 of the apparatus 100 to rock back and forth. The motor 112 is typically powered by a power source 120 , typically of one or more batteries, either single use or rechargeable (inside or outside of the apparatus 100 ), and the motor 112 is typically turned on and off by a switch 122 . The motor 112 is typically controlled by a variable controller (MC) 124 .
[0033] The motor 112 is attached to the rear side 38 of the seat portion 24 in the cavity 36 of the rear end 41 of the apparatus 100 . The attachment of the motor 112 to the rear side 38 of the seat portion 24 is typically by clamps or other mechanical fasteners, such that the motor 112 is typically mounted transversely in the apparatus 100 . This transverse mounting of the motor 112 allows rotation of the motor 112 to be in alignment with the rocking motion of the carrier 20 of the apparatus 100 .
[0034] A stub 130 extends from the motor 112 , with an end of the stub 130 attaching to a cam 132 . The cam 132 is typically in the shape of a circular disk. The motor 112 can rotate the stub 130 (and therefore, the cam 132 ), either unidirectionally, or bidirectionally, depending on the motor selected. For example, the cam 132 rotates in the same direction as the motor 112 and shaft 130 , in the direction of the arrow 136 ( FIG. 3 ). The cam 132 includes an opening (not shown) that aligns with an opening 137 on the shaft 114 , at a first end 114 a , to receive a pin 138 , facilitating a moveable attachment between the shaft 114 and the cam 132 . The pin 138 is typically close to the periphery of the cam 132 , offset from the center on the cam 132 . The second end 114 b of the shaft 114 , opposite the first end 114 a , includes a joint 140 , that is typically pivotally mounted to the end 114 b of the shaft 114 . The joint 140 attaches to the panel 116 , by mechanical fasteners, adhesives, or combinations thereof.
[0035] The variable controller (MC) 124 is such that it can reduce or increase the speed of rotation of the motor 112 . Typically, the controller (MC) 124 is used to slow down the rocking action. This controller (MC) 124 is controlled by a knob 125 , located on an external surface of the carrier 20 of the apparatus 100 . This controller (MC) 124 is turned on and off by the switch 122 , with rocking speed controlled by moving the knob 125 . The controller (MC) 124 is typically designed to begin the rocking motion at a slower rotational speed, and then build up to the desired speed, for example, of one rotation per second. The controller (MC) 124 may also control (by the user turning the knob 125 ), the direction of rotation of the motor 112 .
[0036] The motor 112 is, for example, a DC motor, with sufficient torque to exert approximately 12 pounds of force pushing down on the panel 116 . This is sufficient force for offsetting the infant's or baby's weight, such that the carrier 20 rocks back and forth in the same location, without advancing forward or rearward (from the initial position or location). The motor 112 , alone, or with either or both of the stub 130 and/or the cam 132 , typically form a motor unit.
[0037] The panel 116 typically hides the motor 112 , shaft 114 , cam 132 and the stub 130 . The panel 116 is attached at one of its ends to the body 22 of the carrier 20 of the apparatus 100 by an axle 142 that extends through openings 143 a in the side walls 143 of the panel 116 and into the body 22 of the carrier 20 . This axial attachment allows the panel 116 to be pivotally or rotationally mounted to the carrier body 22 . The width of the panel 116 is such that the panel 116 fits between the rails 32 , 33 .
[0038] The panel 116 is typically a tray-like member, with a sheet like portion 146 , intermediate the side walls 143 . The sheet like portion 146 is shaped to conform with the contour of the rails 32 , 33 , as its outer side 144 , is typically curved convexly along a first portion 116 a , proximate to the rails 32 , 33 . The panel 116 has an inner side (not shown) that is typically concave. This shape allows the panel 116 to protrude from and return to within the cavity 36 , always staying between the rails 32 , 33 , by essentially sliding parallel to the rails 32 , 33 . The panel 116 may have a second portion 116 b of at least its outer side 144 , of a second curvature, to provide additional cover to the rocking mechanism 110 of the apparatus 100 . The panel 116 is typically formed by a single piece, but may be formed of multiple pieces with multiple curvatures.
[0039] The panel 116 is, for example, of a hard resilient plastic, such as polyethylene, and the like, that provides for sliding along a ground surface. The panel 116 is typically made by conventional plastic forming techniques, such as injection or rotational molding.
[0040] The apparatus 100 also includes a rechargeable battery or other similar power source, as the power source 120 . A removable charging cord (not shown) (attachable to an electrical outlet or the like) can be attached to the power source 120 , that, for example, allows charging of the battery overnight with enough charge for daily use (for example, approximately ten hours).
[0041] Turning to FIGS. 4A-4D , an exemplary operation of the apparatus 100 , in a typical rocking cycle, is shown with the apparatus 100 in typical positions, resting on the ground surface GS. The apparatus 100 can be such that the panel 116 moves between an inward or retracted position where the panel 116 remains inward of the rails 32 , 33 , and an outward or extended position, where the panel 116 is outside and beyond the rails 32 , 33 and all positions in-between. When rocking of the carrier 20 of the apparatus 100 is desired, the rocking mechanism 110 , and in particular, the motor 112 , is activated.
[0042] Once activated, the panel 116 is pushed by the motion of the motor 112 and shaft 114 outwardly and downwardly, so that when the motor 112 is operating, the shaft 114 pushes this panel 116 outward, beyond the rails 32 , 33 , to the outward or extended position, for example, the maximum outward or extended position, as shown in FIG. 4A . This outward movement of the panel 116 rocks the carrier 20 of the apparatus 100 forward, as the rails 32 , 33 at the front end 40 of the carrier 20 have moved toward the ground surface GS. The continued revolution of the cam 132 (in the direction of the arrow 136 ) pulls the shaft 114 , such that the panel 116 begins to retract, moving toward the body 22 of the apparatus 100 , as shown in FIG. 4B . In FIG. 4B , the edges of the ground contacting portion 28 formed by the rails 32 , 33 at the rear end 41 of the carrier move toward the ground surface GS, while the rails 32 , 33 at the front end 40 of the carrier 20 move upward.
[0043] The cam 132 continues its rotation (as rotated by the motor 112 ), retracting the panel 116 , to a fully retracted position inside of the rails 32 , 33 , as shown in FIG. 4C . This complete retraction of the panel, to inside of the curvature of the rails 32 , 33 , coupled with gravity, places the rails 32 , 33 , at their rearward portions (proximate to the panel 116 ), again into contact with the ground surface GS (and the rails 32 , 33 at the front end 40 of the carrier 20 move upward), whereby the carrier 20 of the apparatus 100 rocks back in a rearward direction. With the action of the motor 112 , rotating the disk 132 being continuous, the panel 116 is again pushed outward moving the baby and the carrier 20 of the apparatus 100 in an upward direction, with the panel 116 again in a partially extended position, as shown in FIG. 4D . In FIG. 4D , the edges of the rails 32 , 33 at the rear end 41 move out of contact with the ground surface (GS), while the rails 32 , 33 at the front end 40 of the apparatus 100 move downward, toward the ground surface GS.
[0044] This motion cycle occurs approximately sixty times a minute. The apparatus 100 returns to its original position, therefore, completing a cycle, approximately once every second. The rotation speed of the motor shaft 130 is approximately sixty revolutions per minute, compared to the approximate speed of normally manually rocking an infant (baby) in a carrier.
[0045] In an alternate embodiment of the apparatus 100 , the panel 116 can be removed, and the joint 140 can be replaced with, or terminate at a rotatable wheel, or a ball-like tip. All other aspects of this alternate embodiment would be similar to the apparatus 100 .
[0046] FIGS. 5A, 5B , 6 A and 6 B show a second embodiment of a rocking infant carrier apparatus 200 . This embodiment utilizes, for example, the infant carrier 20 detailed above, and shown in FIG. 1 . FIGS. 5A and 6A (in FIG. 6A , the material 219 has been removed) show the apparatus 200 in a position, where the panel 216 is in the inward or retracted position, while FIGS. 5B and 6B (in FIG. 6B , the material 219 has been removed), show the apparatus 200 in an outward or extended position, where the panel 216 is extended beyond the periphery of the carrier 20 of the apparatus 200 . The panel 216 is such that it moves between these retracted and extended, and all positions therebetween, in order to facilitate rocking of the carrier 20 of the apparatus 200 .
[0047] The apparatus 200 is similar to the apparatus 100 detailed above, except for the rocking mechanism 210 , including the panel 216 . In the rocking mechanism 210 , the motor 212 includes a gear box (not shown), for driving a crank 213 , typically “Z” shaped, that connects to a shaft 214 . The motor 212 , alone, or with components such as the crank 213 , typically define a motor unit. The panel 216 functions similarly to the panel 116 , that when coupled to the motor 212 , typically through the crank 213 and shaft 214 , moves the panel 216 to rock the carrier portion 20 of the apparatus 200 . However, in the apparatus 200 , the panel 216 is shaped different from the panel 116 (of the apparatus 100 ). The apparatus 200 may also include a variable controller and controlling knob, associated with the motor 212 , similar to that used with the motor 112 and the apparatus 100 detailed above.
[0048] In the rocking mechanism 210 for the apparatus 200 , the motor 212 mounts to the rear side 38 of the seat portion 24 , typically longitudinally. Mounting of the motor 212 to the rear side 38 of the seat portion is typically by mechanical fasteners, such as screws, brackets, and the like. The motor 212 includes a gearbox (not shown), that attaches to and turns (rotates) a crank 213 , either clockwise or counterclockwise, depending on the gearing of the motor 212 . The crank 213 is received in the shaft 214 in an opening or slot 215 . The shaft 214 is typically two pieces 217 , 218 , but may be a single piece or three or more pieces. These pieces 217 , 218 are typically joined by a member or fastener 218 a , that maintains the pieces 217 , 218 in a fixed relationship with respect to each other. The second piece 218 is attached to the panel 216 , at a moveable joint 218 b (similar to the joint 140 described above and shown in FIG. 3 ) by mechanical fasteners, adhesives, or combinations thereof.
[0049] The motor 212 and shaft 214 typically fit within the cavity 36 of the body 22 , and the panel 216 , at the rear end 41 of the apparatus 200 . There is typically a piece of material 219 , such as cloth or fabric reinforced paper or the like, between the panel 216 and the body 22 , to cover the cavity 36 between the panel 216 and the body 22 . The material 219 is typically folded, so as to be accordion-like or has slack, to allow for expansion, that occurs when the panel 216 moves away from the body 22 during rocking, as the apparatus 200 moves toward the extended position ( FIGS. 5B and 6B ).
[0050] The panel 216 includes a heel portion 230 and a toe portion 232 . The heel portion 230 extends beyond and remains outside of the carrier 20 during operation (rocking) of the carrier 20 of the apparatus 200 . The toe portion 232 is movably attached to the body 22 of the carrier 20 , by an axle 234 , that extends through the panel 216 (through openings 236 , 237 in the sidewalls 238 , 239 of the panel 216 ) and into the body 22 of the carrier 20 of the apparatus 200 . This attachment allows for the panel 216 to move pivotally (rotationally) with respect to the body 22 of the carrier 20 . The toe portion 232 is typically attached to the body 22 , such that it remains within the periphery of the curvature of the rails 32 , 33 .
[0051] The heel portion 230 typically is formed by a linear segment 230 a and a curved segment 230 b . The arrangement of these segments 230 a , 230 b , allows the apparatus 200 to be used on surfaces, such as carpet and the like, allowing sliding of the panel 216 without pulling up or getting caught in the carpet. Additionally, when rocking of the carrier 20 of the apparatus 200 is desired, the panel 216 , moves between fully retracted ( FIGS. 5A and 6A ) and fully extended positions ( FIGS. 5B and 6B ), and all positions therebetween.
[0052] When rocking of the apparatus 200 is desired, the switch 240 (similar to the switch 122 , described above), is activated or turned on, activating the motor 212 . The motor 212 rotates the crank 213 , that pulls the shaft 214 . Specifically, the shaft 214 is pulled such that its pieces 217 , 218 move between a fully retracted position, as shown in FIGS. 5A and 6A , and a fully extended position, as shown in FIGS. 5B and 6B , and all positions therebetween, to cause the carrier 20 of the apparatus 200 to rock back and forth along its curvature (the edges defined by the edges of the rails 32 , 33 at the front 40 and rear 41 ends of the carrier 20 of the apparatus 200 ).
[0053] In FIG. 7 , another apparatus 100 ′, similar in construction and operation to the apparatus 100 (described above, and shown in FIGS. 2, 3 and 4 A- 4 D), is shown. This apparatus 100 ′ is similar in all aspects to the apparatus 100 , except that it lacks a moveable panel, and the motor 112 is coupled to a gear 302 . The gear 302 (having a peripheral surface 302 a ) is meshed with a cam 304 , having a correspondingly configured peripheral surface 304 a . The cam 304 is attached to a shaft 306 , in a moveable attachment by a pin 308 , that extends through aligned openings (not shown) in the cam 304 and the shaft 306 (similar to the pin 138 ) detailed above. The shaft 306 extends through an opening 309 in a cover 310 , that covers the cavity 36 of the apparatus 100 ′, at least partially, and the shaft 306 terminates in a wheel 312 , axially mounted to it. The wheel 312 is such that when the apparatus 100 ′ is rocking, the apparatus 100 ′ will remain in its initial location.
[0054] FIGS. 8A-8C show an apparatus 200 ′, similar in construction and operation to the apparatus 200 , as detailed above and shown in FIGS. 5A, 5B , 6 A and 6 B. This apparatus 200 ′ is similar in all aspects to the apparatus 200 , except that it includes a wheel 402 , typically centrally mounted to the panel 216 . The wheel 402 is typically rotatably mounted at the heel portion 230 , along the linear segment 230 a . Mounting of the wheel 402 is such that the wheel 402 extends slightly beyond the panel 216 , to contact the ground surface (GS), while the panel 216 remains clear of the ground surface (GS), when the panel 216 of the apparatus 200 ′ is in the fully retracted position ( FIG. 8A ), when the panel 216 of the apparatus 200 ′ is in the fully extended position ( FIG. 8B ), and all positions therebetween.
[0055] While a single wheel 402 is shown, multiple wheels are also permissible, as are one or more rollers or the like. When multiple wheels or rollers are used, they are typically mounted symmetrically on the panel 216 .
[0056] In exemplary operations of the aforementioned apparatus 100 , 200 , 100 ′, 200 ′ and alternate embodiments thereto, the apparatus 100 , 200 , 100 ′ and 200 ′ is placed onto the ground surface, with the infant therein, or the infant is placed into the portion 24 of the carrier 20 of the apparatus 100 , 200 , 100 ′, 200 ′. The motor 112 , 212 is activated, typically by turning on the respective switch 122 , 240 and the respective apparatus 100 , 200 , 100 ′, 200 ′ rocks back and forth along the curved rails 32 , 33 at the bottom portion 28 of the body 22 . Rocking speed can be controlled by turning the knob 125 to adjust the controller (MC) 124 . When rocking has lulled the infant to sleep, it can be terminated by deactivating (turning off) the respective switch 122 , 240 , such that rocking of the respective apparatus 100 , 200 , 100 ′, 200 ′ stops.
[0057] There have been shown and described preferred embodiments of a rocking infant carrier. It is apparent to those skilled in the art, however, that many changes, variations, modifications, and other uses and applications for the apparatus and its components are possible, and also such changes, variations, modifications, and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention, which is limited only by the claims which follow. | A rocking infant carrier includes a seat portion for holding an infant, and oppositely disposed curved rails, that contact the ground surface. A panel is movably mounted to the carrier between the oppositely disposed rails. A mechanism for moving the panel, for rocking the carrier, is in the space between the rails and the panel. Rocking occurs as the panel is moved between retracted and extended positions, while the carrier remains in its initial location (position) during the entire time of rocking. Additionally, the rocking is such that it will normally lull an infant to a relaxed state, whereby they fall asleep. | 0 |
BACKGROUND OF THE INVENTION
[0001] This invention relates generally to electric motors and more particularly to stator core interlocks that allow minimal flux leakage.
[0002] Electric motors can vary from small, fractional motors that are found, for example, in washing machines, refrigerators and air conditioners, to large industrial motors that are found, for example, in manufacturing equipment, compressors, fans and the like. A typical motor includes a rotating central portion known as a rotor and a stationary outer portion referred to as a stator. Both the stator and rotor are contained, at least partially within a housing that carries the motor. A stator core is typically formed from a plurality of stacked plates or laminations. The laminations which are generally formed from metal, may be punched or pressed and subsequently stacked one on top of another to form the stator core. Due to the possible asymmetries in the lamination material, the laminations can be rotated so that the stator core, upon final assembly, forms a straight rather than lopsided stack. The laminations are interlocked with one another to form a rigid stator core structure and to prevent the laminations from shifting relative to one another.
[0003] In one known interlocking arrangement, each lamination has a dimple or a recess punched into the surface which forms a corresponding projection on the opposite side of the lamination. The laminations are then stacked one on top of the other with the projections from one lamination engaging and residing within the recess in the next adjacent lamination. In this nested arrangement, the laminations are aligned with one another by engagement of the projections and recesses. This is a common and accepted method for interlocking laminations. However, the common and accepted method does not reduce the flux leakage.
[0004] Therefore, it would be desirable to provide a method for a stator core interlocking arrangement that is cost effective as well as effective in reducing the flux leakage.
BRIEF SUMMARY OF THE INVENTION
[0005] In one embodiment, a stator lamination includes a plurality of notches and interlock tabs. The notches extend outward from the interlock tabs to an outer diameter of the lamination to create a void in a back iron area of the interlock tabs. The laminations are stacked to form a stator core. The stack defines at least one inner lamination having laminations positioned adjacent to both sides of the laminations. Each lamination has notches extending outward from an outside edge of the interlock tabs to the outer diameter of the stator lamination, thus creating a void in the back iron area of the stator lamination adjacent the interlocking tabs. The notch impinges upon the interlock tabs along the length of the stator core, interrupting the flux path through the iron towards the outer diameter of the interlock. Since the flux path is interrupted, the flux is significantly less likely to link the conductive interlocks, and thereby reduces the current flow through the interlocks.
[0006] In yet another embodiment, a method for manufacturing a laminated stator core for an electric motor includes forming a plurality of notches and tabs in the interlock laminations. More particularly, the method includes providing a plurality of generally planar laminations, each lamination having an axis substantially perpendicular to the lamination plane, forming a plurality of notches in the lamination, and forming a plurality of interlock tabs. The laminations are stacked to form a stator core.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] [0007]FIG. 1 is an exploded, perspective view of an exemplary motor, illustrating a stator having a core formed in accordance with one embodiment of the present invention;
[0008] [0008]FIG. 2 is a top view of the stator core shown in FIG. 1;
[0009] [0009]FIG. 3 is an enlarged view of a notch area shown in FIG. 2;
[0010] [0010]FIG. 4 is an enlarged view of an alternative embodiment of the notch area shown in FIG. 2;
[0011] [0011]FIG. 5 is an enlarged view of a further alternative embodiment of the notch area shown in FIG. 2;
[0012] [0012]FIG. 6 is an enlarged view of a still further embodiment of the notch area shown in FIG. 2; and
[0013] [0013]FIG. 7 is a side view of the stator core shown in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
[0014] [0014]FIG. 1 is an exploded, perspective view of an exemplary motor 10 , illustrated in accordance with the principles of the present invention. Motor 10 is enclosed within a housing 12 and includes a rotor 14 and a stator 16 . Stator 16 is mounted to and at least partially within housing 12 . Stator 16 includes a longitudinal axis 18 , there-through. Rotor 14 is positioned at least partially within stator 16 and includes a longitudinal axis 20 collinear with stator axis 18 .
[0015] Rotor 14 is positioned within stator 16 such that a gap (not shown) extends therebetween. The gap is sufficiently large to permit rotor 14 to freely rotate within stator 16 without contacting stator 16 . In addition, the gap is sufficiently small such that a magnetic field which is created in stator 16 can in turn induce an electric current in rotor 14 which generates an opposing magnetic field. Interaction between these two magnetic fields is converted to mechanical energy and results in rotation of rotor 14 . As the gap between rotor 14 and stator 16 increases, the rotor current inducement decreases. Thus, the size of the gap between the rotor 14 and stator 16 must be determined by balancing the need to maintain space between rotor 14 and stator 16 while maintaining rotor 14 and stator 16 sufficiently close to reduce and preferably minimize field losses.
[0016] Rotor 14 includes a rotor core 22 and stator 16 includes a stator core 24 formed from a plurality of plates or laminations 26 stacked together. Laminations 26 are secured relative to one another by an interlocking system. The interlocking system prevents the laminations 26 from rotating, shifting and separating from each other, and thus maintains stator core 24 as a unitary member during motor fabrication.
[0017] [0017]FIG. 2 is a top view of the stator core shown in FIG. 1. Stator core 24 (shown in FIG. 1) includes a plurality of teeth 28 defining a plurality of slots 30 . Teeth 28 are formed at an inner edge 32 of each lamination 26 . Teeth 28 are formed integral with the lamination outer or ring portion 36 . Slots 30 are configured to receive and secure conducting elements (not shown) therein. Stator core lamination 26 defines an outer diameter 40 and an inner diameter 42 of stator core 24 . A group of notches or openings 50 are punched into lamination 26 prior to punching a plurality of stator interlock tabs 52 . Interlock tabs 52 include an outside edge 54 , an inside edge 56 , an axis of symmetry 58 and have an oval shape. Notches 50 are oriented such that they extend outward from outside edge 54 of interlock tab 52 to an outside diameter 60 of stator lamination 26 . Interlock tabs 52 are partially punched through lamination 26 . In the exemplary embodiment, there are six notches 50 and six interlock tabs 52 . When stator core 24 is assembled, each interlock tab 52 enhances the engagement between the laminations, to prevent shifting therebetween. FIGS. 3 through 6 (described below) explain the lamination interlocking arrangement in detail.
[0018] [0018]FIG. 3 is an enlarged view of a notch area 62 (shown in FIG. 2). A stator lamination 64 includes an interlock tab 72 . Interlock tab 72 has an outside edge 74 , an inside edge 76 and an axis of symmetry 78 . A notch 80 extends outward from outside edge 74 of interlock tab 72 to an outside diameter 82 (also numbered as 60 in FIG. 2) of stator lamination 26 shown in FIG. 2. Notch 80 is fully punched through lamination 26 . Interlock tab 72 is partially punched through lamination 26 . Notch 80 has an axis of symmetry 84 that substantially coincides with axis of symmetry 78 of tab 72 . There are six notches 80 and six partially punched interlock tabs 72 .
[0019] [0019]FIG. 4 is an enlarged view of an alternative embodiment of notch area 62 (shown in FIG. 2). A stator lamination 90 includes a notch 92 punched at an angle α. Notch 92 extends outward from an outside edge 94 of interlock tab 96 , at angle α, to an outside diameter 98 of stator lamination 90 . An inside edge 100 of interlock tab 96 is substantially parallel to outside edge 94 . An axis of symmetry 102 of interlock tab 92 does not coincide with an axis of symmetry 104 of notch 92 . Instead, axis of symmetry 102 is positioned at angle α with respect to axis of symmetry 104 .
[0020] [0020]FIG. 5 is an enlarged view of a further alternative embodiment of notch area 62 (shown in FIG. 2). A stator lamination 110 includes a notch 120 . An axis of symmetry 124 of notch 120 is substantially parallel to an axis of symmetry 128 of an interlock tab 130 . Notch 120 is punched at a perpendicular angle to an axis of symmetry 132 of interlock tab 130 . Axis of symmetry 132 is perpendicular to both axes 124 and 128 . Furthermore, axis of symmetry 124 does not coincide with axis of symmetry 128 . Instead axis of symmetry 124 is located a pre-determined distance “D” from axis of symmetry 128 . The stator lamination arrangement in this embodiment provides substantial surface area of interlock tabs for more robust mechanical engagement than other embodiments.
[0021] [0021]FIG. 6 is an enlarged view of a still further embodiment of notch area 62 (shown in FIG. 2). A stator lamination 140 includes a partially punched interlock tab 152 . Notch 50 (shown in FIG. 2) is not punched. Additionally, interlock tab 152 extends inward from an outside diameter 154 of stator lamination 140 .
[0022] [0022]FIG. 7 is a side view 160 of stator core 24 shown in FIG. 1. Each lamination of stator core 24 includes at least two interlock tabs. Interlock tabs are stacked on top of each other to lock adjacent laminations together. For example, a lamination 162 has a corresponding interlock tab 192 . Similarly laminations 164 , 166 , 168 , 170 , 172 , 174 , and 176 have corresponding interlock tabs 194 , 196 , 198 , 200 , 202 , 204 , and 206 respectively. For example, one end lamination 178 receives interlock tab 206 (also shown as number 52 in FIG. 2) of adjacent lamination 176 . Similarly, interlock tab 192 of lamination 162 is received by adjacent lamination 164 . Since lamination 178 is the end lamination of stator core 24 , lamination 178 does not include a punched tab, but instead has a flat surface 220 . Thus, lamination 178 receives interlock tabs 206 of adjacent lamination 176 .
[0023] In the exemplary embodiment, there are at least two interlock tabs per lamination. Interlock tab 192 of lamination 162 is received by lamination 164 . Interlock tab 194 of lamination 164 is received by lamination 166 . The upper surface 222 (shown as 36 in FIG. 2) of lamination 162 (shown as 26 in FIG. 2) is substantially flat and substantially parallel to a second surface 224 of lamination 162 . End lamination 178 has a flat surface 220 and an upper surface 228 , both surfaces substantially parallel. End lamination 178 receives interlock tabs 206 of adjacent lamination 176 . There are no interlock tabs on end lamination 178 .
[0024] End laminations 162 and 178 are formed such that they are engaged by only one adjacent lamination 164 and 176 respectively. On the other side, interior laminations 164 , 166 , 168 , 170 , 172 , and 174 engage two adjacent laminations, one at the top and other at the bottom.
[0025] The embodiments described above relate specifically to stator lamination arrangements in detail. However, the lamination arrangements are equally applicable to rotor lamination, interlock transformer lamination, ballast lamination, automobile and other ignition coils and various other commercially available electrical devices that utilize lamination arrangements.
[0026] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims. | A method for manufacturing a laminated stator core for an electric motor includes providing a plurality of generally planar laminations, forming a plurality of notches into the lamination, and finally forming a plurality of interlock tabs. The notches extend outward from the interlock tabs to an outside diameter of the lamination to create a void in the back iron area of the interlock tabs to reduce the flux leakage. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to a monochromator used in a spectrophotometer or the like.
A monochromator is available in the form of a single monochromator adapted to dispose one dispersion element in an optical path, and a double monochromator adapted to arrange two dispersion elements in series with each other in the optical path. the single monochromator is simple in its structure but involves much stray light whereas the double monochromator is subject to much less stray light but has a lower sensitivity, viz., lower luminous intensity. In view of the fact that these monochromators have both merits and demerits, proper use of one type of monochromator or the other depends on the object to be measured.
Both single and double monochromators which are designed so that the diffraction gratings as dispersion elements are selected and switched over interchangeably in usage have been well known.
In both cases, however, one diffraction grating is used in a single monochromator for switchover while one or both of the diffraction gratings which are provided in pairs are employed in a double monochromator. For this reason, the single monochromator has no other function, and the double monochromator likewise, so that they are only used in their own individual applications and nothing more.
Consequently, inconvenience results when various measurements need to be made, since both the single and the double monochromators need to be prepared beforehand.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a monochromator which is used by selecting a single or double monochromator according to the object to be measured.
A monochromator according to the invention is fabricated so that two spectroscopes each having one or more dispersion elements are disposed in series with each other in an optical path, and that a mirror is positioned in one or both of the spectroscopes and may be positioned equivalently to where the dispersion element(s) are located so that it may be switched over from the dispersion element(s).
Concave diffraction gratings such as spherical, ellipsoidl or toroidal concave diffraction gratings, or plane diffraction gratings such as ethelette, echelle or laminar diffraction gratings have been proposed as dispersion elements. On the other hand, it has been suggested that a planar or concave mirror be employed as a mirror.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention now will be described hereunder with respect to the accompanying drawings, in which:
FIG. 1 is a schematic plan view showing one embodiment of the invention;
FIG. 2 is a sectional view showing a rotary mechanism used in the embodiment shown in FIG. 1; and
FIGS. 3 and 4 are schematic plan views showing further embodiments of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a first embodiment of the present invention, wherein first and second spectroscopes 1, 2 are disposed in series with each other in an optical path. S1, S2, and S3 designate entrance, intermediate, and exit slits, respectively.
The first spectroscope 1 is centered on a rotary bed 3 with a concave grating G1 and a concave mirror M1, either G 1 or M 1 being selected and oriented toward the optical path by rotation of the rotary bed 3. When the concave grating G1 is selected, the rotary bed 3 is rotated with wavelength drive. On the other hand, when the concave mirror M1 is selected, the rotary bed 3 is held fast in such a manner that the concave mirror M1 is caused to have the image of the entrance slit S1 brought to focus upon the intermediate slit S2.
The second spectroscope 2 is centered on a rotary bed 4 with concave diffraction gratings G2, G3 having different blazed wavelengths, either G 2 or G 3 being selected and oriented toward the optical path by rotation of the rotary bed 4. The rotary bed 4 is adapted for rotation with wavelength drive.
Various rotary mechanisms for the rotary bed 4 having a plurality of gratings have been well known. The invention is adapted to use any of these well known mechanisms. So far as the rotary bed 3 is concerned, a well known mechanism similar to the rotary mechanism used for the rotary bed 4 may be employed for selecting one of the concave grating G1 and the concave mirror M1. A different mechanism should be added to hold the concave mirror M1 fast in a predetermined orientation if the latter is selected.
One form of rotary mechanism which can be used for such rotary bed 3 is shown in FIG. 2.
Rigidly mounted on a rotary shaft of a pulse motor 5 is the rotary bed 3 which includes the concave grating G1 and the concave mirror M1. Flanges 6, 7 which corresponds to the concave grating G1 and the mirror M1 are mounted on the circumference of the rotary bed 3 and are detected by a sensor such as a photo-coupler 8. A detection signal from the photo-coupler 8 serves to control the drive of the pulse motor 5.
The rotary bed 3 and the pulse motor 5 are also secured to a rotary shaft 9 having a bearing means on which a sinebar means 10 is mounted. An abutment 11 is taken out when the concave grating G1 is selected but is inserted when the mirror M1 is selected.
More specifically, the concave grating G1 is selected and directed to the optical path to provide wavelength drive for rotation of the sinebar 10, thereby rotating the concave grating G1 with the pulse motor 5. When the mirror M1 is selected and oriented to the optical path, the abutment 11 prevents the sinebar 10 from moving. As a result, concave mirror M1 is held fast in a given orientation.
Alternatively, the rotary mechanism for the rotary bed 4 on which the second spectroscope 2 is disposed may be so formed as to eliminate the abutment 11 in the rotary mechanism shown in FIG. 1.
When the invention is used as a single monochromator, the mirror M1 in the first spectroscope 1 is selected. If the invention is used as a double monochromator, the concave grating G1 in the first spectroscope 1 is selected. In either case, either the concave grating G2 or G3 is selected by the second spectroscope 2.
FIG. 3 shows a second embodiment of the invention, wherein first and second spectroscopes 21, 22 are arranged in series with each other in the optical path. As shown, the first spectroscope 21 includes one concave mirror M2 and two concave gratings G4, G5 having different blazed wavelengths. The second spectroscope 22 carries one concave mirror M3 and two concave diffraction gratings G6, G7 having different blazed wavelengths.
When this embodiment of the invention is used as a single monochromator, the first and second spectroscopes 21 and 22 select the concave mirror M2 and one of the concave gratings G6 and G7, respectively, or alternatively one of the concave gratings G4 and G5 and the mirror M3, respectively.
Further, when the invention is used as a double monochromator, the first and second spectroscopes 21 nd 22 are used to select one of the concave gratings G4 or G5 and one of the concave gratings G6 or G7, respectively.
While the aforementioned embodiments of the invention as described provide spectroscopes with concave gratings and concave mirrors, it is to be understood that a plain diffraction grating may be used in combination with a plain mirror to form Czerny-Turner or Littrow type mountings.
FIG. 4 illustrates a further embodiment in which the spectroscope 31 is provided with a plain diffraction grating G8 and a plain mirror M4 so that the Czerny-Turner type mounting may be applied thereto. Condensing concave mirrors MR1 and MR2 are provided on either side of the optical path from the first spectroscope 31.
A second spectroscope 32 includes three planar diffraction gratings G9-G11 having different blazed wavelengths and is formed with condensing concave mirrors MR3 and MR4 on either side of the optical path therefrom.
The monochromator according to this embodiment acts as a double monochromator when the plain grating G8 is selected by the first spectroscope 31 and also as a single monochromator when the plain mirror M4 is selected.
The embodiments shown in FIGS. 3 and 4 may use the same rotary mechanism for each of the spectroscopes, as in the embodiment of FIG. 1.
According to the invention, a single monochromator unit may be used selectively as a double or single monochromator. For example, such a unit may be used not only as a single monochromator when tightly sensitive measurements are needed, viz., when an integrating-sphere is provided and a light beam is reduced, but also as a double monochromator when a transparent specimen having high absorbance and low transmissivity is measured with close tolerance, or when monochromativity with high purity is required.
As set forth above, the monochromator according to the invention may be used conveniently and usefully according to the purpose of measurement and the object to be measured even though only one unit is provided. | A monochromator, capable of functioning as either a single monochromator or a double monochromator by positioning of either reflective means or dispersion means in the optical path. Both the reflective means and the dispersion means are placed on a rotary bed which may be rotated by rotary drive means so that one of the above-mentioned optical means may be placed in the optical path, whereby the monochromator functions optimally, depending on the object to be measured. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S.C. Section 119(e) of U.S. Provisional Application No. 61/184,456 entitled “Multiproduct Biorefinery for Synthesis of Fuel Components and Chemicals from Lignocellulosics via Levulinate Condensations,” filed Jun. 5, 2009, the disclosure of which is hereby incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This invention was made with government support under the Cooperative Agreement No. DE-FG36-08GO88054 entitled “EERC Center for Biomass Utilization 2009,” awarded by the U.S. Department of Energy. The government has certain rights in the invention.
BACKGROUND
[0003] 1. Field of the Invention
[0004] This invention is directed to an integrated process for production of liquid transportation fuels, fuel additives, or chemicals by the conversion of cellulosic materials. The fuels will be suitable for use in jet fuel, or diesel fuel; the fuel additives will be suitable for use in diesel fuel; the chemical will be suitable for use as plasticizers or amphiphilic solvents.
[0005] 2. Background
[0006] More efficient means for conversions of agricultural, forest, aquaculture algae, and construction waste to fuels and chemicals are sought so that useful biomass-derived products can compete with and be integrated with the production of petroleum-based products. Although cellulose is the most abundant plant material resource, its exploitation has been curtailed by its composite nature and rigid structure. As a result, most technical approaches to convert lignocellulosic material to fuel products have focused on an effective pretreatment needed to liberate the cellulose from the lignin composite and break down its crystalline structure. Besides effective cellulose liberation, an ideal pretreatment has to minimize the formation of degradation products because of their wastefulness and inhibitory effects on subsequent processes. One way to improve the efficiency of biomass conversion schemes (biorefineries) is to integrate the energy-intensive lignocellulose depolymerization and dehydration (LDD) process with power production and/or other biomass processing. Many future biorefinery concepts rely on conversion of lignocellulose to glucose and subsequent fermentation, but this processing requires expensive enzymes and long contact times or produces inhibitors for the fermentation and low-value by-products. Fermentation releases carbon dioxide and produces cell mass, which may be usable only as a livestock supplement.
[0007] Alternative processing for lignocellulosic materials is acid-catalyzed depolymerization and conversion to the C5 product, levulinic acid, or levulinate ester. In general, two methods are used to produce levulinate from lignocellulose. One method uses water with a strong acid catalyst, such as sulfuric acid, to effect the depolymerization and dehydration of lignocellulose to produce the C5 and C1 acids (levulinic and formic acids) (see U.S. Pat. No. 5,608,105).
[0008] However, separation of products from the aqueous product solution is difficult. One patent describes a separation scheme that uses an olefin feed to convert the aqueous acid to esters that can be separated from the water and each other (see U.S. Pat. No. 7,153,996). Of course, a nearby olefin source is required for this process.
[0009] Another method uses an alcohol solvent for the acid-catalyzed depolymerization of cellulose, which results in direct formation of the levulinate ester (see DE 3621517).
[0010] A recent U.S. Department of Energy-sponsored project at the Energy & Environmental Research Center showed that high yields of methyl and ethyl levulinates along with charcoal and resins are obtained from several agricultural and wood (particleboard) wastes using relatively easy purification procedures, with little wastewater production. Valuable furfural and alkyl formates were also formed in addition to recovered resin from the particleboard and charcoal.
[0011] Several levulinic acid derivates have been proposed for fuel applications, such as ethyl levulinate, γ-valerolactone, and methyltetrahydrofuran. However, these components do not exhibit satisfactory properties when blended in petroleum-derived fuels.
[0012] Instead, valeric biofuels have been proposed by hydrogenation of γ-valerolactone to valeric acid, ethyl valerate, butyl valerate, and pentyl valerate ( Angew. Chem. Int. Ed. 2010, 49, 1-6). The valeric platform potentially offers biofuels that can be used as components in both gasoline and diesel for blending. Nevertheless their acceptance as transportation fuels is challenged as they do not readily integrate in the existing petroleum fuel supply infrastructure.
[0013] The potential of levulinic acid and γ-valerolactone for biofuel manufacture has been also addressed by another method which converts γ-valerolactone into butenes via decarboxylation (see Science 2010, 327, 1110-1114). The butenes can provide a feedstock for gasoline but not for diesel or jet fuel unless they are further oligomerized. This multistep process seems to be too involved to be economically attractive.
[0014] Accordingly, a simple integrated method is needed to synthesize diesel and jet fuels, diesel additives, amphiphilic solvents, and plasticizers from C5 intermediates, levulinic acid, or levulinic esters with appropriate reagents that enable easy separation of product streams and simultaneously provide a mixture of the required hydrotreated higher molecular weight compounds.
BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS
[0015] This invention comprises a set of integrated processes for achieving the desired goal of fuel and chemical production in a biorefinery. The biorefinery operates in a unique parallel processing mode wherein the initial biomass feedstocks are disassembled to provide substrates for parallel branches whose products may be reassembled in either a condensation step or a mixed hydrotreating step or a final fuel blending step as illustrated in various examples ( FIGS. 1-6 ). In addition, the product streams of the biorefinery includes longer molecular weight products with a carbon chain length of 8 or higher created from the condensation step and shorter molecular weight by-products from unreacted starting materials.
[0016] Processing of the lignocellulosics can include their conversion to levulinate intermediates that condense with intermediates derived from other processes to produce fuels with the appropriate range of sizes in the target molecular composition, thus generating desirable combustion and physical properties.
[0017] One aspect of this invention is focused on the alternative catalytic processing of lignocellulose that directly produces good yields of a mixture of C5 and C1 esters or acids accompanied by valuable furfural and some carbon and resin. The catalytic processing of cellulosic biomass in alcohols offers a direct conversion to levulinate (C5) and formate (C1) esters that are useful for fuels and chemical intermediates. Levulinates are considered potential platform chemicals. The alkyl levulinates are valuable intermediates for formation of plasticizers.
[0018] Another aspect of this invention is the integration of a pyrolysis pretreatment step of cellulosic biomass. The biomass is depolymerized in such a thermal unit to give a soluble carbohydrate intermediate, such as anhydrosugars, prior to conversion to levulinate. In the thermocatalytic reaction, the anhydrosugars can be directly converted into ethyllevulinate or reagent aldehydes for the condensation step.
[0019] Another aspect of this invention is to convert the C5 acids or esters into fuel blendstocks for the production of finished fuels that meet petroleum-based fuel specifications. The present invention achieves this goal by integrating production of the levulinate derivatives with the processing of the disassembled noncellulosic portions of feedstock via a condensation of appropriate intermediates that results in a range of further intermediates with desired carbon chain lengths for fuels.
[0020] Another aspect of this invention is the integration of the reduction of fatty acid derivatives from the disassembled feedstocks with reduction of the condensation products to produce fuel blendstocks consisting of paraffins, isoparaffins, cycloparaffins, and alkylaromatics all of which are necessary for jet fuels to meet the physical fuel properties as specified for Jet-A or JetA1, for example.
[0021] Another aspect of this invention is production of cyclic ethers via mild hydrotreating of the condensation products. These cyclic ethers are utilized as diesel fuel additives to boost cetane value and reduce particulate emissions from the diesel combustion process. In some embodiments, this method is further integrated and uses the light cyclic ethers, such as methyl tetrahydrofuran, which occur as by-products, as solvent for the isolation of the levulinate products from the depolymerization reaction.
[0022] In some embodiments, this method integrates the catalytic processing of lignocellulosic materials. In order to meet the rigid specification for jet fuels, a fuel must comprise some of each of the types of hydrocarbons described above, as well as an appropriate distribution of carbon chain lengths. Blending of the streams from the parallel processing biorefinery accomplishes the final integration piece.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] For a more detailed description of the preferred embodiment of the present invention, reference will now be made to the accompanying drawings, wherein:
[0024] FIG. 1 is a schematic of an integrated C5 biorefinery for oil seed biomass conversion to fuels via levulinate and isobutyraldehyde.
[0025] FIG. 2 is a schematic of an integrated C5 biorefinery for lignocellulose conversion to fuels via ethoxymethylurfural or furfural.
[0026] FIG. 3 is a schematic of an integrated C5 biorefinery employing the products and by-products for conversion to fuels.
[0027] FIG. 4 is a schematic of an integrated C5 biorefinery utilizing fruit and sugar beet wastes and a solid acid conversion unit for the soluble portion.
[0028] FIG. 5 is a schematic of an integrated C5 biorefinery for algae biomass conversion to fuels via ethyl levulinate and ethoxymethyl furfural or furfural.
[0029] FIG. 6 is a schematic of an integrated C5 biorefinery for lignocellulose conversion to fuels via anhydrosugars and levulinate.
[0030] FIG. 7 is a schematic of the depolymerization/decomposition of cellulose in ethanol and sulfuric acid, followed by a condensation reaction of ethyl levulinate with an aldehyde.
[0031] FIG. 8 is a schematic of a condensation product with furfural and subsequent Diels-Alder reaction and reduction to cycloparaffin.
[0032] FIG. 9 is a schematic of hydrogenation of levulinate intermediates:
[0033] A. Severe hydrogenation to alkanes,
[0034] B. Hydroisomerization to isoparaffins, and
[0035] C. Mild hydrogenation to alkyl tetrahydrofurans.
[0036] FIG. 10 is a schematic for the extraction and purification of the product mixture in unit ( 150 ) from reactor ( 100 ).
DETAILED DESCRIPTION
1. Integrated Biorefinery
[0037] As illustrated in FIGS. 1 and 2 , one of the preferred embodiments for the parallel processing C5 biorefinery is an integrated biorefinery comprising an initial separation (disassembly) unit ( 50 and or 55 ) for certain types of biomass containing oil where noncellulosic feedstocks are separated from cellulosic or lignocellulosic feedstocks, a cellulose depolymerization and dehydration (CDD) unit ( 100 ) that catalytically depolymerizes and decomposes or reforms the lignocellulose; a condensation unit ( 200 ) that condenses the primary product from the first unit with reactant aldehyde, ester, and ketone intermediates produced in a reagent production unit ( 300 ) from preferably renewable resources; and a hydrotreating unit ( 400 ) that converts the condensation products to fuels via hydrotreating. Additional units are added to convert by-products to chemical feedstocks and to separate and blend fuel components. Preferably, a separation unit ( 150 ) is added between the first ( 100 ) and second unit ( 200 ). Other energy crops, such as algae, are processed similarly ( FIG. 6 ).
[0038] Alternatively, the process uses abundant cellulosic or lignocellulosic feedstocks ( FIGS. 2 , 3 ) comprising very low cost or negative cost wood and agriculture residue or grass and other energy crops. Lignocellulosic feedstocks are low in nitrogen and sulfur. The key to processing lignocellulosics to hydrocarbon fuels is the removal of the large amount of oxygen without carbonizing or polymerizing the carbon structures or expending a lot of hydrogen. The catalytic conversion to a levulinate (C5) intermediate is highly efficient in producing a material appropriate for further chemical synthesis because of the functionality retained in the first conversion.
[0039] Subsequent catalytic condensation reactions of the levulinate in the second unit ( 200 ) permit its conversion to higher molecular weight species (see FIGS. 1-8 ). Thus the 5-carbon acyl group of the ester is combined with aldehydes and ketones to form (5+x)-carbon products. The condensation reaction enables a simple separation of the (5+x) carbon products from the residue because of their lower solubility in water. Some of the levulinate condensation products will undergo a second cyclic condensation (Dieckmann condensation) to produce cyclic ketones. In order to prevent that the aldehydes, esters, and ketones undergo primarily a self-condensation reaction, it is important to choose x larger than 3. For providing suitable C9-C16 condensation products that are suitable for use in diesel and jet fuel after hydrotreating them, x should be in the range of 4 to 11.
[0040] Important for the integrated processing scheme are the syntheses of reagents for the condensation with the levulinate produced in a variety of ways from the separation products or by-products of the initial processing. In one embodiment ( FIG. 1 ), ethanol from fermentation ( 700 ) of starches is converted to isobutyraldehyde ( 305 ) and used in the condensation reaction in the second unit ( 200 ).
[0041] In a further embodiment, the sugars and starches are used as a substrate for the production of hydroxymethylfurfural, alkoxymethylfurfural, and alkyl levulinates ( FIG. 2 ). In these reactions, an aqueous or alcohol solution of the sugar or starch is pumped through a bed of solid acid catalyst.
[0042] The final integration occurs in the hydrogenation of the condensation products; the hydrotreating unit ( 400 ) gives both linear and branched hydrocarbons of appropriate chain lengths for JP-8 and other fuels. In addition, cycloparaffins are available from Dieckmann and Diels-Alder reactions of the intermediates prepared from ethyl levulinate. Low molecular weight cyclic ethers from hydrotreating are returned as solvent for the earlier separation.
2. Initial Separation (Disassembly) ( 50 , 55 , 60 )
[0043] In an embodiment of this invention, where the feedstock is an oil seed such as corn, or the mechanical pretreatment unit ( 50 ) may be a wet mill which separates out the fibrous cellulosic material, from the starches and germ plasm, the germ plasm is treated by an oil extraction unit ( 55 ). The oil extraction unit ( 55 ) may be a press, more preferably a hexane- or CO 2 -based extraction unit (see FIGS. 1 and 5 ). The starches and sugars may be fermented in fermentation unit ( 700 ) to produce alcohols, in particular, ethanol.
[0044] When the feedstock is algae, as illustrated in FIG. 5 , the extraction is combined with transesterification to produce fatty acid esters: methyl (FAME) or ethyl (FAEE).
[0045] When integrated with a Kraft process, as illustrated in FIG. 3 , the oil extraction unit ( 55 ) may yield tall oil fatty acids by first separating the raw tall oil soap from the spent black liquor by decanting the soap layer formed on top of the liquor storage tanks and then further extraction of the fatty acids. In an alternative embodiment, the tall oil soap is only filtered. The extracted oil, fatty acids, or tall oil soap may then be hydrotreated in the fourth unit ( 400 ).
[0046] In another embodiment, the biomass feedstock comprises a cellulosic or lignocellulosic material, such as wood, wood pulp, pulping sludge, particleboard, paper, grasses, agricultural by-products such as straw, stalks, cobs, beet pulp, seed hulls, bagasse, or algae, any of which could be a by-product or waste form of the material (see FIGS. 3-6 ). These are reduced to a small, preferably granular size for the catalytic processing through a mechanical pretreatment unit ( 50 ). This pretreatment can be, for example, a simple mill or steam explosion gun. In another embodiment, the milled lignocellulose is further heated rapidly in a reactor ( 75 , FIG. 7 ) to produce a condensable product comprising anhydrosugars, furfural, and lignin-based oils, which are separated.
3. Catalytic Depolymerization/Dehydration Unit ( 100 )
[0047] Processing lignocellulosics to hydrocarbon fuels can include the removal of the large amount of oxygen without carbonizing or polymerizing the carbon structures or expending a lot of hydrogen. The present invention takes advantage of the acid-catalyzed mild thermal processing of levulinate units that maintain the type of oxygen functionality desired for further synthetic reactions.
[0048] The catalytic depolymerization/dehydration unit utilizes a heated reactor ( 100 ) preferably at 120°-200° C. with a liquid or dissolved form of catalyst (preferably sulfuric acid) in FIGS. 1-3 . A heated reactor with a solid acid catalyst bed is utilized in FIGS. 4 , 5 , and 6 where the feedstock is soluble or depolymerized and dehydration to the levulinate form is desired. Feedstock for producing levulinate may be any source of C6 sugar such as cellulosic materials and starches. Examples of sources of C6 sugars that may or may not be pretreated include wood, wood pulp, pulping sludge, particleboard, paper, grasses, agricultural by-products such as straw, stalks, cobs, beet, beet pulp, seed hulls, bagasse, algae, corn starch, potato waste, sugar cane, and fruit wastes, any of which could be a by-product or waste form of the material or a combination thereof.
[0049] Integration with a power plant or a recovery boiler can furnish low-pressure (waste) steam to generate the desired temperatures for the different reactors.
[0050] The reactor of the first unit ( 100 ) may be a pressurized autoclave or, preferably, a continuous reactor. The preferred embodiment in this invention is the continuous reactor, wherein a slurry of the biomass feedstock in acidic water or alcohol is pumped or augured through the heated reactor under mild pressure and wherein the residence time in the reactor is between 20 and 60 minutes.
[0051] The catalytic depolymerization/dehydration unit can be run with either of two different liquid streams: aqueous or alcoholic. In the aqueous medium, equal molar amounts of levulinic acid and formic acid are produced and are soluble in the aqueous acid. In case of lignocellulosic material processing, furfural is also formed from 5-carbon sugars present in the hemicellulose and is removed as overhead and collected during the processing. Separation of the acid products from the aqueous acid solution and from each other is difficult. However, for some acid-catalyzed processes, the process can continue through the next step without separation of the acids because separation is more easily effected on a more hydrophobic product from the subsequent reaction. Only the insoluble char and tars are separated, for example, with a filter and solid- or liquid-phase extraction, respectively. The furfural may be purified by distillation. Levulinic acid may be vacuum-distilled along with some of the water, or it may be extracted from the aqueous acid with an ether or ester solvent, such as methyltetrahydrofuran or gamma valerolactone, derived from the process in a later hydrogenation step. The insoluble char and tar may be further dewatered and may be thermally converted in a recovery boiler to provide process heat or fed to a power plant.
[0052] The reaction medium for the depolymerization/dehydration can also comprise an acid alcohol solution, such as that obtained by adding sulfuric acid and methanol or ethanol. Ethanol may come from the fermentation unit ( 700 ). The products of the reaction are methyl levulinate and methyl formate or the corresponding ethyl esters ( FIG. 7 ). Longer-chain alcohols also can be used as the liquid medium, but they give lower yields of the ester products. The depolymerization/dehydration in ethanol of particleboard and other waste materials to ethyl levulinate ester proceeds in good yield when conducted in ethanol with sulfuric acid catalyst at 200° C. ( FIGS. 1-7 ). Compared to the similar preparation of levulinic acid using an aqueous acid medium, the ethyl levulinate is more easily purified by ( FIG. 10 ) extraction and/or distillation and can be easily separated from the concomitantly formed furfural (from the 5-carbon units present in the hemicellulose and ethyl formate). A preferred solvent for the extraction of levulinate esters and levulinic acid is methyltetrahydrofuran, produced in the hydrotreating unit ( 400 ) from ethyl levulinate or levulinic acid remaining in the condensation product mixture. Another preferred solvent is γ-valerolactone, which is also produced in the hydrotreating unit ( 400 ) from the same source.
[0053] Another embodiment for the first unit ( 100 ) is to distill the levulinic acid product so as to form angelica lactone (see FIG. 2 ). The angelica lactone is highly reactive in subsequent condensation reactions, owing to the acylation reactivity of the enolic lactone group, and also provides a route to products substituted at the alpha position.
[0054] In another embodiment for the first unit ( 100 ), the depolymerization/dehydration is conducted at a lower temperature, wherein ethoxy (or methoxy)methylfurfural is formed in addition to the levulinate. This intermediate is used directly in the condensation reactor or is converted to chemical products and monomers, such as furan dicarboxylate.
4. Condensation Unit ( 200 )
[0055] The third unit ( 200 ) in the integrated system is the reactor for conducting acid- or base-catalyzed condensation reactions ( FIG. 7 ) of the C5 levulinate to produce higher molecular weight species with the chain lengths desired for jet fuel, diesel, amphiphilic solvents and plasticizers. Thus the 5-carbon acyl group of the levulinate is combined with aldehydes, esters, or ketones (C x ) to form (5+x)-carbon products. The condensation reaction is illustrated in FIG. 7 . In FIG. 7 , a branched aldehyde condenses with levulinate to form a mixture of branched ketoesters which are then hydrogenated to form branched alkanes or cyclic ethers. The latter reaction is shown in FIG. 9 . In order to prevent that the aldehydes, esters, and ketones undergo primarily a self-condensation reaction, it is important to choose compounds with reactive carbonyl groups and unreactive alpha carbons that are branched or aromatic at this position. This implies that x is greater than 3. For providing suitable C9-C16 condensation products that are suitable for use in diesel and jet fuel after hydrotreating them, x should be in the range of 4 to 11. In addition, the aldehydes, esters, or ketones need to be branched to reduce the potential of any self-condensation. Also, for producing jet fuel, branched or aromatic aldehydes, esters, or ketones are preferred to produce a highly isoparaffinic fuel blendstock or cycloparaffinic fuel blendstock, respectively, that when blended together meet such important jet fuel criteria as freeze point, flash point, energy density, and physical density.
[0056] Another important aspect of this invention is that the fuel, solvent, and plasticizer must comprise an appropriate distribution of carbon chain lengths to provide for the proper distillation curve for the fuel, the amphiphillic character of the solvent, and the highly elastic features of a polymer from the use of the plasticizer, respectively. Therefore, the relevant aldehydes, esters, and ketones are derived from a limited group of feedstocks and chemical reactions that lead to the required carbon chain length distribution. Feedstocks for the reagent branched aldehydes are alcohols, such as isobutyl alcohol, that are produced by Guerbet reactions of ethanol and subsequently dehydrogenated to aldehydes, and olefins, for example from a petroleum refinery, that are converted to aldehydes by the oxo reaction. Aryl aldehydes are furfural, hydroxymethylfurfural, and substituted benzaldehydes that are produced from 5 and 6 carbon sugars or from lignin, respectively. Cyclic aliphatic aldehydes are produced by Diels-Alder reactions of acrolein (from dehydration of glycerol) with butadiene (from petroleum cracking or from ethanol via the Lebedev reaction). Reactive ketones include those with an adjacent carbonyl (1,2 diketones, 1,2 ketoesters) that are produced by fermentation or pyrolytic reactions of levulinic or, lactic acid. Vinyl esters are also highly reactive reagents; the one utilized in this invention is angelica lactone produced by distillation of levulinic acid over a mineral acid.
[0057] The condensation reaction of leuvelinats have precedence in the chemical literature, but these isolated reaction were not recognized for the potential for fuel or fuel additives synthesis. These reactions include the following: Benzaldehyde and substituted benzaldehydes (Erdman, Kato, Sen, Borshe), furfural (Ludvig & Kehler, Sen; Erdmann), isobutyraldehyde (Meingast), and self-condensation (Zotchik, Blessing), formaldehyde (Olsen) and phenol (Mauz). A recent patent application teaches the dimerization of levulinic acid on a cation exchange resin to form C10 units (Blessing, WO 2006/056591). The reaction proceeds in very low yields, 15% as reported. An older publication reports essentially the same process with a simple sodium base (Zotchik). This application instead utilizes an integrated process where levulinate esters are condensed with aldehydes in high yields and the condensation products are converted to cyclic ether diesel additives and hydrocarbons.
[0058] Product formation and separation are facilitated at this stage because of the low solubility of the longer-chain reaction products in water. Thus when levulinic acid from the first-stage aqueous reaction containing the acid catalyst is reacted with the aldehyde mixture, the products from the second unit ( 200 ) are now more easily extracted from the water with the solvent methyltetrahydrofuran. The acidic aqueous layer contains formic acid in addition to the sulfuric acid. Formic acid is vacuum-distilled along with some of the water in the separation unit ( 250 ), and the sulfuric acid catalyst is then recycled to the first dissociation/depolymerizaton unit after partial evaporation of the water content. Thus the integration of these two steps allows convenient product separation as well as a means of recycling the acid catalyst. No neutralization is needed. Aldol condensation products from the reaction of levulinic acid and an aldehyde conducted with an acid catalyst typically are a mixture of the β-(or branched) and the δ-(or unbranched) forms, as shown in FIG. 7 . To achieve more of the δ-(or unbranched) form, a basic catalyst must be used. This is not feasible without removing the sulfuric acid used in the first-stage unit. Thus an alternative route is used for synthesis of unbranched isomers with an alkaline catalyst. Although some of the aldehyde undergoes self-aldol condensation, the products from this side reaction do not need to be removed since they are also converted to usable fuels in the final step.
[0059] The alternative synthesis route uses an alcohol such as methanol or ethanol in the first-stage depolymerization/dehydration unit ( 100 ) along with the soluble acid catalyst. Following the formation of the esters in the first-stage unit ( 100 ), the esters are extracted and separated by simple distillation—formate ester boiling at low temperature—alcohol and solvent are removed, then furfural. The higher boiling levulinate ester could be distilled or reacted without purification.
[0060] The levulinate ester that is formed in the alternative depolymerization/dehydration unit when alcohol is the vehicle for the biomass slurry is reacted with the aldehyde intermediates using a strong base catalyst to produce mainly the longer-chain esters. Preferably the catalyst for the condensation is a solid base catalyst so that a continuous reaction over the bed of the catalyst is performed, and no catalyst separation or neutralization is needed. The catalyst is preferably a hydrotalcite or a hydrotalcite impregnated with a basic material, such as potassium fluoride. When a soluble catalyst is employed, the catalyst must be removed from the product solution. Typically, the condensate product comprises a mixture of isomeric forms. For example, isobutyraldehyde is attacked by enolate carbanions formed at the delta and beta positions of the levulinate. The proportion of isomers depends on the catalyst used.
[0061] In another embodiment, the furfural by-product or coproduct is also condensed with the levulinic acid or ester to form the furfuryl-substituted levulinates ( FIG. 8 ). Again, depending on the choice of catalyst, β-(or branched) and the δ-(or unbranched) isomers are obtained. Hydroxymethylfurfural also reacts at the aldehyde moiety with levulinates to give a C11 intermediate. Hydroxymethylfurfural is available from renewables by processing sugars with acid catalysts. Fructose has been the preferred sugar substrate for conversion to hydroxymethylfurfural; however, recent reports use CrCl 2 catalyst with glucose as shown in process unit ( 800 ).
[0062] Three options are available for processing of the furfuryl levulinates. One option is mildhydrogenation to tetrahydrofurans. Another option is to open the furan ring to produce C10 or C11 units. The other option is to conduct a cycloaddition at the furan functionality with a dienophile such as acrolein or acrylic acid (Diels-Alder reaction). The cycloaddition product contains the 7-oxa-bicyclo{2.2.1}heptene moiety with a bridging oxide group that is subsequently removed in the hydrogenation step ( 400 ).
[0063] The angelica lactone prepared in the third alternative of the first-stage processing ( 100 ) is condensed with the aldehyde mixture. The resulting products from this reactant are substituted in the alpha position and can generate isoparaffins in the hydrogenation reactor ( 400 ).
[0064] Highly reactive ketones will also condense with the levulinate intermediates. These include biacetyl (2,3-butanedione) and 2,3-pentanedione. Both are actually obtained from other reactions of levulinic acid. These highly reactive ketones condense with levulinic acid, resulting in C9 and C10 chains, respectively. Other branched and cyclic ketones are available from pyrolysis of lignin.
[0065] Another embodiment utilizes the condensation of levulinate with alpha angelica lactone using a Lewis acid catalyst. The reaction occurs between the enolate of the levulinate and the carbonyl of the enol-activated ester carbonyl group to produce a diketone product.
[0066] The condensation of angelica lactone with aldehydes also occurs. The alpha positions are activated by base catalysts, such that condensation with the aldehyde occurs at the alpha position.
[0067] Another embodiment utilizes the condensation (Michael reaction) of levulinate with an unsaturated carbonyl compound, such as ethyl acrylate or acrolein, where an alpha carbon of the levulinate reacts with the beta carbon of the unsaturated carbonyl compound. The preferred catalyst is a coordinating metal ion catalyst to promote enolization of the levulinate. Catalysts include zinc, nickel, and other transition metal ions, as well as titania, alumina, and zirconia.
[0068] Another embodiment produces cyclic ketones via the Dieckmann condensation of beta-ketoesters and beta-diketone [00047] with the levulinate ester carbonyl group. These cyclic ketones have the advantage that they are easily hydrogenated to cycloparaffins without formation of cyclic ethers.
[0069] An alternative condensation method combines an olefinic group with a carbonyl compound. This reactant generates a free radical from reaction of manganese(III) acetate with the carbonyl compound, which subsequently combines with the olefin. With levulinate, this could happen two different ways: 1) reaction of ethyl levulinate radical with an added olefin ( FIG. 9A ) or 2) reaction of an added ester with the double bond of angelica lactone ( FIG. 9B ) which is produced in a prior dehydration reaction from either levulinic acid or levininate ester.
5. Reagent Aldehyde and Ester Production Unit
[0070] Aldehydes are potentially available from a variety of renewable or petrochemical resources. The preferred aldehyde intermediates are those that undergo minimal or no self-condensation. The class comprises aldehydres with no hydrogens on the alpha carbon, such as furfuraldehyde and benzaldehyde, and aldehydes with branching at the alpha carbon, such as isobutyraldehyde and cyclohexanecarboxaldehyde, which inhibits self-condensation.
[0071] Reagent aldehydes are formed by dehydration of alcohols over a Cu or Pt catalyst. Precursor alcohols are prepared via Guerbet synthesis or homologation of lower alcohols with carbon monoxide. For example, isobutanol is prepared brom ethanol and methanol using a solid basic Guerbet catalyst. It is also the main product from H 2 and CO at the Leuna Plant. A variety of higher alcohols are present in fusel oil, a by-product from distillation of ethanol from yeast fermentation. Isobutyraldehyde is prepared commercially by oxo reactions of propylene.
[0072] Aldehydes are also prepared directly from lower alcohols by Guerbet synthesis at higher temperatures (>400° C.).
[0073] Furfural is produced from the thermal decomposition of 5-carbon sugars. Alkoxymethylfurfural is produced from the acid-catalyzed depolymerization of cellulose and starch at lower temperatures.
[0074] Cyclohexenylcarboxaldehydes are produced by the cycloaddition of acrolein (from glycerol or lactic acid) with butadiene, from the condensation of ethanol (Lebedev process), or the reaction of acetaldehyde with an olefin (Prins reaction).
[0075] C6 and C9 aliphatic aldehydes are formed from oxidation of fatty acids or triglycerides, preferably tall oil fatty acids when integrated with the Kraft process.
[0076] Benzaldehydes are available from a variety of renewable sources and by the oxidation of lignin. Lignin may be recovered from solids separated in unit ( 150 ) and processed in the reactor ( 180 ).
[0077] Michael reactions are also conducted with ethyl acrylate, obtained from dehydration of ethyl lactate. Lactic acid from fermentation of the starches is esterified in unit 200 . Ethyl lactate is converted catalytically to ethyl acrylate, which condenses at unsaturated carbon (Michael reaction) in the condensation reactor 200 .
6. Catalytic Hydrogenation Units
[0078] A catalytic hydrogenation is performed on the ketoacid and ketoester intermediate produced in the condensation unit ( 200 ). These oxygen functional groups are reduced with unsaturation, resulting in formation of the mixtures of paraffins, isoparaffins, cycloparaffins, and alkylaromatics in a hydrogen atmosphere in the hydrogenation reactor ( 400 ) ( FIGS. 11A and B). Under milder conditions, a tetrahydrofuran ring forms ( FIG. 11C ). The substituted tetrahydrofurans are utilized as solvents or are blended with hydrocarbon fuels or alcohol-based fuels.
[0079] Hydrotreatment of the C6-C8 condensation products using an isomerization catalyst results in branched hydrocarbons suitable for gasoline.
[0080] Severe hydrogenation of the C9 to C14 condensation products gives both linear and branched hydrocarbons of appropriate chain lengths for kerosene for the production of jet fuel such as Jet A, Jet A1, JP-5, and JP-8. In addition, cycloparaffins are available from Diels-Alder reactions of the intermediates prepared from ethyl levulinate.
[0081] It is advantageous for both fuel properties and processing that the trialkylglycerides or tall oil fatty acids extracted in the oil extraction unit ( 55 ) are directly processed by the hydrogenation reactor ( 400 ) together with the condensation products. Similarly, turpentine extracted from the Kraft process may undergo an aromatization reaction of its main terpene with reagents such as iodine or PCl3, leading to cymene which then can be hydrotreated to cycloparaffin.
7. Chemical Synthesis Units
[0082] Extraction Solvents: The use of methyltetrahydrofuran to extract levulinate from the other reaction components was described. Methyltetrahydrofuran and other furan-derived products can also be utilized to extract fermentation products from their aqueous solutions. Thus butanol present in low concentrations in water can be extracted from the aqueous fermentation broth. Recovery of butanol from the extraction solvent is feasible by distilling if the boiling point of the extracting solution is higher than that of the butanol. Thus the preferred embodiments are the cyclic ethers derived from the levulinate condensation reactions.
[0083] Plasticizers. Several synthesis steps are incorporated into the integrated parallel processing plant design that utilizes intermediate reagents produced from the noncellulosic feedstocks as well as the levulinate from the cellulosic feedstock. One of the embodiments is the use of a long-chain unsaturated fatty ester, such as oleate, in the condensation units ( 200 ) with levulinate to produce a long-chain keto ester. Typically levulinate does not condense with other esters at the ester carbonyl in the acetoacetic type of condensation. Thus the condensation reaction employed is the free radical condensation with the unsaturated portion of an unsaturated or polyunsaturated fatty ester to give a product ester with a very low vapor pressure and comprises an appropriate mixture of flexible alkyl chains and polar groups which allows it to dissolve in and plasticize a polymer material, such as vinyl chloride. The fatty esters are produced in a transesterification unit from extracted vegetable oils or algal oils.
[0084] Another embodiment is the acid-catalyzed reaction of levulinate with a diol or polyol to produce a cyclic acetal (1,3-dioxolane or 1,3-dioxane). One useful embodiment uses ethylene glycol, propylene glycol, or a glycerol monoether or glycidyl ether derived from the noncellulosic biomass, and the product is a dioxolane, alkyldioxolane, or an alkoxymethyl-substituted dioxolane. Other polyol reagents are derived from alkoxy sugars. When the alkyl or alkoxy group in the dioxolane product is long, the vapor pressure is low, and good plasticizer properties are obtained.
[0085] When the alkyl or alkoxyl group is short (H, methyl, ethyl), the dioxolane product serves as an intermediate for chemical synthesis, such as condensation reactions resulting in 2-substituted acrylates. Alternatively, for the case of dioxlanes derived from diols, the dioxolane ester is reacted with glycerol to form a glyceride that is valuable for polyester and polyurethane synthesis. This requires reaction of the glyceride with a carbonyl compound, such as formaldehyde or acetone, to restore the ketone group of the levulinate glyceride. The reaction is driven by distillation of the small dioxolane, which then is utilized as a diesel or gasoline additive, depending on the size and number of the alkyl groups attached.
[0086] Importantly, the reaction or levulinate or levulinic acid with the glycol or glyceryl derivative in the above examples can utilize the crude levulinate mixture obtained directly in the cellulose depolymerization/decomposition as well as the dilute sulfuric acid present in the mixture. The separation of the product from an aqueous phase (by simple decantation) is facilitated by virtue of the hydrophobicity conferred by the long alkoxy group. Further reaction of the decanted levulinate dioxolane with glycerol or with formaldehyde results in the chemical products as described in the previous paragraphs, or alternatively, dilute acid-catalyzed reaction of the decanted levulinate dioxolane product with a small ketone or aldehyde gives the mixture of ethyl levulinate and new dioxolane fuel components. | An integrated method for production of liquid transportation fuels, fuel additives, or chemicals in a biorefinery by the conversion of cellulosic materials is disclosed herein. The method is based on converting a source of C6 sugar such as cellulosic materials and sugars into a mixture of hydrotreated compounds. The biorefinery operates in a unique parallel-processing mode, wherein the initial biomass feedstocks are disassembled to provide substrates for parallel branches whose products may be reassembled in either a condensation step or a mixed hydrotreating step or a final fuel-blending step. The cellulosic materials can be converted to levulinate intermediates that condense with intermediates derived from other processes to produce fuels with the appropriate range of sizes in the target molecular composition, thus generating desirable combustion and physical properties. This method also makes use of methyltetrahydrofuran and other low carbon by-products that are separated for use as amphiphilic solvents. In an embodiment, the method produces cyclic ethers via mild hydrotreating of the condensation products, or long-chain keto ester, useful for plasticizers, by condensing a portion of the levulinate with a reagent containing an unsaturated group. In another embodiment, the method produces a ketal by converting a portion of the condensation product in an acid-catalyzed reaction with a diol. | 8 |
[0001] This is a utility patent application claiming priority from and the benefit of U.S. Provisional Patent Application Ser. No. 61/807,519, filed Apr. 2, 2013; and U.S. Provisional Patent Application Ser. No. 61/880,500, filed Sep. 20, 2013, both of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] Biological fluid concentration assembly, namely, a fluid concentration cup assembly with an hourglass shape, a drive piston, and a side draw fluid removal port.
BACKGROUND OF THE INVENTION
[0003] Biological fluid collection and concentration devices are known. Biological fluids, such as whole blood or bone marrow aspirate, may be collected and concentrated in an assembly, including a cup placed in a centrifuge, so as to separate out the biological fluid components by differing densities. Following centrifugation, a selected part or parts of the now separated biological fluid may be selected for removal from the concentration assembly. Typically, transfer of the biological fluid into the cup and removal after centrifugation of the selected biological fluid from the cup, which is subject to centrifugation, is typically accomplished through the top of the vessel.
SUMMARY OF THE INVENTION
[0004] A fluids concentration cup assembly is disclosed having a cup with an open top to which a lid is removably engaged and an open bottom, which receives a moveable piston therein, in one embodiment, a bottom plate, and, in one embodiment, a piston drive screw. The walls of the cup include an upper portion, a lower portion, and a narrowed portion between the upper and lower portions. The upper and lower portions are typically cylindrical and part of the narrow portion may be cylindrical. In the narrowed portion, a side port, generally perpendicular to a longitudinal axis of the cup, is provided for the side draw of a separated fluid out of the collection cup following centrifugation of the biological fluid in the cup.
[0005] In one embodiment of Applicant's device, the lid is configured for engaging a device, such as a syringe, to inject aspirate or biological fluid, such as whole blood or bone marrow aspirate, into the cup through the lid. After centrifuging, a moveable piston may be manually pushed or screw driven from the bottom up until a selected layer of the differentiated biological fluid is located adjacent the side port. A concentrate withdrawal device (such as a syringe) may be engaged with the side port for removal of the selected fluid. The proper fluid level is selected by pushing up the piston. In one embodiment, the selected fluid is buffy coat.
[0006] Another embodiment of the biological fluids concentration cup assembly may include a drive piston assembly where the drive piston assembly includes a drive piston slideably engaging the lower portion of the cup and coupling threaded members, one manually rotated by the user and the other engaging the piston. Rotation of the one causes the piston to move up and down in the cup.
[0007] A bottom plate may be provided for engaging the open bottom of the cup. The drive piston assembly may include a piston screw drive assembly for moving the piston longitudinally in the lower portion. The piston of the drive piston assembly includes a perimeter for fluid sealing against the walls off the cup, an upper and a lower surface, and wherein the lower surface may have a threaded member depending therefrom. The piston screw drive assembly includes a piston drive screw extending partly within the bottom portion of the cup to engage the depending threaded member and partly without the bottom plate. The piston drive screw goes through to the bottom plate through an aperture in the bottom plate. The piston drive screw has a base with a rim or perimeter, the base laying outside the bottom plate and adjacent thereto. Rotating the base causes the piston to rise up and down, forcing the concentrated (centrifuged) fluid above the piston to rise and fall with respect to the sideport. This allows selective withdrawal of fluid from the sideport.
BRIEF DESCRIPTION OF THE DRAWING
[0008] FIG. 1 is a perspective view of Applicant's fluids concentration cup assembly.
[0009] FIG. 2 is a perspective view of Applicant's fluids concentration cup assembly.
[0010] FIGS. 3A and 3B are sectional views of Applicant's fluids concentration cup assembly with the piston in a collapsed and deployed position, respectively.
[0011] FIG. 4 is a sectional view of Applicant's fluid concentration cup assembly showing a selected intermediate layer, following centrifuging, for removal through a side port thereof.
[0012] FIG. 5 illustrates a manner in which a syringe or other concentrated fluid collection device may engage the side port for selective removal of a fluid layer from a centrifuged aspirate.
[0013] FIGS. 6A and 6B illustrate perspective views of Applicant's cup assembly showing the manner in which a syringe may transfer an aspirate to the cup assembly.
[0014] FIG. 7 illustrates an alternate preferred embodiment of Applicant's device in an exploded perspective view.
[0015] FIGS. 8A and 8B illustrate cross sectional elevational views of alternate preferred embodiments of Applicant's device with a piston in a collapsed or lowered position ( FIG. 8A ) and a raised or upper position ( FIG. 8B ).
[0016] FIGS. 9A and 9B are cross sectional views illustrating an alternate preferred embodiment of Applicant's present invention showing the relationship of the piston to the walls of the container and the side port with the piston in the up position.
[0017] FIG. 10 is an exploded perspective view of an alternative preferred embodiment of a piston drive mechanism having an anti-rotation feature.
[0018] FIG. 11 is a cross sectional view showing the relationship of the Halkey, the Halkey adapter, the side port of the narrow portion and the piston top.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0019] Applicant provides a first embodiment of a fluids concentration assembly 10 , which includes a cup 12 with an open top 20 having a lid 40 engageable thereof and a slideable piston 34 engageable with an open bottom 30 thereof.
[0020] In one embodiment, Applicant's cup includes an upper portion 14 , a lower portion 16 , and a narrow portion 18 . Upper portion 14 is seen to have a general cylindrical shape, with side walls 22 and an open top 20 . Lower portion 16 is seen to be generally cylindrical and having side walls 28 , an open bottom 30 , which is adapted to slideable receive piston 34 therein. Narrow portion 18 may include sloped or cone-shaped top walls 25 , through opening 26 , a cylindrical waist portion 36 , and sloped or cone-shaped bottom walls 35 .
[0021] Narrow portion 18 is seen to have walls defining a diameter or diameters that are less than those defining the upper and/or lower portion. Thus, the term “narrow portion” is, typically referring to a general cylindrical portion with a wider portion below and a wider portion above. The narrowed portion may include only sloped walls 25 / 35 in one embodiment or mixed slanted and generally cylindrical portions. By providing a narrow portion, the vertical dimension or may have longitudinal dimension of a given fluid displaced by piston 34 moving upward in the lower portion is magnified. That is to say, one milliliter of fluid displaced upward in lower portion 16 is exaggerated, in a vertical dimension by movement of the fluid up through the constricted walls of the narrow portion. Thus, a thin layer, such as a buffy coat layer BC, between a red blood cell RBC layer and plasma P, below and above buffy coat, respectively, may be exaggerated (see FIG. 1 ), when BC comes up into the narrowed portion and lies adjacent a side port 38 .
[0022] In one embodiment, lower portion 16 is integral with bottom walls 35 , which may have open top 32 . In one embodiment of Applicant's cup 12 , side port 38 , which includes walls adapted to engage a collection vessel for concentrate out (see arrows, FIG. 1 ), is adapted to be located near the bottom of waist portion 36 , where it engages the open apex of bottom walls 35 . Red blood cells then buffy coat may be drawn off when a buffy coat layer reaches above the top edge of side port 38 . The piston is pushed up (by hand or any suitable device) until the lower boundary of the buffy coat layer (the buffy coat/red blood cell boundary) is positioned and then the side port 38 may be opened to allow removal of the buffy coat and/or the selected portion of the other fluids therefrom. A cap 43 may be provided to the side port so that when the collection device is not engaged, no fluid will flow out.
[0023] Scale lines are seen marked along the side of the outer walls of the container. They may be used to determine the volume of fluid and of the respective portions of separated concentrate. It will be seen that the gap between equal fluid markings will be larger where the volume is narrower or narrows, as the vertical axis if magnified of a fluid volume as it moves from the lower portion of the cone into the waist portion.
[0024] In a second preferred embodiment ( FIGS. 2-6B ), Applicant provides a fluids concentration assembly 110 , which includes a cup 112 with an open top 120 having a lid 140 engageable therewith and a slideable piston 134 engageable with an open bottom 130 thereof of a lower portion 116 .
[0025] In one embodiment, Applicant's cup includes an upper portion 114 , lower portion 116 , and/or a recessed or narrow portion 118 . Narrow portion 118 may include sloped or cone-shaped top walls 118 a and sloped or cone-shaped bottom walls 118 b . Upper portion 114 is seen to have a general cylindrical shape, with side walls 122 , and open top 120 . Lower portion 116 is seen to be cylindrical and having side walls 128 and open bottom 130 , which is adapted to receive slideable piston 134 therein.
[0026] Narrow or recessed portion 118 is seen to have walls defining a diameter or diameters that are less than those defining upper 114 and/or lower portion 116 . Narrow portion 118 may include top walls 118 a engaging the open bottom of upper portion, bottom walls 118 b engaging the open top of the lower portion, and a cylindrical waist 136 (in one embodiment) engaging walls 118 a / 118 b . Walls 118 a / 118 b may be flat, cone shaped or any appropriate shape (but are typically sloped). By providing a narrow portion, the vertical dimension (longitudinal) dimension of a given fluid displaced by the piston moving upward in the lower portion is magnified. That is to say, one milliliter of fluid displaced upward in the lower portion would become “taller” as it is constricted in a vertical dimension by movement of the fluid up through the constricted walls. Thus, a thin layer, such as a buffy coat layer BC, between a red blood cell RBC layer and plasma P, below and above buffy coat, respectively, may be exaggerated (see FIG. 4 ), when BC comes up into the narrowed portion and lies adjacent a side port 138 . This allows easy withdrawal of any selected portion by positioning the layers post-centrifuge.
[0027] In one embodiment (see FIGS. 2 and 5 ) of Applicant's cup 112 , the side port 138 , which includes walls adapted to engage a concentrate collection syringe 150 for concentrate out (see FIG. 5 ), is adapted to be located near the bottom of waist 136 , where it engages or lays adjacent the open apex of walls 118 b . In this manner, for example, plasma, buffy coat or any other selected fluid may be drawn off through side port 138 . For example, when a buffy coat layer reaches the lower edge of side port 138 , it may gravity feed out or suction be fed out into a collection syringe 150 .
[0028] As seen in FIGS. 2 and 5 , scale lines or other indicia 139 are seen marked along the side of the outer walls of the container, including waist 136 . They may be used to determine the volume of fluid and of the respective portions of separated concentrate. It will be seen that the gap between fluid markings will be spaced apart more where the volume is narrower or narrows, as the vertical axis if magnified of a fluid volume as it moves from the lower portion of the cone into the waist portion.
[0029] In a preferred embodiment, the volume of the cup in the space between a bottom surface 140 b of a lid 140 and an upper surface 134 a of piston 134 when the piston is in the collapsed, lowered or Bottom Dead Center (BDC) position is about 80 ml. With this volume, sufficient aspirate (or other biological fluid to be centrifuged) may be received through the lid as set forth herein, for example, about 60 ml. Note that this may leave an air space of about 20 ml, in one embodiment, above the surface of the aspirate and of the concentrated fluids, so as to allow the piston to be driven upward so as to place the bottom of the buffy coat adjacent side port 138 as seen in FIG. 4 . In a preferred embodiment, waist portion 136 has a volume of about 2-10 ml or about 4-8 ml, preferably 6 ml, and a diameter of about 0.778 inches.
[0030] In one method of use, pre-centrifuge, the piston is placed in a low position and an undifferentiated biological fluid is added through the lid by way of a syringe. The unit is then placed in a centrifuge cup and spun until the fluid separates and then it is removed. Upon removal, the piston is raised until a selected layer, such as a buffy coat layer, is adjacent the side port typically with the red blood cells below the side port. A collection syringe is attached to the Halkey and the buffy coat withdrawn. A typical 60 ml of aspirate (in one case) may yield about 2 ml or less of buffy coat. This buffy coat (or other selected fluid) will be placed in the narrow portion, typically the cylindrical waist, and withdrawal may commence, drawing the selected fluid out the side port.
[0031] Lid 140 is seen to have one or more vents 140 a therethrough that may be sealed with vent caps 141 . Vents will vent a pressure differential across the lid. Lid 140 is typically sealingly engaged, as by gluing or the like to open top 120 . Rim 140 b of lid 140 is seen to be notched so as to engage rim 119 of open top 120 . Upper surface 140 c of the lid may be flat and lower surface 140 d may be slightly concave, as best seen in FIG. 3B . Having a concave lower surface 140 d will mean that the entire assembly 110 may be inverted and a Halkey 148 with channel 148 b therethrough may act as a drain to drain fluids from within the cup. Halkey 148 may have a threaded section 148 a for engagement with a syringe 152 (see FIGS. 6A and 6B ). Halkey 148 may also have a foam 148 c , which may act as a fluid barrier under neutral pressures but, under increased pressures, as by that provided by a syringe 152 attached to threaded section 148 a , will be responsive with fluid flow therethrough.
[0032] As seen in FIG. 2 , side port 138 is seen to include walls defining a channel 138 a . Channel 138 a is open to the space within narrow portion 118 and is typically dimensioned to receive snugly and fluidly sealing a Halkey valve 146 (a fluid device interface) therein. Halkey 146 may include foam 146 c , a threaded portion 146 a for engagement with syringe 150 (see FIG. 5 ). A channel 146 b in Halkey 146 is provided for withdrawal of fluids through side port 138 . The side port is removably sealed, as by cap 143 (see FIG. 8A ) threadably engaging threaded portion 146 a . For example, cap 143 may be positioned snugly against the Halkey when assembly 110 is in a centrifuge. Similarly, a cap (not shown) may removably engage threaded portion 148 a of Halkey 148 . An alternate embodiment of side port 138 as seen in FIGS. 7-11 illustrate the use of a Halkey adapter 160 to engage Halkey 146 to channel 138 a . Details of this embodiment are set forth below.
[0033] Turning now to FIGS. 2-4 , it is seen that a bottom plate 142 may be sealingly engaged to bottom rim 131 of open bottom 130 of lower portion 116 . More specifically, it is seen that a notched rim 142 a may fit snugly such that an upper surface 142 b of the rim effectively seals the open bottom accepting a central opening 142 d in the bottom plate 142 . Central opening 142 d extends between upper surface 142 b and lower surface 142 c . Central opening 142 d is seen to engage a vertical neck 145 of a captured piston drive screw 144 which, along with drive piston 134 , constitutes a drive assembly for driving the piston upward or downward in the lower portion 116 (see, for example, FIGS. 3A and 3B ). That is to say, piston 134 may be driven between the collapsed (lower) and deployed (upper) positions ( FIGS. 3A and 3B , respectively) by rotation of a base 147 . Piston drive screw 144 is captured on bottom plate 142 as by the action of resilient wedges 145 c (see FIG. 3B , for example). Wedges 145 c ride on top surface 142 b of the bottom plate 142 when the base 147 is rotated. Base 147 may have a notched rim 147 a which dimension is typically not greater than the diameter of lower portion 116 . Base 147 typically has a flat bottom surface 147 b and a flat top surface 147 c , and is integral with vertical neck 145 . Neck 145 typically has an outer surface 145 a and a threaded inner surface or threaded inner walls 145 b.
[0034] Turning to piston 134 , piston 134 is seen to have upper surface 134 a , lower surface 134 c , and a rim 134 b . Rim 134 b may include a cup shape portion for receipt of an elastomeric O-ring 137 (preferably two, see FIG. 7 ) thereon and piston 134 with O-ring thereon is dimensioned to be fluidly sealing and slidably received within the lower portion 116 , such that the O-ring contacts the inner walls and slides up and down thereon between collapsed or lowered ( FIG. 3A ) and deployed or raised ( FIG. 2B ) positions. Upper surface 134 a of piston 134 may be flat or domed (see FIG. 7 ), and lower surface 134 c may be flat or recessed (see FIG. 8A ) or suitably shaped. Threaded member 134 d extends downward into engagement with threaded inner walls 145 b of neck 145 of the piston drive screw 144 .
[0035] FIG. 4 illustrates the use of the fluids concentration cup assembly 110 . Typically, the piston will be in the collapsed or lowered position when bone marrow aspirate or other fluid is received through the lid (see FIGS. 6A and 6B ). After centrifuging, the piston may be deployed as seen in FIG. 4 to place, for example, the bottom surface of the buffy coat layer adjacent the side port 138 . Withdrawal syringe 150 may be used to engage threaded portion 146 a of Halkey 146 as seen in FIG. 5 to withdraw the buffy coat. FIGS. 6A and 6B illustrate the use of a second or aspirate carrying syringe 152 to transfer a bone marrow aspirate or other fluid, before centrifuging, into the cup 112 by engagement of syringe with Halkey 148 in lid 140 .
[0036] FIGS. 7, 8A, and 8B illustrate that the upper surface of 134 a of piston 134 may be dome or conically shaped, such that it fits within conical or sloped walls 118 b in a snug relationship when the piston is at top dead center (TDC) (see FIG. 9A ). The dome shape of the piston is seen to be a truncated conical shape with a flat top surface that will lay above the lowest most portion of channel 38 a / 138 a (see FIGS. 9A and 9B ). The flat top portion of the piston is seen relationally to the bottom of the side port channel and, when the two are close, it allows for the efficient withdrawal of the buffy coat (or other liquid) as the buffy coat rests on top of the red blood cell and below the plasma, after whole blood has been centrifuged.
[0037] In a preferred embodiment, the narrow portion 18 / 118 includes sloped upper walls on 116 and sloped lower walls on 114 , which meet at a cylindrical waist portion 136 . The side port 138 has a channel 138 a , which is typically cylindrical and whose lowermost portion is right at the top of where the cone portion adjacent open top 132 . Walls 118 a of narrow portion 118 may be angled downward from the horizontal in a range of 20-60°, most preferred 40-50°, and most preferred about 45° from the horizontal. The cup may be made of rigid polycarbonate, especially a clear hydrophobic polycarbonate and may have a height of about 4.875 inches or a preferred range of 3½ to 5¼ inches. The waist portion 136 , in a preferred embodiment, is cylindrical and has a volume preferably between about 2 and about 10 milliliters, more preferred about 5 to about 7 milliliters, and most preferred about 6 milliliters.
[0038] When the piston is at top dead center and bottom dead center, the dimensions set forth in the table may be used, as measured from the upper surface of the piston to the bottom of the tip of the lid.
[0000]
Piston at TDC
Piston at BDC
Broadest Range (approx..)
5-25 mL
10-80 mL
Next (approx..)
7-20 mL
35-65 mL
Preferred (approx..)
10-15 mL
45-60 mL
[0039] In a method of use, a surgeon or other healthcare professional withdraws a bodily fluid, such as whole blood or bone marrow aspirate. The piston is set at BDC and the undifferentiated fluid is injected into the cup through the lid. The cap is centrifuged and then removed. At this point, the user will adjust the bottom of the piston, such that, after centrifugation, the bottom of the buffy coat layer will typically be near the preferred level for withdrawal.
[0040] FIGS. 7-11 show a Halkey adapter 160 with facing walls 160 c with a mouse hole shape (see FIGS. 9A and 9B ), such that fluid is funneled into channel 146 b of Halkey 146 . FIGS. 9A and 9B also show how channel 146 b in the Halkey adapter 160 meets the piston top in flush relation when the piston is in the raised position. It is seen how fluid withdrawn through Halkey 146 (arrows in FIG. 11 ) is funneled to the channel by the sloped facing walls 160 c.
[0041] FIGS. 7-11 illustrate an alternate embodiment adapted to help channel a selected fluid, post-centrifuge, into channel 146 b of Halkey 146 . While the term “channel” is used, a Halkey valve typically, does not have a visible channel under neutral pressure. Indeed, it appears to be filled with a foam-like substance. However, when a pressure differential of a set value is exceeded on the Halkey, such as by a syringe device in withdrawing the fluid from the cup, a channel is provided for a fluid to pass through. More information regarding the Halkey may be found at www.halkeyroberts.com. One Halkey that may be used, with this assembly, is Halkey Roberts Part No. e.245501024 (a bondable, one or two-way needleless valve). In any case, a nose of the Halkey will fit in channel 160 a through Halkey adapter 160 to hold the Halkey in place and grooves 160 b on either side of the side walls will engage ridges 138 b on either side of channel 138 a , so that Halkey 146 fits snugly to Halkey adapter 160 and the adapter is glued or otherwise affixed in the channel such that the facing walls 160 c (see FIGS. 9A, 9B, and 11 ) place the lower edge of channel 160 a adjacent (or just above) the upper flat top of piston 134 when piston 134 is at top dead center. Facing walls 160 c are funnel-shaped (see FIG. 11 ), acting to funnel fluid going through Halkey 146 into channel 146 b . This allows for a smooth, non-turbulent and complete flow of liquid above the piston top when it is at top dead center to flow through channel 146 b into a collection device, such as a syringe 150 , attached to threaded portion 146 a (see FIG. 11 ).
[0042] FIGS. 7-11 illustrate an alternate preferred embodiment of a drive piston assembly for moving the piston 134 longitudinally in the cup. Here, base 147 is seen to be split into two halves 147 d / 147 e that are both manufactured in the same mold (so there is no left or right) and may clip together with resilient prongs and slots as seen in FIGS. 7 and 10 . Lid 164 is seen to have a neck 166 , the lid for sealing the bottom of the cup as by gluing, for example. Threaded section 168 is rigidly attached to base 147 d / 147 e and is seen to engage an inner depending threaded leg 170 (see FIG. 9A ) attached to the bottom of the piston. Threaded leg 170 has threads on inner walls thereof. Threaded section 168 is glued or otherwise affixed to base halves 147 d / 147 e as in FIG. 9A , so that rotation of base 147 d / 147 e causes threaded section 168 (which couples with the thread on threaded leg 170 ) to rotate, moving piston 134 up and down. Neck 166 of lid 164 is seen to have an upper portion 166 a and a lower portion 166 b that may be above and below a flat portion 166 c . Flat portion 166 c may have a notched perimeter as seen in FIG. 9A , the notched perimeter for engaging (fluid tight) the bottom rim of the cup. Outer walls of upper portion 166 a snugly and telescopically engage the outer walls of threaded leg 170 , which is seen to be partly recessed in recessed portion on the underside of piston 134 . Multiple anti-rotation ridges 166 d on the cylindrical inner surface of neck 166 project inward and longitudinally and engage multiple anti-rotation grooves 170 a on the outer surface of threaded leg 170 , such that rotation of the base and threaded section 168 will force the piston to go up and down and prevent it from rotating (a piston anti-rotation feature). The only structure that rotates in this embodiment is base 147 and threaded section 168 of the base. The structure that moves up and down is piston 134 and threaded leg 170 . Thus, threaded members of the piston and rotatable base couple, as do anti-rotation members.
[0043] Although the invention has been described with reference to a specific embodiment, this description is not meant to be construed in a limiting sense. On the contrary, various modifications of the disclosed embodiments will become apparent to those skilled in the art upon reference to the description of the invention. It is therefore contemplated that the appended claims will cover such modifications, alternatives, and equivalents that fall within the true spirit and scope of the invention. | A biological fluid collection cup for use with a centrifuge bucket to separate a biological fluid into its component parts is disclosed. It includes an hourglass shape with a large upper and lower portion and a narrow middle portion. A piston is to slide into and slideably be received in the lower portion and a side port is provided for withdrawal of a fluid from the narrow portion. | 1 |
BACKGROUND OF THE INVENTION
The invention relates to an arrangement for reducing microorganisms. The invention furthermore relates to the use of such an arrangement for therapy, in particular in the mouth, jaw, and facial area.
Known from WO 01/87416 A1 is such an arrangement and a method for reducing or destroying microorganisms, such as bacteria, using a light-activatable substance and photodynamic therapy (PDT). Using the light-activatable substance, in particular a stain, the microorganisms are sensitized and/or stained, and they are killed using irradiation with light of an appropriate wavelength and energy density as a result of the selective action and/or staining. The principle of action of PDT is based on the physical effect of energy transmission to the light-activatable substance, which is also called a photosensitizer. From there, the energy for reactions can be made available on the cell membrane. The energy produced by means of a radiation device, especially a laser device, is thus concentrated on the microorganisms and the equilibrium of reactions that also occur in the non-irradiated “normal” milieu are shifted and as a consequence the microorganisms are destroyed.
Furthermore known from EP 0 637 976 B1 is the use of a light-sensitizing substance or compound or photosensitizer (PS) during production of a medication for use during disinfection or sterilization of tissues in the oral cavity or a wound or lesion in the oral cavity by destroying microbes in a periodontal pocket that are associated with an illness, in the region between the tooth and the gum. The tissue, wound, or lesion is contacted with the photosensitizer, the microbes associated with the illness absorbing the photosensitizer. The tissue, wound, or lesion is irradiated with laser light at a wavelength absorbed by the photosensitizer. The reduction in germs in this combined stain and laser treatment is described for various germs and photosensitzers in the form of solutions with, among other things, methylene blue and toluidine blue in various fairly low concentrations, specifically from 0.01 to 0.00125% (weight per volume), whereby furthermore the effect of the energy density applied is indicated. HeNe lasers with a wavelength of 634 nm and an output of 7.3 mW and GaAs lasers with a wavelength of 660 nm and an output of 11 mW are used as light sources.
BRIEF SUMMARY OF THE INVENTION
Starting at this point, the underlying object of the invention is to embody the arrangement such that effective and controllable therapy is attained with an apparatus that is not very complex and with simple handling. The therapy for local, superficial infections, especially in the mouth, jaw, and facial area, should not be complex and should be highly functional. Moreover, the most homogeneous possible irradiation of the area to undergo therapy, in particular the surface of the oral mucosa, should be attained. With respect to the great distribution and great frequency of infections, especially in the area of the mouth, jaw, and face, including dentogenic infections, the problems that have existed in the past should be avoided or at least reduced.
Using a simple structure and simple handling, the inventive arrangement facilitates functional and practical application of the therapy by means of a light-activatable substance and a radiation device. The light-activatable substance is prepared in solution in a high concentration, usefully filled in a syringe sterilized and ready to use. Advantageously, the concentration of the photosensitizer is provided in a solvent such as an aqueous solution or alcohol or ethanol, with a high value. The concentration, specifically weight per volume, is advantageously greater than 0.1%, usefully greater than 0.5%, whereby the upper limit is advantageously 10%, usefully 5%, especially 3%. A concentration of at least approximately 1% has proved to be particularly suitable. The radiation device, which is in particular embodied as a laser device, is combined with an application system, whereby applicators can preferably be detachably connected to the radiation device. The applicators are advantageously single-use optics by means of which it is possible to irradiate the area to undergo therapy in a targeted and precise manner. The applicators are used only once for treatment so that in particular hygiene requirements are met and undesired transmission of microorganisms is safely avoided without complex measures for any subsequent or repeated sterilization. The applicators contain light conductors, in particular optical fibers, and enable without any problem intraoral light distribution and/or irradiation and can be embodied as pocket probes or surface probes. The radiation device and the at least one applicator are preferably embodied such that the light from the light source can be coupled directly into the light conductor. In one preferred embodiment of the invention, a light conductor or an optical fiber with a high numerical aperture is used, whereby the numerical aperture is preferably greater than 0.5, in particular greater than 0.7. Because of this, there are low losses when the light is coupled into the applicator or light conductor and at the same time it is assured that the light beam exiting the applicator or light conductor opens up.
In one preferred embodiment of the invention, a blocking device is combined with the radiation device such that light cannot exit from the radiation device unless the applicator and/or light conductor is connected. As long as the applicator is not properly connected to the radiation device, the blocking device prevents light from exiting directly out of the radiation device. In one preferred embodiment, the radiation device, in particular its head part, contains a preferably central bore into which the light conductor end of the applicator is inserted and fixed. The blocking device is especially arranged in the beam path of the light from the light source and in the free end and/or in the free end face of the light conductor end. In accordance with the invention, the blocking device is actuated when the applicator is connected and/or when the light conductor end is inserted into the aforesaid bore, such that the beam path is uncovered, in particular by means of the light conductor end. The aforesaid bore and/or the inserted light conductor end are arranged and/or aligned with respect to the light source such that the light from the light source falls on the free end face of the light conductor end, where necessary focused by means of an optical system. The applicators contain a connecting or plug-in apparatus, in particular in the form of a Luer plug, for being received on a head or head part of the radiation device. Furthermore, the applicators are embodied in an advantageous manner at least partially curved such that targeted irradiation of the areas to undergo therapy, in particular in the oral cavity, is facilitated. Furthermore, the applicators are preferably embodied at least partially flexible so that undesired injuries are avoided.
In one preferred embodiment, the light conductor has a defined geometry of the light exit area such that the light exit is matched to the shape of the sites to be irradiated in the area to undergo therapy, whereby either a two-dimensional or physical three-dimensional radiation area is produced. Furthermore, the applicator and/or the light conductor has at its tip a spacer with which an active circle of the exiting light is indicated and/or the correct or prescribed irradiation distance is established. In accordance with another embodiment, the light conductor geometry is such that penetration into narrow cavities and/or pockets of tissue with complex shapes is enabled and/or these can be opened gently. Advantageously, the light conductor has a conical tip, specifically usefully with an angle of 1.5 to 4° to the perpendicular. In addition, it has proved particularly advantageous to provide the light conductor in the area of its tip with a light exit surface having a prescribed microstructure ranging from 10 μm to 200 μm. The tip of the light conductor preferably has a micro-roughness with an Ra value ranging from 10 to 40 μm, preferably 20 to 30 μm. Moreover, the connector body of the applicator is embodied as a plug-in and/or screw-in connector with an integrated stop, thus ensuring defined positioning in the axial direction of the light conductor inserted into the radiation device with respect to the light source.
For the inventive use of the arrangement, the light-activatable substance that preferably contains stain is first applied in a high concentration to the area to undergo therapy and then rinsing is performed with a medium, in particular water and/or with the most alkaline possible pH. Thereafter, the irradiation by means of the light from the radiation device is performed, whereby in a preferred manner optimized cell damage occurs. It has proved particularly effective to first apply the light-activatable substance in a high concentration to the area to undergo therapy and subsequently to rinse with a medium, in particular water, and/or with oxygen partial pressure as high as possible, and finally to perform the irradiation by means of the light from the aforesaid light source, whereby optimized cell damage preferably occurs. Furthermore, it has proved particularly useful that after the light-activatable substance is applied in a high concentration to the area to undergo therapy and furthermore prior to the irradiation by means of the light from the light source, the quantity of light-active substance is reduced, specifically in particular by wiping and/or dabbing and/or suctioning and/or blowing air.
The structure of the arrangement and its inventive use are described in detail in the following. The arrangement contains:
1. Light-activatable substance:
The light-activatable substance present in solution, for instance methylene blue, which preferably contains a stain and is called a photosensitizer, is preferably added to a syringe and sterilized and ready for use. In particular a 26-g cannula is provided for the application to the area to undergo therapy, and it has in particular an exterior diameter of 0.45 mm, a length of 25 to 40 mm, and in particular is embodied angled at 35 to 40 degrees and elastic.
2. Radiation device with light source, in particular laser device or therapeutic laser, preferably in the following embodiments:
a. With optical system, in particular lens packet, and preferably with a threaded connector to the light conductor coupling.
b. With direct beam coupling without lens packet, with clear space in front of the diode so that without attached light conductor only a little light escapes diffuse from the access provided for coupling the light conductor. The arrangement is furthermore preferably such that when using a diode with monitoring the back-scattered light regulates the diode.
The radiation device preferably contains a blocking device, by means of which light is prevented from exiting as long as an applicator is not connected to the radiation device.
3. Application system
Single-use optics or applicators that in particular are each used only once and preferably have a light conductor and plastic covering. These are preferably flexible and/or sterilized and/or ready to use and/or compatible with both of the aforesaid radiation devices. Glass or plastic is provided as the material for the light conductor(s) in particular with a numerical aperture preferably greater than 0.5 μm in order to couple as much light as possible and furthermore to emit the light in a large area. Due to the detachable connection between the radiation device and the applicators, it is particularly important that the applicator in the framework of the invention is used only once and thereafter is disposed of as a comparatively simply constructed and cost-effective component and as a “disposable product”.
Two embodiments of the applicators are usefully provided:
a. Pocket probe with conical emitting area in particular for irradiating the periodontal pocket. In one step the pocket is opened, tissue is pushed to one side, and the area is irradiated with radiation to the front and in a circle. The surface is roughened so that the radiation of the light is diffuse (for instance sanded with sandpaper 100 ).
b. Surface probe, preferably with spacer for irradiating superficial sites,
i. the length of which marks the correct distance to the tissue,
ii. the angle of which marks the area in which the therapeutically required light output is to be applied, whereby overlapping irradiation of an area is reduced.
4. Furthermore, in one preferred further development a therapy controller and/or a program for the PC and/or an independent display and control unit. These provide control and orientation for the operator during the therapy. This permits above all selection of the size of the surface to be irradiated or the number of teeth and in particular displays:
a. the time the photosensitizer takes effect,
b. the time for rinsing the site,
c. the time for irradiating each cm 2 or tooth with an acoustic signal for the end of the irradiation for each tooth or cm 2 ,
d. the end of the treatment.
The components of the arrangement are explained in the following:
The energy source or light source of the radiation device is embodied such that there is sufficiently high penetration of the light in the tissue in the relevant wavelength range since long-wave radiation penetrates deeper into the tissue than short-wave radiation. Sufficiently deep penetration into the tissue with light occurs in the area of the absorption maximum of the light-activatable substance, for instance methylene blue (664 nm in NaCl or 655 nm in 96% ethanol). In the so-called optical window between 600-900 nm, the light is very slightly absorbed by chromophores such as hemoglobin or melanin.
Above all laser systems are suitable as energy or light sources. The laser (light amplification by stimulated emission of radiation) is a light source that can emit monochromatic, coherent, and collimated light at a high power. Coherent light includes temporal and spatial coherence in the wave trains.
Essentially photochemical processes are effective in the range of the inventively provided low-power and low energy densities (0.1-100 mW/cm2). In these cases, the absorption of light does not primarily lead to the tissue heating up. These effects produced in biological materials using a thermal laser applications are called “laser-induced biostimulation”. Such lasers are used as the light source for the photodynamic therapy (PDT) using the photosensitizer. Photothermally induced effects can also occur with these lasers when using higher power density or higher energy density.
In diode lasers, semiconductor crystals are used as the active medium and when excited emit coherent radiation in the VIS or IR range. In these lasers, photons are produced directly using electrical current.
In connection with the photosensitizer that is preferably used, a special diode laser is used for the radiation device, hereinafter referred to as the HELBO TheraLite. The HELBO TheraLite diode laser is suitable in particular for methylene blue.
This laser system is characterized by the following properties:
Light source
Diode
Wavelength
660 nm (+5)
Power
Max. 100 mW
Mode
Cw or continuous
Light output power
>40 mW < 50 mW
Cooling system
Air
Energy supply
Battery or accumulator
The application system inventively enables the transmission of the light or laser radiation. The application system provides the desired beam geometry at the site of application and enables simple handling of the laser radiation for therapy. The optical fiber is part of the application system.
One of the goals of effective and controllable therapy in the oral cavity is attaining the most homogeneous possible irradiation of the surface of the oral mucosa. However, the oral cavity is characterized by complex geometry and by the presence of very differently absorbing structures such as bones, teeth, and mucosa that clearly deviate from plane geometry. This is assured with the inventive applicators.
Optical fiber systems can conduct the required energy even into sites that are difficult to access such as in the oral cavity. For coupling into an optical fiber, the primary beam from the laser in the radiation device is focused on the fiber end either directly or through a lens packet. The numerical aperture of the fiber determines the coupling angle such that the radiation largely enters the light conductor.
The beam divergence of the optical fiber is also determined by the type of coupling into the fiber head and of the radiation device also by the numerical aperture (sine of the aperture angle) of the fiber itself. A higher divergence enables a wider transmission angle.
When fibers having a steep drop in energy, or having widely fluctuating light distribution over the irradiated surface, are used, the irradiation field is frequently irradiated in an overlapping manner.
In comparison to the bare fiber, the preferably provided microlens fiber has the most homogeneous irradiation profile. With an optimized microlens fiber, a power distribution with homogeneity of approximately 96% can be obtained over the entire irradiated surface. Overlapping the irradiation fields is not necessary when using a microlens fiber, so that it is possible to cover the infected area in a highly efficient manner and there are no unnecessary areas of overlap.
The application mode (extraoral or intraoral) is a function of the focus size, which is selected according to the findings.
One preferred alternative is provided by inventive fibers with a very high a numerical aperture with which uniformly irradiated sites can also be produced.
A numerical aperture of at least 0.5, preferably 0.7 or higher, is inventively provided in order to avoid complex grinding of fiber tips and to be able to maintain a clinically reasonable distance of 0.5 to 1 cm for the irradiation of intraoral areas.
In particular the following application system with the applicators, which are embodied as a pocket probe and/or a surface probe, is used in the framework of the invention. These applicators contain plastic light conductors that are embedded in a covering, a coupling surface with a connector to the radiation device, in particular a laser device, and a specifically ground radiation area and/or a radiation area having a microstructure.
The invention is described in greater detail in the following using the special exemplary embodiments depicted in the drawings without this resulting in a restriction.
BRIEF DESCRIPTION OF THE DRAWINGS
Accompanying the specification are figures which assist in illustrating the embodiments of the invention, in which:
FIG. 1 contains a table of measurement results for a pocket probe that was arranged perpendicular to a glass surface at an output power of 15.5 mW;
FIGS. 2 and 3 depict a pocket probe and a spot probe for applicators;
FIGS. 4 and 5 depict the structure and assembly of the application syringe 14 that contains the light-activatable substance in solution;
FIG. 6 depicts the light conductor piece of the applicator, not yet bent and without the connector body, which is arranged in the area 16 ;
FIG. 7 depicts the light conductor piece for the pocket probe, the free end 22 being free of the protective jacket 4 and having a length of 7 mm;
FIG. 8 depicts an applicator similar to FIG. 4 , a spacer 20 being arranged on the free end;
FIG. 9 depicts a bent light conductor piece of a pocket probe similar to that in FIG. 3 , the free light conductor end 8 projecting from the connector body 6 at a predetermined length, in this case 10 mm;
FIG. 10 depicts side elevations of one preferred embodiment of the spacer 20 ;
FIG. 11 depicts elevations of the surface probe with inwardly contracted light conductor with the spacer 20 ;
FIGS. 12 and 13 provide partial depictions of surface probes, whereby in accordance with FIG. 12 the surface probe has a numerical aperture of 0.72;
FIGS. 14 , 15 and 16 depict the optical system of the radiation device, whereby in accordance with FIG. 14 a perpendicular beam divergence angle of no more than 35° is provided and in accordance with FIG. 15 a parallel beam divergence angle of no more than 10° is provided;
FIG. 17 illustrates the radiation device without the optical system, whereby a battery tube 44 for the batteries required for supplying current to the electronics is present in a housing tube 42 ;
FIG. 18 depicts one particular embodiment of the invention and illustrates the radiation or laser device from the side, without applicator;
FIG. 19 depicts the embodiment of FIG. 18 and illustrates two exemplary embodiments of applicators, whereby the applicator A illustrated at the top is a pocket probe similar to that in FIG. 2 , while applicator B, illustrated therebelow, is a surface probe similar to that in FIG. 3 ;
FIG. 20 depicts the embodiment of FIG. 18 and illustrates a locking mechanism containing a rotationally symmetrical locking body 58 that has an “H”-shaped cross-section and that in its center has a hole 60 with a diameter that is 1.01+0.02 mm;
FIG. 21 depicts the embodiment of FIG. 18 and provides the exploded illustration of the locking body 58 ;
FIG. 22 depicts the embodiment of FIG. 18 and illustrates the locking disk 62 in FIG. 22 ;
FIG. 23 depicts the embodiment of FIG. 18 and illustrates a section through the radiation device;
FIG. 24 is an enlargement of the anterior part of the device in FIG. 23 ;
FIG. 25 depicts the embodiment of FIG. 18 and illustrates a section in an axial plane through the locking body 58 , whereby it is easy to see the H-shaped sectional surface;
FIG. 26 depicts the embodiment of FIG. 18 and illustrates a section in an axial plane through the locking disk 62 that contains the hole 106 , already described, in the center; and
FIG. 27 depicts the embodiment of FIG. 18 and illustrates the locking spring 64 .
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 contains a table of measurement results for a pocket probe that was arranged perpendicular to a glass surface at an output power of 15.5 mW. The measured powers are provided in mW depending on the diameter of an optical fiber and the distance from the light source. It should be stated at this point that a photosensitizer with a high concentration is preferably used, specifically preferably greater than 0.1%, in particular on the order of magnitude of 1%, in a solvent, whereby in accordance with FIG. 1 methylene blue in solution is provided for the photosensitizer.
FIGS. 2 and 3 depict a pocket probe and a spot probe for applicators. It is understood that the dimensions provided in millimeters as examples here and in the other figures can be modified where needed. The applicators contain a light conductor 2 embodied as a fiber that is for the most part exteriorly surrounded by a protective jacket 4 . The applicators furthermore have a connector body 6 that is preferably embodied as a Luer plug and that connects or is received in the head of the radiation device. The light conductor 2 passes through the connector body 6 and its end 8 projects beyond by a predetermined length, specifically by 5 mm in accordance with FIG. 2 . The light conductor end 8 is not provided with a protective jacket and when the applicator is connected is inserted into the head part of the radiation device and positioned therein. The light conductor 2 is embodied at least partially flexible and/or contains a curved area 10 . The dimensions of the applicators are provided such that they can be inserted into the oral cavity with no problem.
In the laser used in both applicators, the laser radiation exits in a circle with a 1-mm core diameter due to the material properties and the grinding geometry in the area of the tip 12 at an initial divergence angle ranging from 30 to 60°, preferably 40 to 55 degrees, frontally or in particular for the pocket probe ranging from 220 to 300 degrees, preferably 240 to 290°, in particular 260 to 280 degrees.
These properties render the applicators easy-to-use optical tools for precise irradiation of surfaces that have simple shapes, but also surfaces that have complex shapes.
The structure and assembly of the application syringe 14 that contains the light-activatable substance in solution are depicted in FIGS. 4 and 5 . The syringe 14 that contains the light-activatable substance in solution is supplied ready-to-use. Prior to use, the cap must be carefully rotated to remove it from the tip and the enclosed sterile cannula must be fixed on the Luer lock adapter of the syringe. Care should be taken that the fingers are correctly positioned. Carefully explain the procedure to the patient prior to treatment. Once the area to undergo therapy has been prepared properly in terms of clinical-surgical aspects, open the package; one blister-packet with the light-activatable substance, one blister-packet with a cannula, and any printed material are removed. Read the printed material prior to first use. Maintaining sterile conditions, empty both blister-packages over the sterile surgical tray. Syringe and cannula are thus sterile and ready for use in the sterile area. Carefully remove the silicon stopper from the syringe and fix the cannula by rotating on the Luer cone.
FIG. 6 depicts the light conductor piece of the applicator, not yet bent and without the connector body, which is arranged in the area 16 . The protective jacket 4 is provided between this area 16 and the free end 18 . Furthermore, arranged at the free end 18 is a spacer 20 by means of which a defined distance is maintained from the area to undergo therapy, in this case 5.5 mm.
FIG. 7 depicts the light conductor piece for the pocket probe, the free end 22 being free of the protective jacket 4 and having a length of 7 mm. The free end 22 is ground and has a surface with a 100 grain size, corresponding to processing with abrasive paper. The tip 24 of the free end 22 is embodied stub-like and/or is provided with a radius. The surface preferably has a predetermined micro-roughness. It preferably has an Ra value ranging between 10 and 40 μm, preferably ranging between 20 and 30 μm.
FIG. 8 depicts an applicator similar to FIG. 4 , a spacer 20 being arranged on the free end. In this embodiment, the light conductor end 8 projects from the connector body 6 , specifically at a length of 10 mm.
FIG. 9 depicts a bent light conductor piece of a pocket probe similar to that in FIG. 3 , the free light conductor end 8 projecting from the connector body 6 at a predetermined length, in this case 10 mm.
FIG. 10 depicts side elevations of one preferred embodiment of the spacer 20 .
FIG. 11 depicts elevations of the surface probe with inwardly contracted light conductor with the spacer 20 .
FIGS. 12 and 13 provide partial depictions of surface probes, whereby in accordance with FIG. 12 the surface probe has a numerical aperture of 0.72.
FIGS. 14 through 16 depict the optical system of the radiation device, whereby in accordance with FIG. 14 a perpendicular beam divergence angle of no more than 35° is provided and in accordance with FIG. 15 a parallel beam divergence angle of no more than 10° is provided. As can be seen in particular from the exploded illustration in accordance with FIG. 16 , the laser diode 26 is arranged in a threaded sleeve 28 . This is a multimode laser diode with 100 mW continuous for 670 nm including a monitor diode. There is an objective lens 32 in the tapered part 30 , a lens holder 34 being provided for an additional objective lens 36 . Furthermore provided are an adjusting ring 38 and a receiving body 40 .
FIG. 17 illustrates the radiation device without the optical system, whereby a battery tube 44 for the batteries required for supplying current to the electronics is present in a housing tube 42 . A cap 46 is detachably connected or can be detachably connected to the housing tube 42 via a threaded connector at the posterior end, the lower end in accordance with the drawing, of the housing tube 42 . Furthermore, a key-operated switch 48 is provided at the posterior end of the housing tube 42 or the cap 46 by means of which the irradiation or laser device can be turned on and off. Arranged at the anterior end of the housing tube, which is embodied as a protective housing, is a head part 50 that is embodied for receiving the applicators and for decoupling the light beam using the central bore 52 .
The following light output is available for irradiation using the preferred embodiment of the radiation device, which is also called the HELBOTherLite laser:
Pocket probe
Spot probe
Irradiation
Radial, 250-280 degree range, in
40-60 degree range, in
particular largely 270 degrees
particular largely 50
frontally
degrees frontally
Power density
>40 mW/cm 2
>40 mW/cm 2
The preferably used light-activatable substance is a sterile, isotonic, deep blue odorless aqueous liquid. It contains phenothiazin-5-ium, 3,7-bis(dimethylamino)-chloride for coloring and sensitizing microorganisms for the lethal photodynamic therapy using the radiation device.
1 mL of the solution contains:
1% phenonthiazin-5-ium, 3,7-bis (dimethylamino)-, chloride
Glucose for isotonization
MHPC (methylhydroxypropylcellulose) for adjusting the viscosity
Citrate for buffering the solution
The osmolarity is approximately equal to that of human tissue.
The in solution with the light-activatable substance is packed in a glass syringe and sealed with a stopper made of silicon. The fill quantity is 0.5 mL+/−0.1 mL. The glass syringe is sealed with a blister and is steam-sterilized in a validated sterilization process. The aforesaid solution is usefully packaged in five blister-packs with one printed insert in a box. Five 28 G cannulas that are each also packed in a blister-pack and sterilized are also enclosed.
During the lethal photodynamic laser therapy, the light-activatable substance stains and sensitizes microorganisms in local superficial infections, in particular in the mouth, jaw, and facial areas. Subsequent irradiation with the radiation device eliminates stained microorganisms and restores the natural oral bacteria.
Topical application occurs in the area of the infection without or with a surgical incision and curettage and paralesional as follows: the patient rinses with water twice for 20 seconds. Saliva or blood adhering to the surfaces to be treated is suctioned or dabbed off in order to prevent dilution of the photoactive substance.
The light-activatable substance is slowly applied by means of the syringe, covering the surface of the infected tissue. The quantity must be selected such that the light-activatable substance moistens the surface of the infected areas in a layer that is as thin as possible. Make sure that the folds and pockets in the tissue are completely moistened. Where required, when the morphology is complex, carefully distribute with the air syringe. The light-activatable substance needs at least 60 sec to take effect. After rinsing for at least 3 sec while suctioning excess solution (deposits of stain must be removed!), irradiate with the radiation device. The correct dosage of energy supply, the irradiation, is essential for the germ-reducing effect and thus for treatment results.
The operator controls the therapy using treatment time for a given surface area treated as the critical variable for determining the required energy density (J/cm 2 ). For each cm 2 or tooth there should be at least 1 minute of irradiation time with the radiation device.
The following formulas are used for calculating the irradiated surface A of a lesion with a radius r during the irradiation:
a: with pocket probe: surface of defect F=Width W*Height*2 and thus per quadrant:
Teeth
1
2
3
4
5
6
7
8
Width, cm
0.6
1.2
1.8
2.4
3
3.6
4.2
4.8
Height, cm
0.8
0.8
0.8
0.8
0.8
0.8
0.8
0.8
3D factor
2
2
2
2
2
2
2
2
Surface area, cm 2
0.96
1.92
2.88
3.84
4.8
5.76
6.72
7.68
Power, mW
50
50
50
50
50
50
50
50
Surface density, W/cm 2
0.052
0.052
0.052
0.052
0.052
0.052
0.052
0.052
Irradiation, sec
60
120
180
240
300
360
420
480
Energy density, J/cm 2
3.125
3.125
3.13
3.125
3.125
3.125
3.125
3.125
Irradiation protocol for the pocket probe
B: with the spot probe: Surface of defect F=(πr2)
The power density (FD) is calculated as follows:
FD (Watt/cm 2 )=power (Watt)/irradiated surface (cm 2 )
The energy density (ED) is calculated as follows:
ED (Wattsec/cm 2 )=power (Watt)*time sec/irradiated surface (cm 2 )
The dosimetry selected is consolidated in the following table. As a rule, irradiation is performed at a distance of 0.55 cm and at a power density of 0.051 W/cm 2 a total dose of 3 J/cm 2 is used.
Irradiation unit 1 1 1 2 3 4 5 6 Diameter, cm 1.8 0.9 1 1 1 1 1 1 Radius, cm 0.9 0.45 0.5 0.5 0.5 0.5 0.5 0.5 Distance, cm 1 0.5 0.55 0.55 0.55 0.55 0.55 0.55 Surface area, cm 2 2.5434 0.6359 0.79 1.57 2.355 3.14 3.925 4.71 Power, mW 40 40 40 40 40 40 40 40 Surface density, W/cm 2 0.016 0.063 0.051 0.051 0.051 0.051 0.051 0.051 Irradiation, sec 60 60 60 120 180 240 300 360 Energy density, J/cm 2 0.94 3.77 3.06 3.06 3.06 3.06 3.06 3.06
Irradiation Protocol for Spot Probe
An effective phototoxical effect can be induced if bacteria are stained using light-activatable substances or vital stains such as MB and irradiated with light of a suitable wavelength. Unstained cells do not demonstrate any toxic damage. Photochemical killing of possible pathogenic bacteria is performed at fur farms and zoos in that methylene blue is added to the drinking water.
MB has been used for 25 years as a photosensitizer for local treatment of herpes-induced illnesses. The dark toxicity and phototoxicity (PDT) of intratumorally applied methylene blue was explored in experiments on colon tumors. These tumors were not destroyed by irradiation alone with a low total dose (6 J/cm 2 ) or by administering the substance (20 μg/mL) alone.
Adding MB can lead to systemic secondary effects such as increased perspiration, nausea, and vomiting.
Oral administration can lead to gastrointestinal complaints and to dysuria. The ingredients for preparing the solution are:
Active/inactive ingredients
1 mL contains
Methylene blue × H2O
10.00
Trisodium citrate × 2 H2O
0.433
Citric acid × 1 H2O
1.667
MHPC
10.00
Sodium chloride
9.00
Water for injection
1000
Ingredients of light-activatable substance:
Using the present biocompatibility assessment, the substances used in the preparation are evaluated with respect to their biocompatibility, teratogenity, and mutagenity under the given application conditions as acceptable in terms of the desired treatment goal.
Using topical application of the photosensitizer (PS), there are none of the significant problems associated with systemic use of a medication such as antibiotics, nor of systemically used PS, such as e.g. substance toxicity and generalized multi-week photosensitization of the skin. Topical application increases specificity so that healthy tissue, e.g. mucosa in the area surrounding the lesion, is protected.
The treatment can be repeated due to the minor nature of the secondary effects. The therapy is furthermore distinguished by its non-invasive nature.
The local concentration is also influenced in that as a rule increased salivation is induced in the oral mucosa after local application of the PS. This leads to a decrease in the PC concentration and reduces the stain's penetration into the lesion. Moreover, saliva proteins can deactivate the PS because of non-specific binding. Introducing the PS in a solution, in particular a viscous solution, inventively reduces the mixing, dilution, and reaction with saliva for the treatment period.
After the period for taking effect, which is at least 60 sec, in accordance with the invention the excess PS is removed in order to increase the light transparency of the treated tissue.
Measurements demonstrate that a 100-μm liquid film of the solution with the light-activating substance that stands on the tissue reduces the effective energy density by 97%. In accordance with the Beer-Lambert Law, the light is further weakened when the layer thickness is doubled. Thus therapeutically effective irradiation is not possible with the light-activating substance when there is excess solution.
An energy density of 50-100 J/cm 2 is recommended for effectively applying PDT to oral mucosa lesions. The energy dose should be matched to the type and localization of findings. Since the oral mucosa are generally very sensitive to pain, power densities greater than 150 mW/cm 2 should be avoided. Power densities between 200 and 500 mW/cm 2 can lead to non-specific thermal tissue damage.
The surface area irradiated should be selected to be larger than the surface area of the lesion in order to attain a uniform dose in the area of the lesion.
The light dose of approximately 100 J/cm 2 for the PDT can be attained in different manners: high power density and short exposure times or low power density and long exposure times. Due to the aforesaid thermal damage, high powers are not used. On the other hand, it is not possible to obtain a photodynamic effect when the power densities are too low, even if the irradiation periods are correspondingly long.
Methylene blue solutions are able to reduce the number of all examined microorganisms in the culture medium being used.
Methylene blue solutions reduce almost all Gram positive bacteria in a concentration of 25-44 μmol in vitro.
Completely reducing Gram negative germs requires 3-30 times higher concentrations. P. aeruginosa was reduced from 100 mW/cm 2 by 3.5 log 10 CFU at a concentration of 200˜mol and an energy density of 100 mW/cm 2 .
The observed dark toxicity was higher for toluidine blue (TB) than for methylene blue (MB). This is consistent with the distribution coefficient P that was determined to be 0.33 for TB and 0.11 for MB.
Since log P was <0, both stains can be characterized as hydrophilic and, at least theoretically, should be able to fit the water-filled porin protein channels of Gram negative bacteria.
While dark toxicity for Gram positive bacteria was nearly unrelated to type, the dark toxicity for Gram negative bacteria is quite clearly a function of type and specifically corresponds to the trans-membrane permeability coefficient of the exterior membrane of Gram negative bacteria.
Dark toxicity was a function of both the concentration and the incubation period prior to irradiation.
S. aureus was identified as the most resistant bacterium for the Gram positive group, and it required the highest concentrations for its destruction.
P. aeruginosa was identified as the most resistant bacterium for the Gram negative group, and it required the highest concentrations for its destruction.
In the case of Gram negative bacteria, photodynamic sensitivity is a function of trans-membrane permeability, and hydrophilicity, positive charge, and low molecular weight of the stain molecule promote efficacy.
For the present therapy, only 60-sec periods for taking effect with subsequent rinsing prior to irradiation are provided for the treatment of microbially infected areas.
The selected parameters of therapy, in particular:
1% concentration of the light-activating substance in solution
Energy of 2.4 J
Power density of 50 mW/cm 2
And energy density of 3 J/cm 2
Incubation time of 60 sec with subsequent rinsing of solution are suitable for assuring a positive treatment result. On the other hand, possible risks and secondary effects are limited when these conditions are observed and, when properly explained, seem to be acceptable in light of the expected positive aspects for patients.
PDT is based on a photochemical process in which the photosensitizers (PS) are activated by means of laser radiation and the radiated energy “portions” such that it is available for forming locally toxically acting oxygen radicals. Thermal damage to the tissue can be prevented with certainty at the selected energy and power densities of 3 J/cm 2 and 50 mW/cm 2 , respectively.
The clinical application of PDT is possible since the stain solutions selectively color cell systems, while the interaction with the epithelium is very limited. Studies of normal oral mucosa indicated that the penetration depth of MB solutions after 10-min incubation time was limited to just the first 1-2 exterior layers of cells of the epithelium. Furthermore, the life expectancy of the active radicals and their precursors is microseconds, so that it is practically assured that there are no concomitant destructive effects in healthy tissue due to diffusion, since there is not enough time for this.
The effect is thus linked to the presence of the stain molecule in the PS.
The selection of for instance methylene blue for the photodynamic active substance in the preparation is based, first, on the low toxicity of methylene blue under the selected conditions, and second, on the favorable absorption maximum at 664 nm:
Capable and efficient diodes for producing the laser beam are available for this wavelength
Treatment is performed in the visible light spectrum, which is crucial for the therapy's safety and efficiency
The depth the light penetrates into the tissue in this wavelength range is adequate for also being able to reach penetrating bacterial colonies
The singulet oxygen formation is the critical mechanism for killing the germs, while healthy cells cause these radicals to deteriorate due to catalases
Can, on the other hand also be some protection due to the efficacy of vitamins like vitamin C and E.
Given the results of the spectro-photometric tests of MB with and without irradiation, there was a nearly linear decrease in extinction as applied energy density increased. Photo-bleaching with destruction of the stain molecules occurs to a significant extent at energy densities that are greater than the therapeutically applied energy density by a factor of 7.
A photo-biological effect occurs in this area that promotes tissue regeneration and stabilizes local metabolism
Methylene blue is available in a pure and documented form the use in a preparation leads to stable solutions
These solutions are simple and safe to handle under conditions prevalent in medical surroundings when used with appropriate caution
The waste that occurs during use is relatively harmless
Coordinating stain and light source provides a therapeutically effective system that demonstrates effectiveness against Gram positive and Gram negative bacteria as well as against fungus such as candida albicans and that, by reducing the number of microorganisms, supports the body's own defense for a short period in order to improve clinical symptoms.
Using the HELBO PocketProbe applicators, it is possible to inventively apply an energy density largely ranging from 1 to 7 J/cm 2 , preferably from 2 to 4 J/m2, in particular a largely uniform energy density of 3 J/cm 2 , even in complex sites around and between teeth in the posterior areas of the oral cavity.
By using the photo-dynamic therapy, it was possible to observe rapid freedom from pain and accelerated wound healing due to supporting photo-biological effects.
The only secondary effects observed during the therapy were occasional burns; these healed rapidly after the treatment concluded, however.
One particular embodiment of the invention is described in greater detail in the following using FIGS. 18 through 27 . The radiation device, which is also called the therapy laser hereinafter, is for photo-dynamic therapy (PDT) and is in particular embodied as a laser device. It contains a blocking device by means of which the light path is automatically uncovered when an applicator that contains a light conductor is attached. As long as the applicator and/or the light conductor is not attached to the radiation device/laser device, the inventively embodied blocking device prevents laser light from exiting from the laser device. The blocking device in particular contains a locking body that is embodied and arranged such that laser light cannot exit unless the applicator or light conductor is attached. The locking body of the blocking device is arranged in a changeable position, and it cannot be moved from this position for uncovering the light path unless the applicator or light conductor is properly attached. The blocking device is in particular integrated in the head part of the radiation device. Alternatively, the blocking device can be at another location on the radiation device and/or embodied differently, and in particular can be integrated into the optical system. The inventive radiation device assures that the light is coupled directly from the diode or laser diode into the light conductor such that
1. low losses occur because an optical fiber with a high numerical aperture is used, in particular greater than 0.5, preferably greater than 0.7, which ensures that a relatively large surface area is uniformly irradiated because the light beam opens up when it exits the fiber,
2. because of the installed blocking device, the light cannot exit unless the light conductor is inserted or attached, and otherwise the light cannot exit directly out of the laser device. Thus the laser device can be operated without protective goggles and without having to designate a Laser Protection Representative, as would fundamentally be necessary at the provided laser device output.
Due to the high numerical aperture of the light conductor used, the aforesaid scatter effect is attained when the light exits/when the area to undergo therapy is irradiated and on the side of the applicator or light conductor facing the laser device there is a collective effect such that a lens system between the laser or diode and the light conductor is not necessary.
When using the radiation or laser device and/or when using the arrangement for photo-dynamic therapy, the following listed steps are particularly important:
1. First apply the solution with the photosensitizer in a high concentration to the area to undergo therapy so that the solution penetrates as rapidly as possible, especially into the plaque on teeth.
2. In addition, it is preferred that there be rinsing with a medium, in particular water, with an ion concentration that is as low as possible so that bacteria and/or cell membranes are weakened due to the osmotic pressure gradients thus produced. It should be stated that for instance a physiological table salt solution would not work well due to the relatively high ion concentration. The pH of the medium is preferably alkaline. The pH is preferably 7 to 9. The oxygen partial pressure is preferably high. In the framework of the invention, the medium, in particular prepared tap water, has an oxygen partial pressure ranging from 4 to 6 mg/L for rinsing. The medium is usefully enriched with molecular oxygen up to 14 mg/mL. Furthermore, peroxide enrichment has proved useful in accordance with the invention, specifically as 0.5% to 3% hydrogen peroxide solution.
3. Due to the prior rinsing with a medium of low concentration, optimum cell damage occurs during the irradiation by means of the laser light.
Description of the irradiation device or laser device
The device is operated with batteries or accumulators and for the light or beam source uses a semiconductor laser (laser diode) that is operated continuously (cw). FIG. 18 illustrates the radiation or laser device from the side, without applicator. The beam source is built into a cylindrical protective metal housing 42 . The length of the protective housing containing the housing tube 42 is about 124 mm, the diameter is about 16 mm. After the batteries or accumulators have been inserted, a contact cap 46 is screwed onto the end of the protective housing 42 where the batteries are to be inserted. Placing the key-operated switch 48 formed as the closure cap into the contact cap 46 renders the unit ready to operate. The operating mode is indicated by differently colored LEDs 54 .
The head part 50 is screwed onto the protective housing 42 at the other end of the protective housing 42 and glued thereto so that direct access to the beam source is prevented. The head part 50 receives the applicators and is thus for coupling the laser beam, and it also contains the locking mechanism. Pressing a button 56 activates the semiconductor laser.
Applicators
FIG. 19 depicts two exemplary embodiments of applicators, whereby the applicator A illustrated at the top is a pocket probe similar to that in FIG. 2 , while applicator B, illustrated therebelow, is a surface probe similar to that in FIG. 3 . Both applicators comprise a transparent plastic light conductor with a diameter of about 1 mm, have a Luer plug for being received on the head of the laser device, are bent, and are surrounded with a white protective jacket between Luer plug and beam exit end. The light conductor end (without protective jacket) in the Luer plug is inserted into the head of the protective housing.
Applicator A has a slightly conical tip, the surface of which is roughened on the last 5 mm. The rough surface ensures that the laser light is emitted in nearly all spatial directions, the most energy being emitted in the axial direction of the light conductor. Applicator B has a flat end face as the exit surface for the laser light. In addition, a wire loop is built-in on the light conductor end as a spacer. In contrast to applicator A, the laser light has diverging, conical radiation characteristics, which means more energy is emitted in the axial direction. Therefore applicator B was used for all other measurements, since it contains the greater potential for risk from the standpoint of laser safety.
Blocking device/locking mechanism
The locking mechanism depicted in FIG. 20 contains a rotationally symmetrical locking body 58 that has an “H”-shaped cross-section and that in its center has a hole 60 with a diameter that is 1.01+0.02 mm. The laser diode is positioned in the recess of the “h” that faces away from the beam exit and in the activated condition emits light through the hole 60 in the locking body 58 in the direction of the beam exit.
Located in the depression of the “H” that faces the beam exit is a round locking disk 62 that also has in its center a hole with a diameter that is 1.01+0.02 mm. The exterior diameter of this disk 62 is substantially smaller than the interior diameter of the locking body 58 , so that in accordance with FIG. 20 the disk can be placed in the depression. The locking disk is held eccentricially by means of a wire spring (locking spring), however. Thus this disk 62 covers the hole in the locking body and the laser light cannot exit. The wire spring 64 is conducted in a groove on the circumference of the locking disk. As can be seen from FIG. 21 and the exploded illustration of the locking body 58 and the locking disk 62 in FIG. 22 , the locking body 58 , in whose recess the locking disk is movably arranged, is arranged in a diode holder 68 . In the exploded depiction in FIG. 22 , it is easy to see the two aforesaid holes of the locking body 58 and locking disk 62 .
It is not until the light conductor of the applicator is inserted up to the stop that the locking disk 62 is pressed into the central position so that the hole of the locking disk 62 and the hole of the locking body 58 coincide and the laser light can be coupled into the light conductor. If the light conductor is withdrawn, then the wire spring 64 presses the locking disk 62 back into the starting position and the laser light is blocked. In the framework of the invention, other restoring elements can also be provided instead of the wire spring 64 depicted here in order to make it possible for the laser light to exit only when the applicator and in particular its light conductor end are properly connected to the radiation device.
FIG. 23 depicts a section through the radiation device and FIG. 24 is an enlargement of its anterior part. This radiation device fundamentally corresponds to that explained in the foregoing and additionally contains the blocking device/locking mechanism. Arranged in the battery tube 44 that is enclosed by the housing tube 42 are three batteries 70 that are actuated by means of a battery spring 72 . A socket 74 is arranged in a guide 76 , whereby furthermore present are a disk 78 and a spacing disk 80 . Furthermore, two pins 82 , 83 are provided for contacting with electronics or an electronic bar 84 . The button 56 that can be actuated from outside is arranged on the electronics bar 84 , whereby in particular for sealing of a key film 86 together with a ball 88 are provided. An area with a hammer 92 is provided in the anterior direction adjacent to the interior area with the electronics 84 and separated by means of a rear insulation 90 , whereby an anterior insulation is also present. Two O-rings 96 , 97 are furthermore arranged inside the housing tube 42 . Arranged at the anterior end of the housing tube 42 is the head part 50 , the anterior end of which engages in the connector body or Luer plug 4 of the applicator (not shown here). The diode holder 68 , already explained in the foregoing, with the laser diode 26 is arranged in the head part 50 , whereby an insulating disk 98 and a printed board 100 for the diode, including wires necessary for contacting, are provided to the rear toward the battery tube 44 . In addition, provided in the direction of radiation in front of the laser diode is a protective film 102 by means of which in a preferred manner the laser diode can be protected against exterior influences, an O-ring 104 also being provided. Moreover, the locking disk 62 and the locking spring 64 are arranged in the interior recess of the head part 50 of the locking body 58 , already explained.
FIG. 25 depicts a section in an axial plane through the locking body 58 , whereby it is easy to see the H-shaped sectional surface. It is understood that the dimensions given for the special embodiment in millimeters can also be different.
FIG. 26 depicts a section in an axial plane through the locking disk 62 that contains the hole 106 , already described, in the center. On its exterior circumference the locking disk has a groove 108 in which the wire or locking spring engages.
Finally, FIG. 27 is a depiction of the locking spring 64 . It does not have to be particularly stressed that the dimensions of the locking spring and the other components can also be different for other embodiments.
Functional description—blocking device
The blocking device contains the following individual parts:
Locking plate/locking disk
Spring blocking device/locking spring
Locking holder/locking body
Diode holder/diode holder
Diode
Head R60/head for Luer plug
The parts are arranged as follows:
The diode is inserted in the diode holder and fixed from behind with the ESD bar. The diode is now seated in the diode holder. The diode is oriented over the interior diameter of the diode holder. Now the locking holder can be pushed onto the diode. The locking holder is positioned over the interior diameter of the diode holder. The O-ring in the locking holder absorbs minor shocks in the longitudinal direction.
The locking spring is inserted into the groove of the locking plate. This arrangement is placed into the opening of the locking holder. The head is pushed over the locking holder and the diode holder.
Functional description:
The light conductor is inserted into the light conductor path via the 1.5 mm bore in the head. After approx. 7 mm, the light conductor is positioned via a decrease in the diameter to 1.1 mm. The light conductor is then pushed to the locking plate.
The locking plate is pressed onto the interior edge of the locking holder by the pre-stress of the spring. The plate is always uncentered by this and covers the 1.01 mm bore in the locking holder so that no radiation can exit.
The light conductor strikes the cone of the locking plate and presses the latter against the spring force into the center of the locking holder. After the locking plate has been centered, the 1.01 mm bore of the locking holder is uncovered and the light conductor is pushed through this opening into the coupling area. The light conductor has reached the coupling area when the Luer plug reaches the stop on the head.
When the light conductor is withdrawn, the locking spring returns the plate to the non-central position, re-closing the 1.01 mm bore.
Discussion about the safety of the locking mechanism
The spring wire in the locking spring has a diameter of 0.25 mm. The groove is 0.3 mm. Since the wire has a round shape, it cannot become jammed in the groove. This means the blocking device is reliable. The edges of the locking plate are broken by slide grinding to 0.2 mm.
The spring always presses the locking plate outward. There is even locking without the locking spring due to the position of the laser during operation. The locking plate is pulled downward by its weight, closing the 1.01 mm bore. Because of the special shape of the spring, it is also not possible for the spring to jump out of the groove. The shape of the spring encloses the locking plate and then secures it.
Because of the slight angle, any incline in the plate has no effect on the locking mechanism. The plate moves back to its position the next time the light conductor is inserted.
Soiling on the locking mechanism has no effect on the function of the lock. The only factor that has to be taken into account is the dust from wear in the light conductor. A simple cleaning of the mechanism can be performed during the annual examination.
The only foreign bodies than can occur are 1.1 mm in size, since this is the limiting size for the bore in the head.
Any reduction in the spring force is monitored using tests. Changes caused by falls to the ground are also monitored.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not as restrictive. The scope of the invention is, therefore, indicated by the appended claims and their combination in whole or in part rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope. | The invention relates to a micro-organism reducing device, comprising a radiation device which is provided with a light source, a photosensitive substance which treats the area to be treated and is irradiated by said light source. The aim of said invention is to configure said device in such a way that it is possible to carry out an efficient and controllable treatment by means of operationally low-cost and easily handling apparatus. For this purpose, the inventive device comprises at least one applicator provided with a fiber-optic waveguide. In addition, said applicator and radiation device respectively comprise corresponding liaison bodies contacting one of them in such a way that the light from the light source is emitted towards the treated area by means of the fiber-optic waveguide. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. patent application Ser. No. 10/826,216, filed Apr. 16, 2004, which claims priority from U.S. Provisional Patent Application No. 60/463,123, filed Apr. 17, 2003, both of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates generally to synthetic chemistry. More particularly, the present invention relates to poly(thioesters), monomeric diesters and their derivatives.
BACKGROUND
[0003] Hydroxyl groups that are in the β-position relative to a sulfur atom in an aliphatic chain have unusually high reactivity, and their properties are significantly different from other hydroxyl groups. For example, unlike compounds with hydroxyl groups in other positions, compounds with hydroxyl groups in the β-position relative to a sulfur atom in an aliphatic chain readily undergo self-polycondensation as well as co-condensation with other glycols in the presence of other acids and/or at elevated temperatures, resulting in the formation of poly(thioethers) (F. Richter, et. al., U.S. Pat. No. 2,582,605).
[0004] Di(hydroxyethyl)disulfide, as well as other di(hydroxyethyl)polysulfides are typical compounds with hydroxyl groups in the β-position relative to a sulfur atom. They are known in the art to be precursors for various poly(thioethers), which have been used in lubricants (U.S. Pat. No. 2,582,605), in polyurethanes (U.S. Pat. No. 3,386,963), in mercaptan-terminated oligomers (U.S. Pat. No. 4,124,645), in transmission fluids (U.S. Pat. No. 4,764,299), and in acetal-functional compounds used in window insulation (U.S. Pat. No. 6,383,324).
[0005] The prior art describes several attempts to convert di(hydroxyethyl)polysulfides into various compounds that contain ester functionality adjacent to the —(CH 2 ) n —S— segment. For example, U.S. Pat. No. 6,114,485 discloses compounds that include an —O—C(O)—(CH 2 ) 2 —S— segment in monomeric products, but the chemical structure of these compounds is achieved through a chain of several complex chemical reactions that take multiple steps and over 20 hours of combined reaction time. In addition, the technology described in this patent cannot be used to produce polymeric products with multiple poly(thioester) segments.
[0006] U.S. Pat. Nos. 2,221,418 by Weihe et al. (referred to hereafter as Weihe) and 5,407,972 by Smith et al. (referred to hereafter as Smith) describe products that are produced after (polythio)glycols are mixed with dicarbonic acids and/or their anhydrides. However, these patents do not describe the formation of poly(thioesters) from these products. For example, Weihe describes the formation of an “insoluble balsam”, and Smith describes “polysulfide polymers” produced as the result of the interaction between di(hydroxyethyl)polysulfides and dibasic carbonic acids or their anhydrides.
[0007] Nowhere in Weihe or Smith is described the chemical structure of the resulting products. However, based on the above-described unusual reactivity of hydroxyl groups in the β-position relative to a sulfur atom, and the strong tendency of such hydroxyl groups to homo-condense according to reaction (1), it is highly likely that the products formed by Weihe and Smith under the conditions described in these patents are poly(thioethers), rather than poly(thioesters).
m HO—(CH 2 ) 2 —S x —(CH 2 ) 2 —OH→H(—O—(CH 2 ) 2 —S x —(CH 2 ) 2 ) m —OH+(m−1) H 2 O (1)
In the case where the products were formed with the participation of dibasic carbonic acids, they would likely form a solution of dibasic carbonic acids in solid or semi-solid poly(thioether) resins. In the case where the products were formed with the participation of anhydrides of dibasic carbonic acids, the solid or semi-solid poly(thioether) resins would have a chance to react with anhydrides. This would allow the formation of a randomly-formed compound with no more than two radicals per molecule and a single ester structure for each radical. A regular poly(thioester) polymer would not be formed.
[0008] The absence in the prior art of the description of regular poly(thioesters) produced from compounds with hydroxyl groups in the β-position relative to a sulfur atom is further illustrated by Wilson in U.S. Pat. No. 5,342,724 (referred to hereafter as Wilson). Wilson describes the formation of multiple poly(thioesters) from sulfur-containing diols and dibasic carbonic acids. However, all sulfur-containing diols with hydroxyl groups in the β-position relative to the sulfur atoms were left out from the list of diols mentioned by Wilson, as the state-of-the art technology available at the time did not allow production of poly(thioesters) from such compounds.
[0009] Accordingly, there is a need in the art to develop methods of forming poly(thioesters) from sulfur-containing diols with hydroxyl groups in the β-position relative to the sulfur atoms.
SUMMARY OF THE INVENTION
[0010] The present invention provides poly(thioesters), produced from di(hydroxyethyl)polysulfides and various dibasic carbonic acids or their anhydrides, and their derivatives. The new poly(thioesters) combine properties of polyesters and polysulfides. The poly(thioesters) can be used as components in many compositions, including but not limited to adhesives, sealants, caulks, coatings, plastics, paints and elastomers.
[0011] In one embodiment, the poly(thioesters) have the formula:
R 2 —[—O—A—O—B—] n —O—A—O—R 2
wherein
each R 2 is H or R 1 -ƒ,
wherein R 1 is any bi-valenced organic radical, and ƒ is H or any reactive functional group;
each R 2 is the same or different; A is either X or Y,
wherein X is —(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —, Y is —C(O)—R 1 —C(O)—, m is at least zero, and x is between two and six;
B is either Y or X; O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur; if A is X, then B is Y; if A is Y, then B is X; and
n is at least one, except for the case when A is Y, B is X, R 1 is a dibasic carbonic acid that is a cyclic anhydride or forms a cyclic anhydride, and R 2 is H, in which case n is at least two.
[0021] In another embodiment, the poly(thioesters) have the formula:
ƒ 1 -R 1 —NH—A—O—B—[—O—A—O—B—] n —O—A—HN—R 1 -ƒ 1
wherein
A is —C(O)—R 1 —C(O)—; B is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; ƒ 1 is a hydroxyl, a primary amine group, a secondary amine group or a tertiary amine group; and O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
[0030] In yet another embodiment, the poly(thioesters) have the formula:
R 3 —C(O)—[—O—A—O—B—] n —O—A—O—C(O)—R 3
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 3 is R 1 -ƒ 2 , HN—R 1 -ƒ 3 , or HN—R 4 —NCO,
wherein ƒ 2 is a chemical structure or functional group; η 3 is a chemical structure of functional group; and R 4 is a radical that is located between two isocyanate groups of a di- or poly-isocyanate; and
O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
[0042] In an additional embodiment, the poly(thioesters) have the formula:
H—R 5 —[—O—A—O—B—] n —O—A—R 6 —OH
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 5 is H[O—CH 2 —CHR 3 ] q-k or [O—CHR 3 ] q-k ; R 6 is [O—CHR 3 —CH 2 ] q or [O—CHR 3 ] k ; if R 5 is H[O—CH 2 —CHR 3 ] q-k , then R 6 is [O—CHR 3 —CH 2 ] q ; if R 5 is [O—CHR 3 ] q-k , then R 6 is [O—CHR 3 ] k ; R 3 is either H or methyl; q is at least one; q is greater than or equal to k; and O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
[0057] The present invention further provides novel monomeric diesters. The new monomeric diesters are produced from di(hydroxyethyl)polysulfides and various monobasic carbonic acids or their anhydrides. The monomeric diesters have use as components in many compositions, including but not limited to solvents and plasticizers.
[0058] Monomeric diesters according to the present invention have the formula:
R 7 —C(O)—O—X—O—C(O)—R 7
wherein
X=—(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; R 7 is either H, or any monovalent organic radical; each R 7 is either the same or different; m is at least zero; x is at least one; and
[0064] O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
BRIEF DESCRIPTION OF THE FIGURES
[0065] The present invention together with its objectives and advantages will be understood by reading the following description in conjunction with the drawings, in which:
[0066] FIG. 1 compares IR spectra of products made according to Weihe and poly(thioesters) according to the present invention.
[0067] FIG. 2 compares IR spectra of products made according to Wilson and poly(thioesters) according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0068] The present invention provides poly(thioesters) of the formula:
R 2 —[—O—A—O—B—] n —O—A—O—R 2
wherein
R 2 is H; A is either X or Y,
wherein X is —(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —, Y is —C(O)—R 1 —C(O)—, R 1 is any bivalenced radical, m is at least zero, and x is between two and six;
B is either Y or X; O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur; if A is X, then B is Y; if A is Y, then B is X; and
n is at least one, except for the case when A is Y, B is X, and R 1 is a dibasic carbonic acid that is a cyclic anhydride or forms a cyclic anhydride, in which case n is at least two. Poly(thioesters) according to the present invention are made from reacting two main components. The first component includes di(hydroxyethyl)polysulfides, homopolymers of di(hydroxyethyl polysuflides), or a mixture of di(hydroxyethyl)polysulfides and homopolymers of di(hydroxyethyl)polysulfides. The second component includes dibasic carbonic acids and their anhydrides, or mixtures of dibasic carbonic acids and their anhydrides. The two components are reacted in the presence of a protonic acidic catalyst at a temperature of between about 80° C. and about 130° C.
[0076] Any type of protonic acidic catalyst may be used according to the present invention. Preferably, the acidic catalyst is a nonoxidizing protonic acidic catalyst. More preferably, the acidic catalyst is methanesulphonic acid. When methanesulphonic acid is used as the catalyst, the two components may be reacted at a temperature of between about 80° C. and about 180° C.
[0077] Any di(hydroxyethyl)polysulfides (or homopolymers thereof) may be used according to the present invention. Preferably, the di(hydroxyethyl)polysulfide is a di(hydroxyethyl)disulfide, a di(hydroxyethyl)trisulfide, or a di(hydroxyethyl)tetrasulfide.
[0078] Any dibasic carbonic acid or its anhydride may be used according to the present invention. Preferred dibasic carbonic acids are C 2 to C 40 saturated and unsaturated acids, substituted and unsubstituted carboxylic diacids and their anhydrides. Examples include, but are not limited to, fatty acid dimers, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, maleic, fumaric, phthalic, isophthalic, terephthalic, hemimellitic, trimellitic, trimesic, nonane-dicarbonic, decane-di-carbonic, brassylic, dithiodiacetic, dithiodipropionic, and dithiodibutyric acids and their anhydrides. In addition, mixtures of dibasic carbonic acids or their anhydrides may be used to make poly(thioesters) according to the present invention.
[0079] Though the chemical reactions shown below illustrate the interaction between di(hydroxyethyl)polysulfides and dibasic carbonic acids, any person skilled in the art can understand that similar reactions can occur when the anhydrides of dibasic carbonic acids are taken in the place of the acids themselves.
[0080] The structure, molecular weight and other properties of poly(thioesters) can be varied by a person skilled in the art within a wide range of parameters to achieve targeted properties of the final polymer. The mechanisms that allow such a variation in properties include selecting a dibasic carbonic acid with a particular structure, and properly choosing its molar ratio with di(hydroxyethyl)polysulfide or its homopolymer. These mechanisms make it possible to obtain both carboxyl- and hydroxyl-terminated poly(thioesters) with different pre-regulated lengths of polymeric chain, as well as high molecular weight poly(thioester) polymers. In particular, varying the structure of the carboxyl-carrying participants in the reaction, and the molar ratio of the reactants, allows producing poly(thioesters) with the
desired type of termination (carboxyl- and hydroxyl-terminated compounds), desired structure of repetitive polymeric segment, and desired number of such segments per molecule, i.e. molecular weight of the product.
[0084] Varying the molar ratio of components between 1:1 and 2:1 allows the production of poly(thioesters) containing the desired number of polysulfide segments and ester groups. If the molar ratio of reactants is close to 2:1, low molecular weight or oligomeric compounds are produced. If the molar ratio of reactants is close to 1:1, high molecular weight thermoplastic poly(thioesters) are produced.
[0085] Carboxyl-terminated poly(thioesters) are produced from di(hydroxyethyl)polysulfides and dibasic carbonic acids according to reaction (2), when the molar concentration of the carboxyl group in the reaction mixture is higher than the molar concentration of the hydroxyl group.
(n+1) HO—A—OH+n HO—B—OH→H[—O—A—O—B—] n —O—A—OH+(n+1) H 2 O (2)
where
A=—C(O)—R 1 —C(O)— B=—((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 — m≧0 1≦n≦25
[0090] Hydroxyl-terminated poly(thioesters) are produced according to the reaction (2),
where A=—((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —, and B=—C(O)—R 1 —C(O)—
[0092] High molecular weight poly(thioesters) are produced when the molar concentration of the hydroxyl group in the reaction mixture approximately equals the molar concentration of the carboxyl group, i.e. when in the reaction (2) n>25. In the case of high molecular weight poly(thioesters), if one component is taken in slight excess, its termination will be prevailing. High-molecular weight poly(thioesters) are thermoplastic materials that can be formed by extrusion, injection or compression molding or other similar techniques.
[0093] Poly(thioesters) according to the present invention can be used as the basis of many different compositions. Low molecular weight, or oligomeric compounds can be used as components in various adhesive, sealant, caulk, coating, paint, elastomer or other compositions. The carboxyl-terminated poly(thioester) oligomers can be chain extended and crosslinked, for example, by polyaziridines, epoxies and inorganic salts, oxides and hydroxides. The action of di- and/or polyisocyanates will convert oligomeric hydroxy-terminated poly(thioesters) into solid polyurethanes with a poly(thioester) backbones.
[0094] High molecular weight thermoplastic poly(thioesters) can be used for the production of flexible plastics, or used as an additive, which imparts targeted properties on such materials as polyethylene terephthalate, and cured unsaturated polyesters, vinyl esters, or other similar plastics.
[0000] Products Derived from Carboxyl-terminated Poly(thioesters)
[0095] Carboxyl-terminated poly(thioesters) can further react with hydroxyl-containing substances using an esterification mechanism to form compounds of the formula:
R 2 —[—O—A—O—B—] n —O—A—O—R 2
wherein
each R 2 is R 1 -ƒ,
wherein R 1 is any bi-valenced organic radical, and ƒ is H or any reactive functional group;
each R 2 is the same or different; A is —C(O)—R 1 —C(O)—; B is —(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —;
wherein m is at least zero; x is between two and six; and
O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
[0105] The esterification mechanism takes place in typical conditions for such reactions, familiar to any person skilled in the art. Reaction (3) describes such reactions
ƒ-R 1 —OH+H[—O—A—O—B—] n —O—A—OH+HO—R 1 -ƒ→ƒ-R 1 —[—O—A—O—B—] n —O—A—O—R 1 -ƒ+2 H 2 O (3)
where ƒ is a chemical structure or functional group that introduces special properties and characteristics, allowing further utilization of the newly produced compound. The structure of ƒ includes, but is not limited to hydroxyl, acrylic, methacrylic, allyl, vinyl, maleic, activated halogen, nitrile, cyclocarbonate, mercaptan and tertiary amine groups.
[0106] Examples of carriers of various ƒ functionalities include:
For hydroxyl functionality—any diol, polyol, or organic oxide; For acrylic functionality—hydroxy acrylate; For methacrylic functionality—hydroxy methacrylate; For allyl and vinyl functionalities—any compound containing both a hydroxyl group and an allyl or vinyl group, such as monovinyl ether of diethyleneglycol; For cyclocarbonate functionality—glycerol carbonate; For amine functionality—N,N′-dialkylethanolamine; For activated halogen functionality—a monoester of any glycol and chloroacetic acid; For maleic double bond functionality—maleic anhydride; For nitrile functionality—ethylenecyanohydrin; and For mercaptan functionality—mercaptoethanol.
[0117] One important example of reaction (3) is when ƒ is another hydroxyl group. Carboxyl-terminated poly(thioesters) can react with an individual polyol, or mixture of polyols, forming, depending on the poly(thioester)/polyols molar ratio, a blocked polymer, which includes poly(thioester) and polyether blocks. The molecular weight of the final product, and the proportion of the polyester/polyether segments in it can be pre-determined by the molar ratio of the reactive component. For example, if one takes 2 moles of component A and one mole of component B, the resulting product will mostly contain molecules with molecular weight equaled to twice the molecular weight of A plus one molecular weight of B. This is the lowest molecular weight product obtained by polycondensation (in this case it is not “polycondensation”, but plain condensation). In contrast, if one takes 1 mole of A and 1 mole of B, one would theoretically get one polymeric molecule with molecular weight approaching infinity. Any ratio between 1:1 and 2:1 will result in a product with a definite molecular weight, so that a person skilled in art can, by choosing the ratio of components, choose the molecular weight of the final product. It must be noted that if one of the polyols that participates in this process has functionality higher than 2, the resulting products have a degree of branching, which is pre-determined by the molar amount of the high functionality polyol.
[0118] The products of reaction (3) with compounds other than polyols can also be used in various reactive formulations cured by the radical mechanism in the cases of acrylic, methacrylic, allyl and vinyl-terminated substances, by the action of air moisture in the cases of alkoxysilane-terminated substances, by diamines in the case of cyclocarbonate-terminated materials, and by the anionic mechanism in the case of tertiary amine- terminated materials.
[0119] Carboxyl-terminated polythioesters can further react with any compound with amine group(s) through an amidation mechanism to form compounds of the formula:
ƒ 1 —R 1 —NH—A—O—B—[—O—A—O—B—] n —O—A—HN—R 1 -ƒ 1
wherein
A is —C(O)—R 1 —C(O)—; B is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; ƒ 1 is a hydroxyl, a primary amine group, a secondary amine group or a tertiary amine group; and O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
The amidation reactions take place in typical conditions for such reactions, familiar to any person skilled in the art. Reaction (4) describes such reactions.
ƒ 1 —R 1 —NH 2 +H[—O—A—O—B—] n —O—A—OH+H 2 N—R 1 -ƒ 1 →ƒ 1 -R 1 —NH—A—O—B—[—O—A—O—B—] n-1 —O—A—HN—R 1 -ƒ 1 +2 H 2 O (4)
where ƒ 1 is a hydroxyl, or a primary, secondary or tertiary amine group.
[0128] An important example of reaction (4) is when ƒ 1 is a primary or secondary amine group. Carboxyl-terminated poly(thioesters) can react with diamines, forming, depending on the poly(thioester)/diamine molar ratio, either amidoamine, or polyamide with poly(thioester) segments. If an amidoamine is desired, in order to generate a product with the least amount of undesirable byproducts, it is beneficial to react the carboxyl-terminated poly(thioester) with a diamine that has unequal reactivity of amine groups, i.e. either has one primary and one secondary amine group, such as in N-aminoethyl piperazine, or one sterically hindered amine group, such as trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1.3-pentanediamine and isophorone diamine. On the other hand, if the goal of the technological process is to produce polyamide with poly(thioester) segments, it is better to use in reaction (4) a diamine with two primary amine groups with equal reactivity.
[0129] Amidoamines produced as the result of reaction (4) can be used as is, or in a mixture with other products, for example as curing agents for epoxy coatings and adhesives formulations.
[0000] Products Derived from Hydroxyl-Terminated Poly(Thioesters)
[0130] Hydroxyl-terminated poly(thioesters) can further react with any compound typically reactive with hydroxyl groups, providing compounds with new types of functionalities. These reactions can utilize an esterification mechanism following reaction (5), an etherification mechanism following reactions (6), (7) or (8), or an isocyanate mechanism following reactions (9) or (10).
[0131] Hydroxyl-terminated poly(thioesters) can react using an esterification mechanism to form compounds of the formula:
ƒ 1 -R 1 —C(O)—[—O—A—O—B—] n —O—A—O—C(O)—R 1 -ƒ 2
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; ƒ 2 is a chemical structure or functional group; and O, H, C, and S, have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
The esterification reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art, and is described in reaction (5).
ƒ 2 -R 1 —C(O)OH+H[—O—A—O—B—] n —O—A—OH+HO(O)C—R 1 -ƒ 2 →ƒ 2 -R 1 —C(O)—[—O—A—O—B—] n —O—A—O—C(O)—R 1 -ƒ 2 +2 H 2 O (5)
where ƒ 2 is a chemical structure or functional group that introduces special properties and characteristics, allowing further utilization of the newly produced compound. The structure of ƒ 2 includes, but is not limited to hydroxyl, carboxyl, acrylic, methacrylic, allyl, vinyl, maleic, activated halogen, nitrile, cyclocarbonate, and mercaptan.
[0140] Examples of carriers of various ƒ 2 functionalities include:
For carboxyl functionality—any bi-functional carbonic acids, for example, maleic or succinic acids, or dimers of fatty acids; For hydroxyl functionality—any compound that has both a hydroxyl and carboxyl group, for example, glycolic acid; For acrylic functionality—acrylic acid; For methacrylic functionality—methacrylic acid; For active halogen functionality—chloracetic acid, or its analogs; For allyl, vinyl and other double bond functionalities—any unsaturated carbonic acid; For maleic double bond functionality—maleic acid; For nitrile functionality—monoesters of any dicarbonic acid and ethylenecyanohydrin; and For mercaptan functionality—mercaptopropyonic acid.
[0150] The case where ƒ 2 is a carboxyl (i.e. the first reagent in reaction (5) is a dibasic carbonic acid, which can be either the same or different from the dibasic carbonic acid used in the production of the second reagent in reaction (5)) is of special interest. Introduction of a dibasic acid as a second reagent in reaction (5) allows changing the molecular weight of the produced polymer by choosing the structure of R 1 and molar ratio of the participants in reaction (5). Any person skilled in the art will recognize that it is possible to produce similar reaction products if, instead of dibasic carbonic acids, the second reagent in reaction (5) is anhydrides of such acids.
[0151] The produced polyesters with poly(thioester) blocks can be used as such, or as additives to other plastics. In the case when the hydroxyl-terminated poly(thioesters) react with maleic acid, the produced segmented unsaturated polysulfide-containing polyester can be cured by all the conventional methods of curing of unsaturated polyesters, and used as a copolymerizable additive to the conventional unsaturated polyesters.
[0152] The special properties of hydroxyl groups located in the β-position to the disulfide group, as taught by the U.S. Pat. No 2,582,605, allows them to easily participate in the reactions of etherification with other alcohols, glycols and polyols, to form compounds of the formula:
R 2 —[—O—A—O—B—] n —O—A—O—R 2
wherein
each R 2 is R 1 -ƒ,
wherein R 1 is any bi-valenced organic radical, and ƒ is H or any reactive functional group;
each R 2 is the same or different; A is —(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—;
wherein m is at least zero; x is between two and six; and
[0161] O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
[0162] The etherification reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art, and is described in reaction (6).
ƒ-R 1 —OH+H[—O—A—O—B—] n —O—A—OH+HO—R 1 -ƒ→ƒ-R 1 —[—O—A—O—B—] n —O—A—O—R 1 -ƒ+2 H 2 O (6)
where ƒ is a chemical structure or functional group that introduces special properties and characteristics, allowing further utilization of the newly produced compound. The structure of ƒ may be, but is not limited to hydroxyl, acrylic, methacrylic, allyl, vinyl, maleic, activated halogen, nitrile, cyclocarbonate, mercaptan and amine groups.
[0163] Examples of carriers of various ƒ functionalities include:
For hydroxyl functionality—any diol, polyol, or organic oxide; For acrylic functionality—hydroxy acrylate; For methacrylic functionality—hydroxy methacrylate; For allyl and vinyl functionalities—any compound containing both a hydroxyl group and an allyl or vinyl group, such as monovinyl ether of diethyleneglycol; For cyclocarbonate functionality—glycerol carbonate; For amine functionality—N,N′-dialkylethanolamine; For activated halogen functionality—a monoester of any glycol and chloroacetic acid; For maleic double bond functionality—maleic anhydride; For nitrile functionality—ethylenecyanohydrin; and For mercaptan functionality—mercaptoethanol.
[0174] The case where ƒ is a hydroxyl is of a special interest, as it allows changing the molecular weight of the produced polymer by choosing the structure of R 2 and the molar ratio of the participants in the reaction (6).
[0175] Another type of etherification reaction takes place when a hydroxyl-terminated poly(thioester) is treated with either ethylene oxide, or propylene oxide, to form compounds of the formula:
H—R 5 —[—O—A—O—B—] n —O—A—R 6 —OH
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 5 is H[O—CH 2 —CHR 3 ] q-k ; R 6 is [O—CHR 3 —CH 2 ] q ; R 3 is either H or methyl; q is at least one; q is greater than or equal to k; and O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
[0188] This etherification reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art, and is described in reaction (7).
where
R 3 is either H, or methyl, q≧1, q≧k,
This reaction produces derivatives of poly(thioesters) that are useful, for example, in coatings formulations.
[0192] Another possible type of useful derivatives of hydroxyl-terminated poly(thioesters) can be produced by their reactions with formaldehyde to form polyacetals with a poly(thioester) backbone, as described in the following formula:
H—R 5 [—O—A—O—B—] n —O—A—R 6 —OH
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 5 is [O—CHR 3 ] q-k ; R 6 is [O—CHR 3 ] k ; R 3 is either H or methyl; q is at least one; q is greater than or equal to k;
and O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
[0204] This etherification reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art, and is described in reaction (8).
q R 3 CHO+H[—O—A—O—B—] n —O—A—OH→H[O—CHR 3 ] q-k —[—O—A—O—B—] n —O—A—[O—CHR 3 ] k —OH (8)
[0205] The hydroxyl groups of the hydroxyl-terminated poly(thioesters) readily participate in reactions with compounds containing isocyanate groups. Of these compounds the most important and frequently used are those made from di- and polyisocyanates, of the formula:
R 3 —C(O)—[—O—A—O—B—] n —O—A—O—C(O)—R 3
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 3 is HN—R 1 -ƒ 3 ,
wherein ƒ 3 is a chemical structure of functional group; and
O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
[0215] These compounds can be made through the isocyanate reaction shown in reaction (9). This reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art.
ƒ 3 -R 1 —NCO+H[—O—A—O—B—] n —O—A—OH+OCN—R 1 -ƒ 3 →ƒ 3 -R 1 —NH—C(O)—[—O—A—O—B—] n —O—A—O—(O)C—HN—R 1 -ƒ 3 (9)
where ƒ 3 includes, but is not limited to isocyanate, epoxy, acrylic, methacrylic, alkoxysilane, mercaptan, cyclocarbonate, tertiary amine, vinyloxy, and mixtures thereof.
[0216] A very important case is when ƒ 3 is another isocyanate group. Depending on the molar ratio between the hydroxyl-terminated poly(thioester) and isocyanate-containing compound, the reaction can either terminate in an isocyanate prepolymer with a poly(thioester) backbone (reaction (10)), or in a polyurethane with polythioester segments.
[0217] When hydroxyl-terminated poly(thioester) and isocyanate-containing compound are taken in the molar ratio close to 1:2, the reactions between them result in the formation of an isocyanate prepolymer of the formula:
R 3 —C(O)—[—O—A—O—B—] n —O—A—O—C(O)—R 3
wherein
A is —((CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; B is —C(O)—R 1 —C(O)—; R 1 is any bi-valenced organic radical; m is at least zero; n is at least one; x is between two and six; R 3 is HN—R 4 —NCO,
wherein R 4 is a radical that is located between two isocyanate groups of a di- or poly-isocyanate; and
O, H, C, S, and N have their normal meaning of oxygen, hydrogen, carbon, sulfur and nitrogen.
[0227] This reaction takes place in typical conditions for such reactions, familiar to any person skilled in the art and is described in reaction (10).
OCN—R 4 —NCO+H[—O—A—O—B—] n —O—A—OH+OCN—R 4 —NCO→OCN—R 4 —NH—C(O)—[—O—A—O—B—] n —O—A—O—(O)C—HN—R 4 —NCO (10)
where R 4 is a bivalent radical located between two isocyanate groups of a diisocyanate, preferably of a diisocyanate with unequal reactivity of isocyanate groups, such as 2,4-toluene diisocyanate, isophorone diisocyanate, or trimethylhexamethylenediisocyanate.
[0228] The isocyanate prepolymers produced by the reaction (10) can be
a) converted into polyurethanes with poly(thioester) blocks by reactions with a diol chain extender, and polyol crosslinkers; b) converted into poly(urea-urethanes) with poly(thioester) blocks by reactions with aromatic diamine chain extenders and crosslinkers; c) converted into reactive and non-reactive functional oligomers with poly(thioester) backbones by the methods described in the U.S. Pat. No 6,369,188. The functionality of the produced urethane-functional polysulfide-containing compounds includes, but is not limited to epoxy, acrylic, methacrylic, alkoxysilane, mercaptan, cyclocarbonate, tertiary amine, vinyloxy, and mixtures thereof.
When hydroxyl-terminated poly(thioester) and isocyanate-containing compound are taken in close-to-equimolar amounts, the reactions between them result in the formation of a polyurethane with polythioester segments. These polyurethanes have improved properties due to the presence of polysulfide blocks.
Production of Monomeric (Polythio)Diesters
[0232] The present invention also provides monomeric (polythio)diesters of the formula:
R 7 —C(O)—O—X—O—C(O)—R 7
wherein
X=—(—(CH 2 ) 2 —S x —(CH 2 ) 2 —O—) m —(CH 2 ) 2 —S x —(CH 2 ) 2 —; R 7 is either H, or any monovalent organic radical; the two R 7 s are either the same or different;
m is at least zero;
x is at least one; and
[0238] O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon, and sulfur.
[0239] In order to produce these products, dihydroxyethylpolysulfide and/or its homopolymers react with individual mono-basic carbonic acids, such as acetic, chloroacetic, propyonic, fatty, etc. acids, their anhydrides, or mixtures of such acids or anhydrides under conditions similar to those described above for dibasic acids. The (polythio)diesters are produced according to reaction (11)
R 7 —C(O)OH+H[—O—A—O—B—] n —O—A—OH+HO(O)C—R 7 →R 7 —C(O)[—O—A—O—B—] n —O—A—O(O)C—R 7 (11)
where R 7 is H or any monovalent organic acid. In one embodiment, R 7 is a monobasic carboxylic acid having between two and nineteen carbons.
[0240] The produces low viscosity polysulfide-containing diesters that are very effective solvents and plasticizers for a wide variety of polymeric products.
EXAMPLES
[0241] The majority of experimental work on the products described in this patent was based on a commercially-available DiHEDS, a product of the Chevron Phillips Chemicals LP, which contains approximately 95-97% of di(hydroxyethyl)disulfide, and 3-5% of the higher molecular weight di(hydroxyethyl)trisulfide and other, higher molecular weight di(hydroxyethyl)polysulfides. However, in regards to the subject of this invention, all di(hydroxyethyl)polysulfides behave similarly.
[0242] Di(hydroxyethyl)polysulfides with sulfidity higher than that of DiHEDS, which were used to create some of the poly(thioesters) that are the subject of this invention, were obtained by dissolving elemental sulfur in DiHEDS at 115-120° C.
[0243] The homopolymers of di(hydroxyethyl)polysulfides (polythioethers) that were used to create some of the poly(thioesters) that are the subject of this invention were obtained by polyetherification of DiHEDS (Reaction 1) in the presence of acidic catalysts (preferably phosphoric acid) at 140-180° C.
[0244] Any person skilled in the art will recognize that most of the processes described in the present invention can take place not only at 80-130° C., in the presence of acidic catalysts, but also outside of this preferred range of temperatures. However, at temperatures below 80° C. the reaction rate slows down to a degree that the chemical production process becomes impractical, and at temperatures above 130° C. the input of the reaction of homopolycondensation of di(hydroxyethyl)polysulfides (i.e. formation of poly(thioethers)) becomes more and more pronounced, and the determination of the chemical structure of the products formed at higher temperatures becomes more and more problematic. An exception is when the reaction is conducted with methanesulphonic acid as the catalyst. In this case, the homopolycondensation reaction is minimal up to about 180° C.
Example 1
Production of Carboxyl-terminated Poly(thioester) from Di(hydroxyethyl)disulfide and Fatty Acid Dimer
[0245] 27 g of di(hydroxyethyl)disulfide (DiHEDS, produced by Chevron Phillips Chemicals LP, Regular grade) and 200 g fatty acid dimer (CAS # 61788-89-4, Pripol-1013 from Uniqema, ICI Company) were combined in a jacketed reaction vessel and agitated. The molar ratio of components was 1:2.
[0246] 0.2 g of 98% p-toluenesulfonic acid monohydrate (CAS # 6192-52-5, obtained from Sigma-Aldrich) was used as a catalyst. The esterification reaction proceeded at 125-130° C. (260-270° F.) for 3-4 hours with constant mixing. 10 mm Hg vacuum was applied in order to facilitate the removal of water from the reaction mixture. For process control during this stage the concentration of carboxyl groups was monitored (ASTM D 465).
[0247] The process ended when the concentration of acid approached the calculated acid number of the carboxyl-terminated polythioester, and no further distillate was formed. The acid number of the produced material equaled 83.6 mg KOH/g, while the projected acid number was 83.58. The material produced was a brown liquid with 6000 cPs viscosity.
Example 2
Production of Hydroxyl-terminated Poly(thioester) from Di(hydroxyethyl)disulfide and Succinic Anhydride
[0248] 308 g di(hydroxyethyl)disulfide (DiHEDS, CPChem L.L.C., Water-free grade) and 100 g of succinic anhydride (Sigma-Aldrich # 108-30-5) (molar ratio 1:2) were combined in a reaction vessel and heated to 120° C., followed by the addition of 4 g of catalyst, methanesulfonic acid (CAS # 75-75-2, Sigma-Aldrich). The system was mixed for 1 hr under 10 mm Hg vacuum and mixing continued at 120° C. until no more water was distilled from the reaction mixture. For process control the concentration of carboxyl groups was monitored by ASTM D 465. At the end of the process the residual concentration of carboxyl groups was negligible. The produced substance was a clear yellowish viscous (2000 cPs) liquid, which later crystallized into a white hard waxy material.
Example 3
Production of Hydroxyl-terminated Poly(thioester) from Di(hydroxyethyl)disulfide and Adipic Acid
[0249] 600 g di(hydroxyethyl)disulfide (DiHEDS, CP Chem L.L.C. Water-free grade) and 474 g of adipic acid (Adipure by DuPont, CAS # 124-04-9) (molar ratio 6:5) were combined in a reaction vessel and 3.13 g of methanesulfonic acid (CAS number 75-75-2, Sigma-Aldrich) added. The mixture was heated to 120° C. with mixing for 1 hr, under 10 mm Hg vacuum and reaction maintained at 120° C. until no more water was distilled from the reaction mixture. For process control the concentration of carboxyl groups was monitored by ASTM D 465. At the end of the process the residual concentration of carboxyl groups was negligible. The produced substance was a clear yellowish viscous (˜3000 cPs) liquid, which later crystallized into a white hard waxy material.
Example 4
Production of Hydroxyl-terminated Poly(thioester) from Di(hydroxyethyl)disulfide and Maleic Anhydride
[0250] 1900 g di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-free grade) and 907 g of maleic anhydride (Alfa Aesar, CAS # 108-31-6) (molar ratio 4:3) were combined in a reaction vessel. The mixture was heated to 57° C. with mixing for 1 hr, under Argon, until maleic anhydride dissolved. The reaction mixture was intensely agitated for 40 minutes without external heat source, and the temperature has ridden to 80° C. 14 g of methanesulfonic acid (Chevron Phillips Chemicals, CAS number 75-75-2,) were added and the mixture was heated to 90° C. for 10 minutes. Argon was turned off when the condensation products were observed on the walls of the reactor, and 10 mm Hg vacuum was applied for 1 hour at 80° C., until no more water was distilled from the reaction mixture. For process control the concentration of carboxyl groups was monitored by FTIR. At the end of the process the residual concentration of carboxyl groups was negligible (the peaks 1785 and 1850 cm −1 attributed to the maleic anhydride and 1705 cm −1 attributed to the carboxyl's carbonyl group have disappeared). The produced substance was a clear not very viscous (˜800 cPs) liquid.
[0251] The spectrum of this product is shown in FIG. 1 alongside with a spectrum of a material produced from the same raw materials under conditions described by Weihe (U.S. Pat. No. 2,221,418, Example 4—equimolar amounts, 5 hours @140° C.), which is an extremely viscous (>500,000 cPs) dark brown balsam. These spectra clearly demonstrate that the compositions of matter generated from the same raw materials under different conditions are quite dissimilar. Similar spectral differences are present in the products of interaction of succinic anhydride and di(hydroxyethyl)disulfide when they were obtained under conditions described by Smith (180-220° F. in the presence of triethylamine).
Example 5
Production of Hydroxyl-terminated Poly(thioester) from Di(hydroxyethyl)disulfide, Succinic Anhydride and Dimethylolpropionic Acid
[0252] 308 g di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-free grade), 400 g of succinic anhydride, and 402 g of dimethylolpropionic acid (DMPA, GEO Specialty Chemicals, CAS # 4767-03-7) (molar ratio 2:4:3) were combined and heated to 130° C. with mixing for 2.5 hr, under 10 mm Hg vacuum. Under these conditions, all hydroxyls of DiHEDS have reacted with the carboxyl groups of the succinic acid, forming a carboxyl-terminated polythioester dissolved in the residual dimethylolpropionic and succinic acids.
[0253] Then the temperature was increased to 180° C., 1% of methanesulphonic acid catalyst was added to the reaction mixture, and mixing continued at 180° C. until no more water was distilled from the reaction mixture. At this stage of the process, dimethylolpropionic acid, acting as a diol, has reacted with the residual succinic acid and carboxyl-terminated polythioester, forming an oligomeric resin with a polythioester backbone that is terminated with two hydroxyl and three carboxyl groups.
[0254] The concentration of carboxyl groups was monitored by ASTM D 465. At the end of the process the residual concentration of carboxyl groups was equal to the concentration of the DMPA carboxyls. The produced material was an amber highly viscous (200,000 cPs) liquid.
EXAMPLE 6
Production of Polysulfide-containing Amidoamine from the Carboxyl-terminated Poly(thioester)
[0255] To the product from the Example 1 without isolation or cooling was added N-aminoethylpiperazine (AEP, CAS # 140-31-8, Huntsman Corp. or Air Products and Chemicals, Inc) in the amount of 1.05 mol AEP per one mol of carboxyl. Assuming the targeted acid number of 83.58 mg KOH/g was reached in the first stage, the ratio is 20.4 parts of AEP per 100 parts of produced polyester. A typical second stage reaction time is 2-3 hours at 155-160° C. under atmospheric pressure. After reaching the targeted amine number, which for this product is 71.2 mg KOH/g, the reactor pressure was reduced to at least 10 mm Hg. to distill off the water produced in the second stage reaction. The temperature during the vacuum period is maintained at 155-160° C. For process control in this stage the amine number is monitored by ASTM D 2073. The process ends when the amine number approaches the targeted amine number and no more water was being removed under vacuum. The produced material was a brown semi-solid substance with a melting range 40-50° C. that was soluble in conventional diamines.
Example 7
Production of Polysulfide-containing Isocyanate Prepolymer from Hydroxyl-terminated Poly(thioester)
[0256] 400 g of poly(thioester) from Example 2 were melted at 60° C. and mixed with 15 g 3ST 25 Zeochem Purmol Zeolite powder (produced by Zeochem, Louisville, Ky.) to remove traces of water. The mixture was later combined in a reaction vessel with 234 g of isophorone diisocyanate (Vestanat® IPDI, Degussa Corp., CAS # 4098-71-9) (molar ratio 1:2.05). The reaction mixture was heated to 90° C. and agitated for 3 hrs under argon flow. The concentration of isocyanate groups was monitored by ASTM D 2572-97. At the end of the process the concentration of isocyanate groups was 2.4 N, which is equal to half of the initial concentration of isocyanate groups. The produced material was a whitish opaque very viscous (150,000 cPs) liquid.
Example 8
Production of Polysulfide-containing Isocyanate Prepolymer from Hydroxyl-terminated Poly(thioester)
[0257] 445 g of poly(thioester) from Example 3 were melted at 60° C. and mixed with 15 g 3ST Zeochem Purmol Zeolite powder (produced by Zeochem, Louisville, Ky.) to remove traces of water. The produced mixture was combined in a reaction vessel with 372 g of methylene-bis(cyclohexylisocyanate) (Desmodur W, Bayer Corp., CAS # 5124-30-1) and heated to 90° C. and stirred for 1 hr, under argon flow.
[0258] 95.2 g of dimethylolpropionic acid (DMPA, GEO Specialty Chemicals, CAS # 4767-03-7), 200 g of N-methyl pyrrolidinone (NMP BASF, CAS # 872-50-4) and 36 g of triethylamine (TEA, J T Baker, CAS #121-44-8) were added to the reaction mixture. The temperature was reduced to 70° C. and the reaction mixture was mixed at this 5 temperature for 1 hour under argon. The concentration of isocyanate groups was monitored by ASTM D 2572-97. At the end of the process the concentration of isocyanate groups was 0.68 N, which exactly equaled the calculated concentration of terminal isocyanate groups in the produced prepolymer with pendant carboxyl groups inhibited from reaction by the triethylamine. The produced material was a whitish viscous liquid with viscosity of approximately 70,000 cPs.
Example 9
Production of Hydroxyl-terminated Poly(thioester) from Di(hydroxyethyl)polysulfide and Adipic Acid
[0259] 504 g of di(hydroxyethyl)polysulfide (obtained by dissolving 1 mol of sulfur in 1 mol of DiHEDS) and 313 g of adipic acid (Adipure by DuPont, CAS # 124-04-9) (molar ratio 5:4) were combined in a reaction vessel and 3 g of 70% solution of methanesulfonic acid (produced by Chevron Phillips Chemical) were added to the reaction mixture. The mixture was heated to 120° C. with mixing for 1 hr, under 10 mm Hg vacuum and reaction maintained at 120° C. until no more water was distilled from the reaction mixture. For process control the concentration of carboxyl groups was monitored by ASTM D 465. At the end of the process the residual concentration of carboxyl groups was negligible. The produced substance was a brown viscous liquid, which did not crystallize. The spectrum of this material is shown in FIG. 2 .
[0260] By way of comparison, di(hydroxyethyl)disulfide (a compound excluded by Wilson from the list of sulfur-containing diols) and adipic acid were combined under conditions described by Wilson (180° C., nitrogen atmosphere followed by vacuum, lead acetate/antimony oxide catalyst). The spectrum of the resulting materials is shown in FIG. 2 , alongside with a spectrum of the inventive product. The resulting polymers proved to have absolutely dissimilar structures.
Example 10
Production of the Maleic-terminated Polythioester with Di(hydroxyethyl)polysulfide/Adipic Acid Polyester Backbone
[0261] 673 g of poly(thioester) from Example 9 were combined with 105 g of maleic anhydride. and heated to 90° C. with stirring under argon, until FTIR spectrum has shown complete disappearance of the peaks 1785 and 1850 cm −1 attributed to the anhydride group of maleic anhydride.
[0262] The produced material was a whitish viscous liquid with viscosity of approximately 10,000 cPs, which demonstrated the typical reactions of maleic-terminated oligomers.
Example 11
Production of Carboxyl-terminated Poly(thioester) from Di(hydroxyethyl)polysulfide and Adipic Acid
[0263] 452 g of di(hydroxyethyl)polysulfide (obtained by dissolving 1 mol of sulfur in 1 mol of DiHEDS) and 532 g of adipic acid (Adipure by DuPont, CAS # 124-04-9) (molar ratio 2:3) were combined in a reaction vessel and 5.3 g of 70% solution of methanesulfonic acid (produced by Chevron Phillips Chemical) were added to the reaction mixture. The mixture was heated to 115° C. with mixing for 1 hr, under 10 mm Hg vacuum and reaction maintained at 115° C. until no more water was distilled from the reaction mixture. For process control the concentration of carboxyl groups was monitored by ASTM D 465. At the end of the process the molar concentration of carboxyl groups was 2.8, while theoretically it should be 2.71. The produced substance was a brown viscous liquid, which did not crystallize.
Example 12
Production of the Mercaptan-terminated Polythioester with Di(hydroxyethyl)polysulfide/Adipic Acid Polyester Backbone
[0264] 900 g of poly(thioester) from Example 11 were combined with 190 g of bis-mercaptoethanol (BME, produced by Chevron Phillips Chemical). Additional 2.3 g of 70% solution of methanesulfonic acid (produced by Chevron Phillips Chemical) were added to the reaction mixture, which was heated to 90° C. with stirring under argon for 1 hour. Then 10 mm Hg vacuum was applied and reaction maintained at 90° C. until no more distillate was produced, and until FTIR spectrum has shown complete disappearance of the 1705 cm −1 peak, which is attributed to the carboxyl's carbonyl group.
[0265] The produced material was a brow viscous liquid with viscosity of approximately 10,000 cPs, which demonstrated the typical reactions of mercaptan-terminated oligomers.
Example 13
Production of a Monomeric Diester from Di(hydroxyethyl)disulfide and Acetic Acid
[0266] 154 g di(hydroxyethyl)disulfide (DiHEDS CPChem L.L.C., Water-free grade) and 120 g of glacial acetic acid (molar ratio 1:2) were combined in a reaction vessel and heated to 75° C., followed by the addition of 0.85 g of catalyst, methanesulfonic acid (CAS number 75-75-2, Sigma-Aldrich). The system was heating to 90° C. and mixed for 1 hr. The temperature was raised to 103° C. and 10 mm Hg vacuum was applied. The system cooled down to 75° C., and extra 50 g of glacial acetic acid were added. The reaction mixture was reheated, and vacuum was applied. This operation (including the addition of extra portions of acetic acid) was repeated 3 times, until changes in the FTIR spectrum after each reheating cycle became unnoticeable. The produced substance was a clear low viscosity liquid with specific gravity 1.21-1.22, which was a very effective plasticizer for a wide variety of halogenated polymers.
[0267] It is evident from the above results that the subject compounds can be readily prepared in good yield under convenient conditions. The subject monomers provide desirable properties to a large number of products enhancing the properties of products prepared from conventional monomers. By replacing all or a portion of diols or dibasic acids used in making condensation polymers, the resulting products have improved physical and chemical characteristics. By modifying the subject monomers with addition polymerizable monomers, the properties of the resulting polymeric product are similarly enhanced.
[0268] As one of ordinary skill in the art will appreciate, various changes, substitutions, and alterations could be made or otherwise implemented without departing from the principles of the present invention. Accordingly, the scope of the invention should be determined by the following claims and their legal equivalents. | The present invention provides poly(thioesters) and monomeric diesters, produced from di(hydroxyethyl)polysulfides and various mono- and di-basic carbonic acids or their anhydrides, and their derivatives. The new compounds combine properties of polyesters and polysulfides. The poly(thioesters) can be used as components in many compositions, including but not limited to adhesives, sealants, caulks, coatings, plastics, paints and elastomers. The monomeric diesters find use in compositions such as solvents and plasticizers. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/947,595, filed Jul. 2, 2007, which is incorporated herein by reference.
BACKGROUND
A rope is a large stout cord of strands of fibers or wire twisted or braided together for strength. The making of rope dates to ancient times. Originally, strands of fibers were twisted by hand, until the Egyptians developed tools to make ropes from papyrus fibers and leather strips. Hemp, used in Asia and adopted in Europe, became the chosen material for ropes until recently, when it was replaced by Manila hemp, an unrelated plant from the Philippines. Synthetic fibers supplanted Manila hemp as the prime rope material in the 1950s.
Working with ropes is a vital part of many industries and particularly essential to seafaring. Nineteenth century sailors knew and used hundreds of knots, some simple and others exceedingly complicated, each for a specific purpose. Accidents are common on ships, such as when a seaman falls into the water—for which an English word “overboard” was coined to succinctly capture the situation in the twelfth century. In cold waters, as the victim is experiencing hypothermia, his hands and fingers lose dexterity and he cannot hold on to a thin rescue rope that is thrown towards him. Larger diameter ropes, however, are too heavy to throw to a long distance where the victim may be located in the waters.
SUMMARY
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
In accordance with various aspects of the invention, an article of manufacture form of the invention includes an inflatable rope, which comprises a bladder formed from plastic to receive, transport, and contain an inflatable medium. The inflatable rope also comprises a sheath formed from a weave of man-made fibers that expands or compresses. The inflatable rope further comprises a fitted, perforated plastic layer into which the bladder and the sheath are rolled or folded so as to allow the inflatable rope to be wound into a spool housed in a drum.
In accordance with another aspect of the invention, a system form of the invention includes a system for hurling an inflatable rope, which comprises the inflatable rope having three layers including a bladder, a phosphorescent sheath, and a fitted, perforated plastic layer and being wound into a spool. The system also comprises a drum for storing the spool and for containing a source of radiation to irradiate the phosphorescent sheath through the fitted, perforated plastic layer. The system further comprises a device that propels a distal end and a portion of the inflatable rope toward a person in water.
In accordance with another aspect form of the invention, a method form of the invention includes a method for containing a chemical spill, which comprises unwinding a spool of a first inflatable rope made from an ultra high molecular weight polyethylene to encompass an area of the chemical spill in water. The method also comprises pumping a nostril of the first inflatable rope with an inflatable medium while a curtain attached to the bottom of the first inflatable rope unfurls toward the water. The method further comprises turning on light emitting diodes on the top of the first inflatable rope to aid in visibility of the location of the first inflatable rope and the chemical spill.
DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a pictorial diagram illustrating an exemplary application of an inflatable rope, according to one embodiment of the present invention;
FIG. 2 is a pictorial diagram illustrating an exemplary application of an inflatable rope, according to one embodiment of the present invention;
FIG. 3 is a perspective diagram illustrating exemplary layers of an inflatable rope, according to one embodiment of the present invention;
FIG. 4 is a perspective diagram illustrating exemplary layers of an inflatable rope, according to one embodiment of the present invention;
FIG. 5 is a perspective diagram illustrating an exemplary inflated inflatable rope, according to one embodiment of the present invention;
FIG. 6 is a perspective diagram illustrating exemplary layers of an inflatable rope including an exemplary threaded nostril;
FIG. 7 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
FIG. 8 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
FIG. 9 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
FIG. 10 is a pictorial diagram of an exemplary inflatable rope with an exemplary lanyard, according to one embodiment of the present invention;
FIG. 11 is a pictorial diagram of an exemplary containment boom, according to one embodiment of the present invention; and
FIG. 12 is a pictorial diagram of exemplary containment booms, according to one embodiment of the present invention.
DETAILED DESCRIPTION
Unpredictability is one among many risks facing those at seas and even on minor waterways. Ocean marine insurance, one of the oldest forms of insurance, recognizes the need for mitigating against loss from the dangers experienced by boats, cargo, and passengers. One of those dangers is illustrated by FIG. 1 in which a person 102 is overboard. A boat 100 includes a vehicle from which the person 102 fell off, or a ship from a rescuing organization, such as the Coast Guard. When the person 102 is overboard and he wears a radio-frequency tag, a radio-frequency receiver on the boat 100 will annunciate an alert signal to others on board the boat 100 .
On the boat 100 are several deckhands. Generally, it will take too long to steer the boat 100 to orient the boat to rescue the person 102 . A quicker rescuing operation is needed. In the case illustrated in FIG. 1 , some of the deckhands recognize that the person 102 is in the water and one of the deckhands has picked up a device 104 that hurls a projectile, which can propel an inflatable rope 108 towards the person 102 . In one embodiment, the inflatable rope 108 can be hurled up to about 200 feet from the boat 100 . Any suitable device that hurls a projectile, such as the inflatable rope 108 , can be used. One suitable device includes a grapnel launcher manufactured by H. Henriksen Mekaniske Verksted A/S, but any suitable devices can be used.
The device 104 is fitted with a drum 106 in which the inflatable rope 108 is stored in a spool like fashion. The inflatable rope 108 has a distal end and a proximal end. The spool is wound into a cylinder-like shape so that the distal end protrudes from the center of the spool at one end of the spool and the proximal end protrudes from the center of the spool at the other end of the cylinder. The spool is placed inside a drum 106 , which is coupled to the device 104 , so as to allow the device 104 to propel, at first, the distal end of the inflatable rope, and after which, a portion of the inflatable rope connected to the distal end toward the person 102 .
The inflatable rope 108 as hurled from the device 104 is manufactured so that it is initially small in diameter so as to easily cut through the air to quickly reach the person 102 . Its small shape is maintained by a small diameter, elongated plastic bag that has a perforation to allow the inflatable rope 108 to tear the small diameter, elongated plastic bag, and emerge when it is inflated. When a desired portion of the inflatable rope 108 has been propelled toward the person 102 , the inflatable rope 108 is inflated using its proximal end 108 a. FIG. 1 shows a deckhand holding and coupling the proximal end 108 a of the inflatable rope 108 to a source of air (not shown) or other medium (gas, solid, or liquid) to inflate the inflatable rope 108 .
In one embodiment, the proximal end 108 a can be coupled to a wench-like mechanism to pull the person 102 toward the boat 100 . In another embodiment, the device 104 can include a wench that retrieves the hurled portions of the inflatable rope 108 and thereby pulls the person 102 to safety. FIG. 2 illustrates the inflated inflatable rope allowing the person 102 to grab hold for the deckhands to pull the person 102 to safety. In one embodiment, the inflatable rope 108 can be inflated so that it expands to about 150% of its original, uninflated size.
The inflatable rope 108 , in its natural, uncompressed, and uninflated form, includes at least two layers 108 b, 108 c as illustrated in FIG. 3 . The layer 108 b is a bladder formed from a suitable material into which a gas, such as air, can be pumped to cause the layer 108 b to expand into a suitable diameter, such as 3 inches. Any suitable material may be used to form the bladder of the layer 108 b, such as plastic, as long as it allows the bladder to receive, transport, and contain an inflatable medium. The layer 108 c is a sheath, which is woven from man-made fibers, such as polyethylene terephthalate, a thermoplastic polymer resin in the polyester family. The weave of the sheath of the layer 108 c provides the tensile strength of the inflatable rope 108 while the bladder of the layer 108 b allows the inflatable rope 108 to be inflatable or compressible. Any suitable weave pattern can be used as long as it allows the sheath of the layer 108 c to expand with the expansion of the bladder of the layer 108 b.
Both the sheath of the layer 108 c and the bladder of the layer 108 b can lay flat allowing both layers 108 b, 108 c to be rolled or undulated to form multiple compressed folds. The shape of the layers 108 b, 108 c formed after being rolled or folded can be maintained by slipping a fitted, perforated plastic layer 108 d over the rolled or folded layers 108 b, 108 c. The inflatable rope 108 with the three layers 108 b, 108 c, and 108 d can be wound into a spool, a center of which at one end protrudes the distal end of the inflatable rope 108 and at the other end protrudes the proximal end. As previously discussed, the distal end of the inflatable rope 108 along with a portion of the inflatable rope 108 will be hurled to the person 102 while the proximal end of the inflatable rope 108 remains behind to be tethered to the boat 100 and is coupled to a source of air or other medium to inflate the inflatable rope 108 .
As the inflatable rope 108 is pumped with air or another suitable medium, the layer 108 d is torn off along the perforated path allowing the sheath of the layer 108 c and the bladder of the layer 108 b to emerge. See FIG. 5 . The inflated inflatable rope 108 floats and allows a portion of the person 102 to be lifted from the water. A threaded nostril 110 , as shown in FIG. 6 , allows the proximal end of the inflatable rope 108 to be coupled to a source of air. In one embodiment, the sheath of the layer 108 c is painted with a phosphorescent paint, which allows the sheath to absorb radiation at one wavelength followed by a reradiation at another wavelength in a visible color, such as yellow or orange, that continues for a noticeable amount of time after the incident radiation stops. In this embodiment, the spool containing the phosphorescent inflatable rope also contains a source of incident radiation in the drum 106 to charge, periodically and continuously, the phosphorescent paint on the sheath of the layer 108 c.
The sheath of the layer 108 c, in one embodiment, is solid and in a color, such as yellow or orange. In another embodiment, as illustrated in FIG. 7 , a v-shape pattern is periodically repeated on the sheath of the layer 108 c. The v-shape pattern may be comprised of a solid color different from the color comprising the remaining portions of the sheath of the layer 108 c. In a further embodiment, the remaining portions of the sheath of the layer 108 c include the word “exit,” which is repeated along the two spines of the v-shape pattern. The v-shape pattern, alone or in combination, with the word “exit” allow the inflatable rope 108 to be used by firemen to deliver water to quench a fire in a direction opposite to the apexes of the v-shape pattern and at the same time guide people, who follow the direction pointed by the apexes of the v-shape pattern away from the fire to safety.
A candy stripe pattern is available, in an additional embodiment, to mark the sheath of the layer 108 c. See FIG. 8 . For some population of people, the candy stripe pattern may be more visually arresting to the eyes. In an added embodiment, the portions of the sheath of the layer 108 c that lack the candy stripe pattern may include the word “caution” periodically repeated. FIG. 9 illustrates another stripe pattern, in as yet another embodiment, that periodically repeats. Many other patterns are possible as long as they functionally alert people to a situation that requires caution.
The inflated inflatable rope 108 is shown in FIG. 10 . The nostril 110 is shown at the proximal end of the inflated inflatable rope 108 . As previously discussed, the nostril 110 allows air or another medium to be delivered into the bladder of the inflatable rope 108 so as to inflate it. A distal end of a lanyard 1002 is attached to the distal end of the inflatable rope 108 . In one embodiment, the lanyard 1002 is manufactured from the same material used to manufacturer the sheath of the layer 108 c. Preferably, the lanyard 1002 has a similar or longer length than the inflatable rope 108 . When the inflatable rope 108 is hurled to the person 102 , in a further embodiment, the distal ends of the inflatable rope 108 and the lanyard 1002 are propelled together toward the person 102 . A proximal end of the lanyard 1002 is tethered to the boat 100 so as to allow the inflatable rope 108 to be manipulated directionally by the lanyard 1002 . More than one lanyard can be coupled to the inflatable rope 108 to provide different controlling options.
An inflatable rope 1100 can be used as a containment boom, which is a temporary floating barrier used to contain an oil or chemical spill. The inflatable rope 1100 includes elements similar to those of the inflatable rope 108 , such as a bladder, a sheath, and a nostril 1110 . Preferably the sheath of the inflatable rope 1100 is made from an ultra high molecular weight polyethylene, which is highly resistant to corrosive chemicals. The inflatable rope 1100 includes a curtain 1104 , which is unfurled when the inflatable rope 1100 is inflated with air or another medium through the nostril 1110 . The curtain 1104 preferably is created from the ultra high molecular weight polyethylene used for the sheath of the inflatable rope 1100 . In one embodiment, the inflatable rope 1100 is wound into a spool and is stored in a 55 gallon drum or similar canister. The curtain 1104 has a length similar to the length of the inflatable rope 1100 . The top of the curtain 1104 is attached to the bottom of the inflatable rope 1100 using a suitable fastening means, such as Velcro. The bottom 1104 a of the curtain 1104 is preferably weighted so as to ease the process of unfurling and to maintain the drape of the curtain 1104 in the vertical direction to contain the spill. A number of light emitting diodes 1102 are periodically placed along the inflatable rope 1100 to allow visibility at night. In an embodiment, the light emitting diodes 1102 are placed between the bladder and the sheath.
A system 1200 of inflatable ropes 1100 a, 1100 b expand an area within which a spill can be contained. Both the inflatable ropes 1100 a, 1100 b include nostrils 1100 a, 1100 b, adapted to receive air or another medium to inflate the inflatable ropes 1100 a, 1110 b. Check valves (not shown) are provided at ends 1202 , 1204 , to regulate air or another medium that inflates the inflatable ropes 1100 a, 1100 b, and are adapted to close when the pressure in both inflatable ropes 1100 a, 1100 b is approximately equal. Light emitting diodes 1102 are provided on the top of the inflatable ropes 1100 a, 1100 b to provide visibility at night. The system 1200 allows each inflatable rope to be a component that can be interfaced together to expand to contain an enlargement of a spill.
While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention. | An inflatable rope comprises three layers, a bladder, a sheath, and a fitted, perforated plastic bag to keep the inflatable rope in a compressed form. The compressed form can be hurled through the air at great distance to a person overboard. The inflatable rope can be inflated to a size that eases the ability of the person, who has lost dexterity in frigid water, to hold on to it for rescuing. | 3 |
FIELD OF THE INVENTION
This invention relates to a bracket useful to form a free-standing structure and to a free-standing structure including the bracket.
DESCRIPTION OF PRIOR ART
Formation of scaffolding as an aid in construction work generally and in cleaning is, of course, well known. Generally speaking the scaffolding has either been relatively complex in structure or, at least, difficult to put up, particularly in large industrial scaffolding such as would be used in the refinishing of a building surface. However, even with small buildings, for example, houses, scaffolding structures have been relatively complex and have involved in many instances the mounting of the scaffolding on a wall of the house. Inside the house it is generally preferred to use step-ladders rather than to use scaffolding that must be located on the wall of a room. However, the use of scaffolding, which permits the use of a platform, is clearly desirable in internal work in a house since far greater areas can be dealt with without adjustments such as having to move a step ladder.
SUMMARY OF THE INVENTION
The present invention seeks to provide brackets useful to form a free-standing structure on legs and to a free-standing structure having legs and using the above brackets.
Accordingly, in a first aspect the present invention is a bracket useful to form a free standing structure on legs, the bracket comprising a cross piece to carry a platform; means defining a pathway to receive a leg at each end of the cross piece; a sleeve pivotally mounted on the pathway and extending, when the bracket is in its useful position, around a leg; and a lever extending from the sleeve to permit pivoting of the sleeve to grip a leg positioned in said pathway and to permit the bracket to be moved up and down the leg.
Preferably the above bracket includes upstanding members at each end of the cross piece to maintain a platform in position on the cross piece. The platform would, of course, extend to another bracket, spaced from the first bracket, to provide a free-standing scaffold or structure.
The means defining the pathway preferably comprises an open-faced channel having a back and sides and able to receive a leg of substantially rectangular cross sections. The sleeve is pivotally mounted on the back of the channel and extends around and across the open face to contact the leg. An advantage of the rectangular cross section is that a simple piece of two-by-four lumber can be used to form the legs and such lumber is freely available on any building site.
It is preferable that the channels extend outwardly and downwardly from the cross piece in order to provide a stable structure and to assist engagement by the sleeve. Furthermore, the cross pieces should be inclined relative to the pathways so the legs extend longitudinally and outwardly downwardly when a platform is in position. This again provides a more stable structure and assists engagement by the sleeve.
In one aspect of the above invention the pathway may include a runner to abut an edge of a leg when the bracket is in its useful position supporting a platform. There are spaced, fixed sleeves extending from the runner around the pathway and the pivotal sleeve is pivotally mounted between the fixed sleeves. Such a device desirably has a recess adjacent each end of the cross piece to receive a bracing member. The bracing member extends from the first bracket to another, like bracket spaced from the first bracket. The bracing member is substantially perpendicular to the cross piece. This embodiment is of advantage particularly in larger structures, for example, to be used outside. The recess may be provided with a clamp to hold a bracing member in place.
The invention also includes a free standing structure having legs adjacent to each corner and carrying a platform. The legs are carried by brackets that support the legs in position, one bracket at each end of the platform.
BRIEF DESCRIPTION OF THE DRAWINGS
Aspects of the invention are illustrated, merely by way of example, in the accompanying drawings, in which:
FIG. 1 is a view of a free-standing structure according to one aspect of the present invention;
FIG. 2 is a perspective view of a bracket used in the free-standing structure of FIG. 1; and
FIG. 3 illustrates a further aspect of the invention;
FIG. 4 is an enlarged view of a portion of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1 and 2, FIG. 1 shows a free-standing structure 2 having legs 4 adjacent each corner and carrying a platform 6. There are brackets 8 supporting the legs 4 in position, one bracket 8 at each end of the platform 6. As illustrated in FIGS. 1 and 2 each bracket 8 comprises a cross piece 10 to carry the platform 6. Cross piece 10 comprises spaced bars 12 in FIG. 2. There are means defining a pathway to receive a leg 4 at each end of the cross piece 10. In FIGS. 1 and 2 the means comprises an open channel member 14 having a back 16 and sides 18 and able to receive a leg 4 of substantially rectangular cross section, for example, a piece of common two-by-four lumber. There is a sleeve 20 in the form of a substantially U-shaped bracket mounted on the back 16 of the open-faced channel 14 to extend, as illustrated in FIG. 1, around a leg 4. A lever 22 extends from the sleeve 20 to permit pivoting of the sleeve 20 to grip a leg 4 in position in said pathway and, as described later, to permit the bracket 8 to be moved up and down a leg 4.
There are upstanding members 24 at each end of the cross piece 10 to maintain the platform 6 in position on the cross piece 10. As shown particularly in FIG. 2 one such upstanding member may be attached by welding to the cross piece 10 but the other is desirably provided with downwardly extending studs 26 and is provided with recesses 28 to fit over the spaced bars 12 that form the cross piece 10. There is a bar 30 provided with holes 32 to receive the studs 26. Nuts are engaged on the studs 26 to lock the bracket 30 against the bars 12 and thus locate the movable upstanding member 24 at a desired position.
The sleeve 20 is pivotally mounted on a rod 34 welded at 36 to the back 16 of the channel 14. There is a spring 38 that abuts the back 16 of the channel 14 and a projection 40 on the lever 22 attached to the sleeve 20. The spring 38 urges the sleeve 20 to the position shown in FIG. 2.
In the embodiment of FIGS. 1 and 2 the relative positions of the channels 14 and the cross pieces 10 are such that the legs extend outwardly and downwardly from the cross pieces 10 and away from each other. This disposition of the legs 4 is shown particularly in FIG. 1.
Furthermore, the cross pieces 10 are inclined relative to the tops of the channels 14 so the legs 4 extend longitudinally and outwardly downwardly from the platform 6 when the platform 6 is in position, as shown in FIG. 1.
To use the bracket illustrated in FIG. 2 to produce the structure illustrated in FIG. 1 the legs 4 of the approximately same cross section as the channels 14 are positioned within the channels 14. The levers 22 of the sleeves 20 are urged upwardly from the position shown in FIG. 2 so that the fronts of the sleeves 20 are at the maximum possible distance from the backs 16 of the channels 14. This facilitates introduction of the legs 4 into the channels 14. A leg 4 is positioned in each channel 14, and the levers 22 are released to assume the position shown in FIG. 2. Each bracket 8 may then be raised up a leg 4 by forcing lever 22 upwardly. This moves the sleeve 20 around the pivot point defined by the point on leg 4 where the sleeve 20 contacts the leg 4. At the uppermost position of the lever 22 the lever may be released and the spring 38 will urge it back to the position shown in FIG. 2. The movement may then be repeated until the bracket has been moved up a leg 4 a sufficient height. It will, of course, be appreciated that each channel may be positioned independently for each leg 4. Thus, the device is useful on ground that is not level and, furthermore, can also be arranged so that the platform 6 is sloped. The arrangement of the sleeve 20 and of the disposition of the legs 4 relative to the platform 6 ensures an extremely stable structure, easily able to carry considerable loads.
The embodiment of FIG. 3 is of use, for example, outside a house and generally where a large platform area is required. The platform is not shown in FIG. 3.
The device of FIG. 3 (a portion of which is enlarged in FIG. 4) features the legs 4 and the cross pieces 10 shown in FIGS. 1 and 2. In FIG. 3 the pathway is formed by a runner 42 to abut and edge of a leg 4 when the bracket is in the useful position shown in FIG. 3. There are spaced, fixed sleeves 44 extending from the runner 42 around the pathway. A sleeve 46 having a lever 48 is pivotally mounted between the fixed sleeves 44 on the runner 42. Bracing members 50 are attached to the runner 42 and to the cross piece, for example, by welding. There is a recess 52 adjacent each end of the cross piece 10 to receive a bracing member 54 extending from one bracket 8 to another bracket 8, spaced from the first bracket. The bracing member 54 is typically substantially perpendicular to the cross pieces 8. A clamping member 56 may be threaded into a wall of a recess 52 to guide bracing member 54 in place. Braces 58 may be pivotally attached to the base of the runners 42 to be temporarily attached to the bracing members 54 to reinforce the structure. This precaution may be necessary because, as indicated above, the embodiment of FIG. 3 is typically used with larger platforms. There is also a projection 60 formed on the cross piece 10 so that when the bracket of FIG. 3 is not in use the braces 58 may be attached to the bracket 8 to maintain the bracket 8 reasonably compact for storage.
The device of FIG. 3 is used precisely as in the device of FIG. 1, that is each bracket is moved up a leg 4 by operating the lever 48 in a manner analogous to that described for FIGS. 1 and 2.
Although not as clearly shown as in FIG. 2 it should be emphasized that the legs 4 in FIG. 3 extend outwardly from the platform, both to facilitate the grip of the sleeves 46 on the legs 4 and to provide a more stable structure.
The device of FIG. 3 receives a platform (not shown in FIG. 3 for the sake of clarity). Typically planks supported on the cross pieces 10 are used.
It should be noted that the structure of FIG. 3 has no equivalent to the upstanding member 24 of FIGS. 1 and 2. The legs 4 restrict the platform in FIG. 3 and can do so in the embodiment of FIG. 1 if required. | A bracket useful to form a free standing support on legs. The bracket comprises a cross piece to carry a platform. A pathway to receive a leg is positioned at each end of the cross piece. A sleeve is pivotally mounted on the pathway and extends when the bracket is in use, around a leg. A lever extends from the sleeve to permit pivoting of the sleeve to grip a leg positioned in the pathway and to permit the bracket to move up and down the leg. The free standing feature, together with ease of adjustment represents a considerable advantage. | 4 |
The present utility application hereby formally claims priority of U.S. Provisional Patent application No. 61/133,763 filed Jul. 2, 2008 on “Yarn Made From A Blend Of Cotton, Nylon And Silver And Process For Manufacturing Thereof” filed by the same inventor listed herein, namely, I. Michael Indiano, and said referenced provisional application is hereby formally incorporated by reference as an integral part of the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention deals with the field of yarns made from various component materials usually fibrous materials and a novel process for making this yarn is such a manner that it is stable to facilitate weaving and has unique antimicrobial characteristics. The yarns made according to the present invention can be utilized for various purposes such as forming woven fabrics and other materials and can be formed with various characteristics depending upon the various fibers utilized in the process for making of the yarn. The yarn and process for making yarn of the present invention is particularly useful for making fabric and material which is capable of destroying or inhibiting the growth of various types of undesirable microorganisms.
2. Description of the Prior Art
Various yarn compositions and processes for making yarns and carding machines used in the process for making yarns have been patented such as shown in U.S. Pat. No. 2,245,359 patented Jun. 10, 1941 to C. G. Perry on “Yarn Making”; and U.S. Pat. No. 3,251,178 patented May 17, 1966 to J. Stirling on an “Apparatus For Making Rope Strand Or Yarn”; and U.S. Pat. No. 3,347,727 patented to E. Bobkowicz et al on Oct. 17, 1967 and assigned to Emilian Bobkowicz; and U.S. Pat. No. 3,998,988 patented Dec. 21, 1976 to A. Shimomai et al and assigned to Teijin Limited on a “Conjugate Fiber, Fibrous Material And Fibrous Article Made Therefrom And Process For Production Thereof”; and U.S. Pat. No. 4,017,942 patented Apr. 19, 1977 to M. Clayton et al and assigned to The English Card Clothing Company on a “Textile Carding”; and U.S. Pat. No. 4,042,737 patented Aug. 16, 1977 to K. F. Forsgren et al and assigned to Rohm and Haas Company on a “Process For Producing Crimped Metal-Coated Filamentary Materials, And Yarns And Fabrics Obtained Therefrom”; and U.S. Pat. No. 4,388,370 patented Jun. 14, 1983 to V. S. Ellis et al and assigned to Imperial Chemical Industries Limited on “Electrically-Conductive Fibres”; and U.S. Pat. No. 4,756,941 patented Jul. 12, 1988 to F. P. McCullough et al and assigned to The Dow Chemical Company on a “Method And Materials For Manufacture Of Anti-Static Carpet And Backing”; and U.S. Pat. No. 5,234,720 patented Aug. 10, 1993 to R. D. Neal et al and assigned to Eastman Kodak Company on a “Process Of Preparing Lubricant-Impregnated Fibers”; and U.S. Pat. No. 5,372,739 was patented Dec. 13, 1994 to R. D. Neal et al and assigned to Eastman Chemical Company on a “Lubricant-Impregnated Fibers, Lubricant, And Processes For Preparation Thereof”; and U.S. Pat. No. 5,549,957 patented Aug. 27, 1996 to E. J. Negola et al on a “Bulked Continuous Filament carpet Yarn”; and U.S. Pat. No. 5,677,058 patented Oct. 14, 1997 to R. D. Neal et al and assigned to Eastman Chemical Company on a “Lubricant Impregnated Fibers And Processes For Preparation Thereof”; and U.S. Pat. No. 6,035,493 patented Mar. 14, 2000 to W. C. Carlton on a “Textile Carding And Relevant Apparatus”; and U.S. Pat. No. 6,723,428 patented Apr. 20, 2004 to S. W. Foss et al and assigned to Foss Manufacturing Co., Inc. on “Anti-Microbial Fiber And Fibrous Products”; and U.S. Pat. No. 6,815,060 patented Nov. 9, 2004 to Y. Yuuki and assigned to Asahi Kasei Kabushiki Kaisha on “Spun Yarn”; and U.S. Pat. No. 6,841,244 patented Jan. 11, 2005 to S. W. Foss et al and assigned to Foss Manufacturing Co., Inc. on “Anti-Microbial Fiber And Fibrous Products”; and U.S. Pat. No. 6,946,196 patented Sep. 20, 2005 to S. W. Foss and assigned to Foss Manufacturing Co., Inc. on “Anti-Microbial Fiber And Fibrous Products”.
SUMMARY OF THE INVENTION
Most generally the present invention utilizes cotton, nylon and silver fibers which are physically mixed together in a large container and then sprayed with a liquid ceramic which forms a physical mixture of the component fibers within the liquid ceramic material.
This material is removed from the container or vat in batches each normally being approximately 20 to 100 pounds per batch of material. These batches of this coated fibrous mixture are then placed in a uniquely configured carding machine which has very large teeth for gently and slowly opening of the fibers of the cotton, nylon6 and silver such that a completely homogeneous mixture of these three components and the liquid ceramic spray can be achieved. This mixing into a completely homogeneous blend of opened fibers of the various components can take as many as seven individual carding steps in the carding process and can take as long as a period of three hours.
The carding machine itself utilizes a uniquely configured card, sold commercially under the trade name “Wolf card” utilizes unusually large teeth to prevent damaging of the individual component fibers and, in particular, prevent damaging of the silver fibers while at the same time achieving a fully opened and blended homogeneous final mixture of all the component fibers.
This fully opened and blended fiber is then spun into yarn using a sequence of individual steps. The finally formed yarn is then coated with a paraffin and ceramic wax mixture. The paraffin component of the mixture lubricates the spinning yarn to allow it to be easily used to make fabrics or other materials and also facilitates winding of this final yarn onto cones. The ceramic component of this coating is applied for sealing and encapsulating the finally formed yarn. After heating this ceramic material chemically and molecularly bonds the yarn together by encapsulating thereof in order to maintain the overall integrity of the structure of the yarn. This chemical and mechanical bonding is enhanced by the subsequent heating of the finally formed yarn to a temperature of approximately 180 degrees in a heating chamber which slightly melts the nylon and also stabilizes the yarn by chemically and mechanically bonding the ceramic material for the purpose of encapsulating the yarn.
It is an object of the present invention to provide a yarn made from a homogeneous blend of cotton, nylon and silver fibers.
It is an object of the present invention to provide a yarn made from a unique combination of cotton, Nylon6 and silver by a unique process not known heretofore.
It is an object of the present invention to provide a blend of individual fibers of cotton, nylon and silver having a limited length normally between 30 and 60 millimeters individually.
It is an object of the present invention to provide a yarn made from a blend of cotton, nylon6 and silver fibers as well as a process for manufacturing thereof wherein the finally formed yarn is substantially capable of destroying or inhibiting the growth of microorganisms.
It is an object of the present invention to provide a unique process for making a uniquely formed yarn made from a novel carding machine utilizing a Wolf card with oversized teeth which allows for a slow gentle processing of the fiber mixture for opening and blending of the individual component fibers to facilitate forming of a finally blended material which is completely homogeneous while at the same time preventing damage to any silver component or other fibrous component thereof while also preventing the silver from agglomerating.
It is an object of the present invention to provide a yarn made from a blend of cotton, nylon and silver as well as a process for manufacture thereof wherein a paraffin and ceramic wax mixture is applied to the finally formed yarn to facilitate lubrication thereof and for encapsulating thereof to maintain integrity of the structure of the resultant yarn.
It is an object of the present invention to provide a yarn made from a blend of cotton, Nylon6 and silver and a process for manufacturing thereof wherein the finally formed yarn is steam heated within the heating chamber to a temperature of as high as 180 degrees Fahrenheit to slightly melt the nylon and to stabilize the yarn structure by chemically and mechanically bonding it within the ceramic material which has been applied to the yarn and encapsulates the yarn.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention provides a unique composition for a yarn made from a blend of cotton, silver and nylon, preferably Nylon 6 material, as well as a novel sequence of process steps for the manufacturing thereof. This preferred embodiment described herein is only a single example of the unique construction for yarn combining this above-described blend. This disclosure illustrate only a example of a novel type of processing that can be utilized for the manufacturing of such yarn. It should be appreciate that other similar steps can be included in other similar methods and still come within the general overall contemplated concept of the present disclosure herein for the method of produce yarn shown herein as well as for the composition of the yarn so produced.
Usually the blend from which the yarn is made will include cotton and nylon fibers which are purchased in lengths of approximately 30 to 60 millimeters in length. This specific length is preferred but other lengths somewhat outside of the range defined above will also provide usable. Silver is then purchased in longer fiber lengths which are then cut to be complementary to the length chosen for the cotton and Nylon6 fibers. As such, normally the various fibers used for forming yarn in this invention will include fibers all of approximately the same length, but this requirement can vary significantly depending upon the application and use for the finally formed yarn.
In the preferred configuration the cotton fibers, otherwise known collectively as cotton staple, will comprise approximately 65% of the initial mixture of fibers used to ultimately form the yarn. The Nylon fibers will preferably be chosen as Nylon6 fibers due to the better characteristics thereof, particularly the lower melting point when compared to other available Nylon materials. These fiber of Nylon6 is usually referenced as Nylon6 staple and will comprise approximately 30% of the initial yarn mixture. This silver staple component will then be added to an extent such as to comprise approximately 5% of the fiber mixture. Therefore the overall ratio of cotton staple to Nylon6 staple to silver staple in the initial mixture of fibrous components will be 65% to 30% to 5%, respectively.
Of the various Nylon fibers available for use in the present invention, Nylon6 has been chosen as preferable for the Nylon fiber yarn component because it has a lower melting point and since a slight melting of the nylon will occur during the final heating step of the present yarn making process when the component fibers are encapsulated with a ceramic fixing material. For this reason Nylon6 is the preferred material for the Nylon component of the composition of the yarn of the present invention.
The proper proportion of cotton staple, Nylon6 staple and silver staple are initially physically placed within a container or large vat and are mixed. This physical mixing can take place manually utilizing a manual tool such as a large wooden spatula or can use any other system for physically mixing the fiber components together initially. It should be appreciate that such physical mixing of the fibers has physical limitations due to the fibrous nature of the components and thus only a moderately thorough physical mixture can be achieved at this time. Once a moderate mixing of the fibrous components within the vat has been completed, the entire content of the vat is then sprayed with a clear translucent liquid ceramic material. This material is quite similar to a paint without a pigment since it is clear and translucent. This liquid ceramic spraying step coats all of the mixture of the fibrous materials throughout the container or vat. These fibrous materials which are now coated with the clear translucent liquid ceramic spray will then physically be mixed again in a similar manner as performed previously in order to further mix both the fibers with the liquid ceramic material sprayed into the vat.
The next step in this process is to initiate the blending of this fiber mixture by opening of the fibers. Individual batches of any size but preferably 20 pounds to 100 pound of the fiber mixture are removed from the vat and placed into the blending chamber of a carding machine. The carding machine for the present invention, preferably, is a Wolf carding machine which uses a type of card having special coarse teeth for the purpose of very gently and slowly opening and blending the mixture of different fibers. This type of carding machine is utilized specifically to open the fibers such that they can be homogeneously blended together. This opening and homogeneous blending occurs very slowly with the use of such a coarse card in the carding machine and, thus, requires a longer period of time with a number of individual passes of the batches of fibrous material used for effectively opening and blending the mixture. As many as seven individual carding steps may be required over as long as a three hour period to achieve full and complete homogeneous opening and blending of the fibrous mixture due to the fact that a card is being used for this carding process utilizes very coarse or open teeth as opposed to a fine toothed card which is utilized for other processes and achieves mixing and blending faster. In the present invention it is important to appreciate that such a fine toothed card not be utilized because such a card will lead to clogging or agglomerating of the silver fibers together which would prevent the thorough mixing thereof homogeneously throughout the overall fibrous mixture.
The Wolf carding machine described in this invention is commonly used for carding other materials such as wool. By modifying the configuration of the teeth to be more coarse, it can be used to provide a slower carding process as needed for the present combination of cotton staple, Nylon6 staple and silver staple. Once the carding of the needed amount of the mixture in the vat is finalized, then all the fibers will be opened and the final mixture will be completely homogeneous. It is then possible to spin the blended fiber into yarn by a process of sequential steps.
Initially the blended homogeneous fiber material is formed into a sliver form which is somewhat tighter than the initial final carded mixture. It is then made further tighter by placing it into a roving form. This roving is then wound onto roving spools or bobbins and it moves into a spinning frame to facilitate spinning directly into the final yarn form. The final spinning form takes the blended fiber which has been formed into sliver and spins it into yarn.
At this stage the yarn needs to be lubricated to facilitate use weaving and further processing thereof in forming of fabrics and material and to facilitate winding thereof onto cones. For this purpose a paraffin and ceramic wax mixture is applied onto the spinning yarn as it is wound onto the cones. The paraffin component of the wax mixture lubricates the yarn to allow it to be more easily knitted for being formed into woven materials and facilitates the direct placement on the cones themselves. The ceramic component, however, is utilized for seal the yarn for by encapsulating thereof and for maintaining the basic structure of the yarn.
The so formed yarn is then steam heated within a heating chamber at a temperature of approximately 180 degrees Fahrenheit which slightly melts the nylon6 to stabilize the yarn and also molecularly bonds the ceramic material which is positioned encapsulating the yarn which chemically retains and further bonds the nylon fibers, the cotton fibers and especially the silver fibers within the yarn to stabilize the final yarn product. As such, the final yarn product is stabilized by the ceramic component of the final coating and is lubricated by the paraffin component of the final coating and in this manner provides an anti-microbial capability not known or available heretofore.
While particular embodiments of this invention have been described above, it will be apparent that many changes may be made in the form, arrangement, sequencing and positioning of the various elements of the combination of element subject to this patent application. In consideration thereof, it should be understood that preferred embodiments of this invention disclosed herein are intended to be illustrative only and not intended to limit the scope of the invention. | The present invention provides a novel process for making yarn from a unique combination of fibers of cotton, nylon (preferably nylon6) and silver and a process for forming this yarn utilizing a unique sequencing of individual steps. The final yarn product is extremely strong, stable and useful for being woven into various fabrics and/or materials and, most particularly, possesses enhanced antimicrobial properties. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of commonly assigned U.S. Provisional Application No. 60/669,524 entitled “A System and Method for Photolithography in Semiconductor Manufacturing” filed on Apr. 8, 2005, the entirety of which is hereby incorporated by reference herein.
BACKGROUND
Since the inception of the semiconductor industry, photolithography has been used for forming the components of integrated circuits. Generally, light beams pass through a mask, which has been patterned with a magnified image of the relevant integrated circuits. The light beams are then focused by a projection lens onto a wafer, resulting in an image of the integrated circuits in the photoresist layer of the wafer.
Among other factors, mask defects constitute a source of yield reduction. Specifically, the deviation of the mask image will result in the imperfection of the image on the wafer.
Even though the defects of the mask image are detected during mask verification and validation, traditional approaches for wafer fabrication fail to take advantage of such information. As shown in FIG. 1 , after a customer 2 completes the design of the integrated circuits, the design data may be stored in a tape and forwarded to a mask formation unit 4 for purposes of generating a corresponding mask. Then, the completed mask may be dispatched to a wafer fabrication unit 6 to be used for semiconductor integrated circuit fabrication. Because mask formation is often imperfect and causes deviation in mask dimensions, wen the wafer fabrication facility performs mask verification and validation, a trial-and-error process is often used, which results in wasted time, funds and energy. The resultant product cycle time for product verification and validation and time-to-market is prolonged. This problem is only aggravated by the shrinking device dimensions.
BRIEF DESCRIPTION OF THE DRAWINGS
Aspects of the present disclosure are best understood from the following detailed description when read with the accompanying figures. It is emphasized that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion.
FIG. 1 is a simplified diagram of selected components of a semiconductor manufacturing facility;
FIG. 2 is a simplified flowchart of an embodiment of a new method of photolithography;
FIG. 3 is a simplified flow diagram of selected components of a semiconductor manufacturing facility.
DETAILED DESCRIPTION
It is to be understood that the following disclosure provides many different embodiments or examples for implementing different features of the disclosure. Specific examples of components and arrangements are described below. These are, of course, merely examples and are not intended to be limiting. In addition, the present disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. Moreover, the formation of a first feature over or on a second feature in the description that follows may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed interposing the first and second features, such that the first and second features may not be in direct contact.
In one embodiment, the present disclosure relies on the collaboration between the mask formation unit 4 and the wafer fabrication unit 6 . Instead of merely forwarding the completed mask to the wafer fabrication unit 6 , data indicating mask defects are also forwarded to the wafer fabrication unit 6 . As a result, prior to the first run of the exposure process, the wafer fabrication unit 6 may derive compensation energy based on the mask defects, and optimize the base energy accordingly.
Referring now to FIG. 2 , shown therein is a simplified flowchart of an embodiment of a new photolithography method 10 . Referring also to FIG. 3 for a simplified diagram of a data flow diagram. In step 12 , the wafer fabrication business unit 6 defines a test CD line pattern target width 32 for a particular mask and provides this target width to the mask formation business unit 4 . The mask formation business unit 4 makes the mask according to specifications from the customer and takes measurements of the mask test CD line width of the mask in step 13 . The measurement may be conducted by one or more metrology instruments and/or other methods known in the art. The resultant mask may include defects, which may be caused by erred design of mask patterns, flaws occurred during the pattern generation process, fabrication process, handling of the mask, and other defective manufacturing steps. In one example, during the fabrication of the mask, defects of the mask may be caused by bubbles, scratches, pits, fractures, and other factors. The wafer fabrication unit 6 transmits the test CD line target to the mask formation unit 4 . The transmission of this data may be done electronically such as using file transfer protocol (FTP), electronic mail, or another suitable way. A more formalized communication portal or interface may also be provided between the customer 2 , mask formation unit 4 , and wafer fabrication unit 6 . In step 14 , the measured line width is compared with the pre-defined mask CD line target width. In step 15 , a delta, delta_DOM, between the measured line width is compared with the pre-defined mask CD line target width is determined.
The mask that has been constructed as well as the delta width 34 are then supplied to the wafer fabrication business unit 6 in step 16 . The transmission of this data may be done electronically such as using file transfer protocol (FTP), electronic mail, or another suitable way. In step 17 , a compensation energy is calculated based on the delta width. The compensation energy is an amount to be applied to a base energy that is representative of the intensity of the photolithography light. Therefore, an adjustment or modulation of the base energy will vary the intensity of the light used in photolithography. In one embodiment, the calculation may include the following formula: compensation energy=ƒ(delta_DOM), wherein ƒ is a linear or nonlinear function. The function ƒ may be derived based on a variety of factors, such as the specific manufacturing technology, the mask layer, and/or a variety of other factors. Further, the function ƒ may be refined to achieve greater precision by several approaches, such as regressing the original formula in a polynomial form or other forms by a statistical tool, and/or using a greater collection data to refine the function as the manufacturing activity progresses. The function ƒ may also be determined by a number of methods, such as experiments, first data analysis, and/or other methods. For example, for the manufacturing of 0.15 μm logic devices, the function ƒ may be: compensation energy=33.83×delta —DOM− 2.0726. As noted above, the function ƒ is not fixed. For example, in another case, if delta_DOM is equal to about 0.002 um, the resulting compensation energy may be determined to be about 2.73426 mj. In step 18 , the base energy is adjusted by the amount of the compensation energy so that the wafer is exposed using the. adjusted base energy. The adjusted base energy may be equal to the sum of the original base energy and the compensation energy. Alternatively, the adjusted base energy may be equal to the difference between the original base energy and the compensation energy. The exposure may be accomplished by any methods know in the art, and may include dry lithography or wet lithography. In the case of wet lithography, the wavelength of the radiation may be 193 nm, 157 nm, and/or other figures.
The method 10 described above may be utilized in the manufacturing of a variety of semiconductor devices, such as memory devices (including but not limited to a static random access memory (SRAM)), logic devices (including but not limited to a metal-oxide semiconductor field-effect transistor (MOSFET)), and/or other devices. The transfer of various data may be performed via electronic transmissions such via electronic mail, web interface (Hypertext Transfer Protocol (HTTP) or Hypertext Transfer Protocol Secure (HTTPS)), File Transfer Protocol (FTP), Extensible Markup Language (XML), and/or any other suitable means now known or to be developed.
Many variations of the above example are contemplated herein. In one example, the mask formation unit 4 and the wafer fabrication unit 6 may belong to one business entity. In another example, deviation of the mask dimension delta_DOM may include any data relating to mask defects that may be used to adjust the lithography process other than or including the base energy. In another example, the mask formation unit 4 may simply forward data relating to the mask 24 , while the wafer fabrication unit 6 may compare the data with the original specification to determine the CD line width deviation or delta. Therefore, a variety of modifications are contemplated by the present disclosure.
Although only a few exemplary embodiments of this disclosure have been described in details above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this disclosure. Also, features illustrated and discussed above with respect to some embodiments can be combined with features illustrated and discussed above with respect to other embodiments. Accordingly, all such modifications are intended to be included within the scope of this disclosure. | A method for photolithography in semiconductor device manufacturing comprises defining test critical dimension target for a photolithography mask, measuring a mask critical dimension, comparing mask critical dimension to the test critical dimension target and determining a critical dimension deviation, determining a photolithography light base energy in response to the critical dimension deviation, and exposing the wafer according to the photolithography light base energy. | 6 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to printing presses, to web-fed printing presses, and to improvements in the construction of a folding station customarily appended to a web-fed printing press for cutting and folding the printed web into multiple-page signatures. More particularly, the invention deals with a perforator incorporated in the folding station for creating a series of incisions longitudinally and medially of the web description of the Prior Art, in order to expedite the subsequent folding of the web.
[0003] 2. Description of the Prior Art
[0004] The art of longitudinally perforating the printed web of paper, and folding the same along the series of perforations, at the folding station (shown in FIG. 1 of the drawings attached hereto) of the rotary printing press has been known and practiced extensively. Japanese Patent No. 3,034,702 represents a typical prior art device directed to the art, teaching use of a pair of cylinders placed opposite each other via the web. One of the cylinders carries a perforating tool, a sawtooth-edged perforating blade of annular shape arranged circumferentially thereon, and the other a bed or anvil with a groove therein to receive the sawtooth edge of the perforating blade via the web. The opposed pair of the blade cylinder and anvil cylinder are positioned between a former, by which the printed web is doubled along its longitudinal centerline, and an opposed pair of a folding cylinder and jaw cylinder by which the doubled web is cut transversely and again folded into eight-page signatures.
[0005] This prior art device is objectionable, among other reasons, for its large space requirement. Placed as above between the former and the folding and jaw cylinders, the blade cylinder and anvil cylinder make the folding station, and therefore the complete printing press system, inordinately bulky.
[0006] This drawback is absent from Japanese Unexamined Patent Publication No. 10-114,048, which suggests use of one blade cylinder and one anvil cylinder for both transversely and longitudinally perforating the web. The singular blade cylinder carries on its surface both a transversely perforating blade, which extends linearly along the cylinder axis, and a longitudinally perforating blade of annular shape extending circumferentially. The singular anvil cylinder has formed on its surface both an anvil of linear shape for the transversely perforating blade, and another anvil of annular shape for the longitudinally perforating blade. The web is therefore perforated both transversely and longitudinally as it passes between these dual blade cylinder and dual anvil cylinder.
[0007] Although so simple and compact in construction, this second prior art device has a serious inconvenience arising from the fact that not all the printings are necessarily perforated longitudinally besides being perforated transversely. The longitudinally perforating blade must therefore be detached from the blade cylinder when the web needs only transverse perforation, and remounted when it needs both transverse and longitudinal perforations.
[0008] Japanese Patent No. 3,166,087 utilizes preexisting feed roller means which lie between the noted former and the noted pair of folding cylinder and jaw cylinder in order to feed the web into and through the folding station. The feed roller means include one feed roller and, held against this feed roller, a pair of nip rollers of smaller size which are mounted on a common shaft with an axial spacing therebetween. A longitudinally perforating blade is mounted on the nip roller shaft, and an associated anvil on the drive roller.
[0009] An objection to this patent concerns the fact that the nip roller pair together with their supporting shaft are jointly movable toward and away from the drive roller in order to adjust to the variable thickness of the web traveling therebetween. As a result, according to this prior art device, the longitudinally perforating blade on the nip roller shaft incised the web to a variable depth depending upon the thickness of the web, sometimes failing to create perforations of sufficient size for the web to be subsequently folded correctly.
SUMMARY OF THE INVENTION
[0010] The present invention has it as an object to incorporate a longitudinal web perforator into the folding station of a web-fed printing press without adding to the size of the machine.
[0011] Another object of the invention is to make it unnecessary to dismount, and subsequently remount, the longitudinal web perforator in cases where the web does not need longitudinal perforation.
[0012] Still another object of the invention is to make the longitudinal web perforator independently adjustable to the variable thickness of the web, always cutting sufficiently deep into it in order to assure infallible folding of the web along the perforations.
[0013] Stated in its perhaps broadest aspect, this invention concerns an apparatus for longitudinally perforating a paper web or like material at a folding station of a rotary printing press. Included is a rotary, longitudinally perforating blade rotatably supported opposite a feed roller which forms part of feed means for feeding the web into and through the folding station. An anvil is formed on the feed roller for engaging the perforating blade via the web being thereby perforated. The perforating blade is moved by retractor means into and out of perforating engagement with the anvil on the feed roller.
[0014] In a preferred embodiment the feed means additionally include a pair of nip rollers movable into and out of rolling engagement with the feed roller via the web in positions spaced apart from each other axially of the feed roller. Positioned between this pair of nip rollers, the perforating blade is mounted to a rotary blade carrier shaft for joint travel therewith into and out of perforating engagement with the anvil on the feed roller, totally independently of the feed means.
[0015] Thus the longitudinal perforator means according to the invention are compactly incorporated with the preexisting web feed means without adding to the size of the folding station. The perforating blade itself is nevertheless movable toward and away from the feed roller independently of the pair of nip rollers and associated means. Consequently, although the nip rollers may vary their positions relative to the feed roller according to the thickness of the web, the blade can be urged by the retractor means toward the feed roller to incise the web thickness to a required depth. The web of variable thickness will therefore be invariably perforated and folded properly.
[0016] The longitudinally perforating blade must be retracted away from the feed roller not only when the web is threaded through the folding station preliminary to each printing assignment, but, as has been mentioned, when the web does not need longitudinal perforation. Employed for blade retraction in the preferred embodiment of the invention are a pair of fluid-actuated cylinders under the control of a solenoid valve, so that all that the operator has to do is to actuate this valve as by the manipulation of a hand switch.
[0017] The above and other objects, features and advantages of this invention and the manner of realizing them will become more apparent, and the invention itself will best be understood, from a study of the following description and appended claims, with reference had to the attached drawings showing the preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a diagrammatic side elevation of the known folding station of a web-fed printing press suitable for incorporating the longitudinally perforating means according to the invention;.
[0019] [0019]FIG. 2 is an enlarged perspective view, with a part shown broken away to reveal other parts, of part of the folding station incorporating a preferred form of longitudinal web perforator means according to the present invention;
[0020] [0020]FIG. 3 is a top plan of the showing of FIG. 2;
[0021] [0021]FIG. 4 is a vertical section taken along the line IV-IV in FIG. 3, showing the longitudinally perforating blade in its working position for perforating the web in cooperation with the anvil on the feed roller;
[0022] [0022]FIG. 5 is a side elevation of the showing of FIG. 2, seen in the direction of the arrow V therein; and
[0023] [0023]FIG. 6 is a view similar to FIG. 4 except that the longitudinally perforating blade is shown retracted away from the feed roller.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Folding Station
[0024] It will redound to a full appreciation of the advantages of the instant invention to show and describe the general configuration of the folding station of a web-fed printing press. FIG. 1 shows the printed web of paper W traveling down the folding station F. Positioned most upstream of the folding station F is a former 37 by which the web W is longitudinally doubled over itself. The doubled web W passes via a pair of feed rollers 38 to a transverse perforator 40 comprising a transverse perforating blade cylinder 40 a and an associated anvil cylinder 40 b . As the web W passes between these cylinders 40 a and 40 b , the transverse perforator 40 creates successive rows of perforations transversely of the web at constant longitudinal spacings. The web W is to be subsequently folded again along these transverse perforations into eight-page signatures.
[0025] Disposed downstream of the transverse perforator 40 , a cutter/folder mechanism 39 comprises a cutting cylinder 39 a for cutting the folded web W into successive predetermined lengths of individual sections and pushing each section along its perforated median line off the cylinder surface. A jaw cylinder 39 b is positioned opposite the cutting cylinder 39 a for receiving the pushed midpart of each section and creasing and folding the same along the transverse perforations into an eight-page signature. The successive eight-page signatures are deposited as at 41 on a conveyor 42 extending horizontally from under the jaw cylinder 39 b , thereby to be transported to a subsequent processing station.
[0026] For further folding the eight-page signatures into sixteen-page ones, there is provided a chopper folder 43 over the conveyor 42 . The chopper folder 43 includes a folding blade 43 a which acts on the successive eight-page signatures 41 on the conveyor 42 into sixteen-page ones. This folding into sixteen-page signatures requires that the web be previously perforated longitudinally somewhere between former 37 and cutter/folder mechanism 39 .
Embodiment of the Invention
[0027] The construction of the folding station F as so far described with reference to FIG. 1 is conventional, and therein lies no feature of the instant invention. The invention particularly concerns means incorporated in the folding station F for longitudinally perforating the folded web W in order to enable the same to be subsequently cut and further folded twice as above into sixteen-page signatures. FIGS. 2 - 6 are all directed to show how such longitudinally perforating means are built into the folding station F.
[0028] It will be observed from FIGS. 2 - 4 that the web W, previously doubled over itself by the former as in FIG. 1, is therein shown traveling down its predefined path between a pair of confronting framing walls 35 and 36 . Mounted between these framing walls 35 and 36 are web feed means WF comprising a feed roller 1 and a pair of nip rollers 5 and 5 a for feeding the web W downwardly. Transverse perforator means TP are conventionally provided downstream of the web feed means WF for cutting transverse rows of perforations 34 a , FIG. 2, in the web W at constant spacings. The transverse perforator mean TP include a blade cylinder 25 and anvil cylinder 27 on opposite sides of the predefined web path.
[0029] Positioned in close proximity of the web feed means WF are longitudinal perforator means LP forming the gist of this invention. For creating a longitudinal row of perforations 34 b , FIG. 2, centrally in the web W, the longitudinal perforator means LP include a sawtoothed perforating blade 11 and an anvil or bed 3 on the feed roller 1 . The longitudinally perforating blade 11 rotates in synchronism with the transverse perforator means TP by being driven therefrom via drive linkage means seen at D in FIGS. 2, 3 and 5 . Further the longitudinally perforating blade 11 is angularly displaceable by retractor means R into and out of perforating engagement with the web W. When retracted, the longitudinally perforating blade 11 permits the web W to be threaded between itself and the feed roller 1 .
[0030] Hereinafter in this specification the above listed web feed means WF, transverse perforator means TP, longitudinal perforator means LP, drive linkage means D, and longitudinal perforator retractor means R will be explained in more detail, in that order and under separate headings. Comprehensive operational description will follow the detailed explanation of the listed means.
Web Feed Means
[0031] With reference to FIGS. 2 - 4 the web feed means include the feed roller 1 rotatably supported between the pair of framing walls 35 and 36 , and the pair of nip rollers 5 and 5 a for pressing the web W against the feed roller 1 in positions spaced axially of the feed roller. The feed roller 1 has a pair of trunnions projecting from its opposite ends and rotatably journaled in the framing walls 35 and 36 . One of the trunnions has an extension projecting outwardly of the wall 35 and having a timing belt pulley 4 mounted fast thereon. A timing belt 28 extends over this pulley and a drive pulley, not shown, to impart rotation to the feed roller 1 .
[0032] The pair of nip rollers 5 and 5 a are rotatably mounted each at one end of a pair of parallel levers 6 or 6 a (hereinafter referred to as the nip roller levers). Medially pivoted on a crossbeam 7 extending between the pair of walls 35 and 36 , the two pairs of levers 6 and 6 a have their other ends pivotally coupled respectively to the piston rods 8 and 8 a of fluid-actuated cylinders 9 and 9 a (hereinafter referred to as the nip roller cylinders). These nip roller cylinders 9 and 9 a have their head ends pivotally coupled to brackets 10 and 10 a on the walls 35 and 36 , respectively, so that the pair of nip rollers 5 and 5 a are angularly displaceable toward and away from the feed roller 1 with the extension and contraction of the nip roller cylinders.
[0033] It is understood that, upon extension of the nip roller cylinders 9 and 9 a to cause retraction of the nip rollers 5 and 5 a , either the nip roller levers 6 and 6 a or the nip roller cylinder piston rods 8 and 8 a come into abutment against limit stops, not shown, on the framing walls 35 and 36 to limit the retraction of the nip rollers. The nip rollers 5 and 5 a should be so retracted to such an extent as to be spaced from the feed roller 1 a sufficient distance for the web W to be threaded therethrough preparatory to printing. Then, upon contraction of the nip roller cylinders 9 and 9 a , the nip rollers 5 and 5 a will travel back to their working position, urging the web W against the feed roller 1 under pressure from the nip roller cylinders. The web W will be frictionally fed downwardly through the folding station as the feed roller 1 is driven via the timing belt 28 .
Transverse Perforator Means
[0034] Themselves conventional in the art, the transverse perforator means TP include the blade cylinder 25 and anvil cylinder 27 which are both rotatably supported by and between the pair of framing walls 35 and 36 . The blade cylinder 25 underlies the feed roller 1 , as best shown in FIG. 4, and the anvil cylinder 27 is positioned opposite the blade cylinder 25 via the web W. The blade cylinder 25 has mounted thereon a transversely perforating blade 24 extending parallel to the cylinder axis. The anvil cylinder 27 has formed thereon a grooved bed or anvil 26 for receiving the blade 24 on the blade cylinder 25 via the web W.
[0035] Thus, as the blade cylinder 25 and the anvil cylinder 27 rotate in the directions indicated by the arrows in FIG. 4, the web W will be perforated transversely at constant spacings. FIG. 2 shows at 34 a one such row of transverse perforations that have been cut in the web W. It is understood that the blade cylinder 25 and anvil cylinder 27 are driven at the same peripheral velocity as the feed roller 1 in order to assure smooth travel of the web W.
Longitudinal Perforator Means
[0036] Reference may be had to FIGS. 2 - 4 and 6 for the following description of the longitudinal perforator means LP. Employed for creating the longitudinal row of perforations 34 b in the web W as in FIG. 2 is the noted sawtoothed perforating blade 11 of annular shape concentrically mounted fast to a disclike blade holder 12 together with a blade retainer 12 a . The perforating blade 11 may be either of one-piece construction or a combination of two or more discrete sectors. The blade holder 12 is nonrotatably mounted to a blade carrier shaft 13 extending parallel to the feed roller 1 . The blade carrier shaft 13 has its opposite ends rotatably journaled in bearings on a pair of swing arms 16 and 16 a which are pivoted respectively on the pair of trunnions 27 a of the anvil cylinder 27 of the transverse perforator means TP. The perforating blade 11 is therefore angularly displaceable with the carrier shaft 13 into and out of perforating engagement with the web W. Further the perforating blade 11 is to rotate with the blade carrier shaft 13 relative to the swing arms 16 and 16 a , by being driven by the drive linkage means D to be detailed subsequently.
[0037] The present invention makes use of the feed roller 1 as anvil cylinder against which the web W is perforated by the longitudinal perforating blade 11 . To this end the feed roller has the aforesaid annular bed or anvil 3 , complete with a groove 3 a extending throughout its length, formed circumferentially on the feed roller surface for engaging the sawtoothed edge of the perforating blade 11 .
[0038] The longitudinally perforating blade 11 has a series of rather blunt-ended teeth 11 a . The pitch of these teeth 11 a is an integral submultiple of the distance between any two neighboring ones of the transverse perforations 34 a created in the web W. The web will be perforated longitudinally as the toothed blade 11 incises the same on entering the groove 3 a in the anvil 3 on the feed roller 1 .
Drive Linkage Means
[0039] The drive linkage means D from transverse perforator means TP to longitudinal perforator means LP appear in FIGS. 2, 3 and 5 . Employed for driving the longitudinally perforating blade 11 in synchronism with the transversely perforating blade and anvil cylinders 25 and 27 is a timing belt 29 on the outside of the framing wall 35 . The anvil cylinder 27 of the transverse perforator means TP has a trunnion 27 a projecting outwardly of the framing wall 35 . A timing belt pulley 31 is mounted fast on this projecting end of the trunnion 27 a . Another such pulley 15 is mounted fast on the extension 14 of the longitudinally perforating blade carrier shaft 13 which also projects outwardly of the framing wall 35 . The timing belt 29 extends around these pulleys 15 and 31 . The timing belt 29 is tensed by a tension pulley 18 on a shaft 17 which is cantilevered to one, 16 , of the pair of swing arms 16 and 16 a supporting the longitudinally perforating blade carrier shaft 13 .
[0040] [0040]FIG. 5 best indicates that the framing wall 35 has an inverted-L-shaped slot 35 a formed therein. Both the extension 14 of the longitudinally perforating blade carrier shaft 13 and the cantilever shaft 17 extend through this slot 35 a with such clearance that the required pivotal motion of the pair of swing arms 16 and 16 a is not in any way hampered by the drive means D.
[0041] It is understood that the anvil cylinder 27 of the transverse perforator means TP is itself conventionally driven at the same peripheral velocity as the traveling speed of the web F. This rotation of the anvil cylinder is transmitted via the timing belt 29 to the carrier shaft 13 and thence to the longitudinally perforating blade 11 . The pulleys 15 and 31 are of the same diameter, tooth pitch, etc., so that the longitudinally perforating blade 11 will rotate at the same angular velocity as the anvil cylinder 27 of the transverse perforator means TP. Furthermore, the shortest distance between the axis of the longitudinally perforating blade 11 and the web W, when that blade is in the working position Q, FIGS. 3 and 4, is the same as that between the axis of the anvil cylinder 27 and the web.
[0042] Consequently, driven by the drive means D, the longitudinally perforating blade 11 will create longitudinal perforations 34 b in prescribed positional relationship to the transverse perforations 34 a . The longitudinal perforations 34 b are to come into exact register when, after being perforated transversely and horizontally, the doubled web is cut into individual sheets, and the sheets folded into eight-page signatures along the transverse perforations 34 a . When the eight-page signatures are subsequently folded along the longitudinal perforations 34 b into sixteen-page signatures, an adhesive may be impregnated through the longitudinal perforations which are registered at the folds, thereby bonding together all the pages of the signatures into book format.
[0043] The required positional relationship between transverse perforations 34 a and longitudinal perforations 34 b is obtainable if the noted distance between the axis of the longitudinally perforating blade 11 and the web W differs from that between the axis of the anvil cylinder 27 and the web. In this case the drive means D may be modified to include pulleys of such relative diameters and tooth numbers that the peripheral speed of the longitudinally perforating blade 11 matches that of the anvil cylinder 27 .
Longitudinal Perforator Retractor Means
[0044] The longitudinally perforating blade 11 is nonrotatably mounted as aforesaid on the blade carrier shaft 13 which in turn is rotatably supported by and between the distal ends of the pair of swing arms 16 and 16 a on the pair of trunnions 27 a of the anvil cylinder 27 of the transverse perforator means TP. Pivotally coupled respectively to these swing arms 16 and 16 a are the piston rods 19 and 19 a of a pair of fluid-actuated cylinders 20 and 20 a which are seen in all of FIGS. 2 - 4 and 6 . These cylinders 20 and 20 a will be hereinafter referred to as the longitudinal perforator cylinders in contradistinction from the nip roller cylinders 9 and 9 a . The longitudinal perforator cylinders 20 and 20 a have their head ends pin-jointed to respective brackets 21 and 21 a on the framing walls 35 and 36 .
[0045] Thus, with the extension and contraction of the longitudinal perforator cylinders 20 and 20 a , the pair of swing arms 16 and 16 a will swing about the axis of the anvil cylinder 27 together with the longitudinally perforating blade 11 . FIG. 4 shows the longitudinal perforator cylinders 20 and 20 a fully extended, with the longitudinally perforating blade 11 urged to the working position Q in which its teeth 11 a are received in the groove 3 a in the anvil 3 on the feed roller 1 after penetrating the web W. It is understood that limit stops, not shown, are provided for limiting the swinging motion of the swing arms 16 and 16 a , or the extension of the longitudinal perforator cylinders 20 and 20 a , when the longitudinally perforating blade 11 arrives at the working position Q.
[0046] In FIG. 6 are shown the longitudinal perforator cylinders 20 and 20 a fully contracted to bring the longitudinally perforating blade 11 to the retracted position S, in which the blade is sufficiently spaced from the feed roller 1 for the web W to be threaded therebetween prior to printing. It is understood that limit stops, not shown, are also provided for limiting the swinging motion of the swing arms 16 and 16 a , or the contraction of the longitudinal perforator cylinders 20 and 20 a , when the blade 11 comes to the retracted position S.
[0047] For such travel of the longitudinally perforating blade 11 between working position Q and retracted position S, the longitudinal perforator cylinders 20 and 20 a may be placed in and out of communication with a pressurized fluid source and a fluid drain, both not shown, as by a solenoid valve. The solenoid valve is controllerable by an electric switch to be manipulated by the operator.
Operation
[0048] The longitudinally perforating blade 11 must be retracted as in FIG. 6 for threading the web W through the folding station, and through the complete printing press, preparatory to printing. To this end the pair of longitudinal perforator cylinders 20 and 20 a may be contracted thereby causing the pair of swing arms 16 and 16 a to turn from their FIG. 4 position to that of FIG. 6. The pair of nip rollers 5 and 5 a must also be retracted out of rolling engagement with the feed roller 1 . This retraction is possible by extending the pair of nip roller cylinders 9 and 9 a . The longitudinally perforating blade 11 may be retracted earlier than the pair of nip rollers 5 and 5 a , in order that the longitudinally perforating blade carrier shaft 13 may not interfere with the retraction of the nip rollers.
[0049] Following the completion of web threading, the nip roller cylinders 9 and 9 a may both be contracted thereby urging the nip rollers 5 and 5 a against the feed roller 1 via the web W. As the printing press is subsequently set into operation, the printed web W will be fed into and through the folding station by the web feed means WF. The transverse perforator means TP will conventionally operate to create the transverse rows of perforations 34 a in the web W at constant spacings longitudinally of the web.
[0050] The operator may switch the unshown solenoid valve to cause extension of the longitudinal perforator cylinders 20 and 20 a . Thereupon the pair of swing arms 16 and 16 a will travel from their FIG. 6 position to that of FIG. 4 thereby carrying the longitudinally perforating blade 11 into perforating engagement with the anvil 3 on the feed roller 1 via the web W. The blade 11 will then start perforating the web longitudinally. The longitudinal row of perforations 34 b will extend through one of the spaces between the transverse rows of perforations 34 a .
[0051] Notwithstanding the foregoing detailed disclosure it is not desired that the present invention be limited by the exact showing of the drawings or the description thereof. A variety of modifications or alterations will suggest themselves to one skilled in the art on the basis of this disclosure. Let us consider for example one of the most important functional features of the invention, that is, that the longitudinally perforating blade 11 is retractable independently of the pair of nip rollers 5 and 5 a . This objective is achieved in the illustrated embodiment by mounting the blade 11 on the blade carrier shaft 13 rotatably supported by and between the pair of swing arms 16 and 16 a . The same goal is attainable in various other ways such as by eccentrically mounting the blade carrier shaft 13 to the nip roller shaft 7 via a pair of eccentric bearings thereon.
[0052] These and other modifications, substitutions and changes are intended in the foregoing disclosure. It is therefore appropriate that the present invention be construed broadly and in a manner consistent with the fair meaning or proper scope of the claims which follow. | A rotary printing press has a folding station where the printed web is perforated both transversely and longitudinally in order to expedite subsequent folding thereof into signatures. In order to incorporate a longitudinal perforator into the folding station without adding to its size, a longitudinally perforating blade similar to a circular saw is mounted to a blade carrier shaft which is rotatably supported opposite a feed roller by which the web is frictionally fed into and through the folding station. An annular, longitudinally grooved anvil is formed circumferentially on the feed roller for engaging the longitudinally perforating blade via the web being thereby perforated. The longitudinally perforating blade is movable with the blade carrier shaft into and out of perforating engagement with the anvil on the feed roller. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to an overhead door holder assembly, and more particularly, to modular door holder assemblies having interchangeable sliding elements with reduced sliding friction.
Temporarily holding a door in an open position is often necessary for convenience and safety, and one commonly employed method uses an overhead door control device that includes a pivoting arm attached between an upper portion of a door jamb and an upper part of a door. When the door is to be held open at an angle that does not exceed about 110 degrees, such a device is efficient, effective, and convenient to install and maintain. Overhead door control devices are less subject to damage by vandalism or accidents, and do not present a potential stumbling hazard.
However, many conventional overhead door control devices have components that are difficult to install, maintain, or replace. What is needed is an overhead door holder assembly that is durable, has minimal wear sliding component, does not require lubrication, and is easy to install, adjust or replace with minimal effort and expertise. The door holder must be set to permit easy engagement of the door holder, to hold the door against minor amounts of jostling contact without release, and yet to still permit closing the door without undue effort. Ideally, such a door holder will include mechanisms that prevent its damage from violent or forceful door opening.
The foregoing illustrates limitations known to exist in present devices and methods. Thus, it is apparent that it would be advantageous to provide an alternative directed to overcoming one or more of the limitations set forth above. Accordingly, a suitable alternative is provided including features more fully disclosed hereinafter.
SUMMARY OF THE INVENTION
In one aspect of the present invention, this is accomplished by providing an overhead door holder assembly, for attachment between a door jamb and a door, for selectively holding the door in an open position, including a jamb bracket attached to the door jamb and a jamb arm pivotally attached to the jamb bracket; a channel assembly having a channel therein; a slide assembly pivotally attached to the jamb arm for movement in the channel in response to opening or closing of the door, with the slide assembly supporting at least one low friction polymeric block in contact with the channel walls.
The foregoing and other aspects will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a generalized perspective view of an overhead door holder assembly;
FIG. 2 is a top view of the overhead door assembly of FIG. 1, showing the stop spring and slide assembly set in the channel of the channel assembly;
FIG. 3 is a side view of the channel assembly, showing a polymeric block attached to the slide assembly to provide low friction and low wear engagement with the channel assembly;
FIG. 4 is side view of an alternative modular slide assembly constructed by modification of the slide assembly of FIGS. 1-3;
FIG. 5 is an exploded perspective view of another modular slide assembly suitable for placement in the channel assembly; and
FIGS. 6 and 7 illustrate the slide assembly of FIG. 5 seated in a channel assembly, with the friction cam rotated to different positions in each of the Figures.
DETAILED DESCRIPTION OF THE INVENTION
As illustrated in FIGS. 1, 2, and 3, an overhead door holder assembly 10 has a channel assembly 22 positioned in a door inset 20 at an upper edge 13 of a door 12. The channel assembly 22 is attached to the door 12 so that its longitudinally extending and generally U-shaped channel 23 is upwardly open. Positioned for sliding movement within the channel 23 is a slide assembly 26.
In accordance with the present invention, the slide assembly 26 has an attached polymeric block 27 for contacting the channel assembly 22 to reduce sliding friction and wear. Typically, the low friction polymeric block is constructed from durable, inexpensive, and low friction materials such as nylon filled thermoplastic. A favored nylon filled thermoplastic is Nylatron®, produced by Polymer Corporation, of Reading, Pennsylvania. Use of the polymeric block 27 extends the useful wear life of the channel assembly 22 and slide assembly 26, eliminates the need for periodic lubrication with oils or solid lubricants such as graphite, and reduces noise of door opening or closing.
The door holder assembly 10 also includes a jamb bracket 16 permanently affixed by screws, bolts, rivets, or other fasteners to a door jamb 14. A jamb arm 18 is pivotally connected at one end to the jamb bracket 16 and at its opposite end to the slide assembly 26 by pin 19. In preferred embodiments, the jamb bracket 16, jamb arm 18 and channel assembly 22 are formed from extruded brass or other durable, wear resistant material such as steel.
When the door 12 is closed, the slide assembly 26 is positioned in the channel 23 distant from the spring support 24. As the door 12 is opened, as shown in FIG. 1, the pivoting connection of the jamb arm 18 between the jamb bracket 16 and the slide assembly 26 allows the slide assembly 26 to move along the channel 23 toward a spring support 24. When force is applied to open the door, the slide assembly 26 moves along the channel toward the spring support 24 until the slide assembly contacts and rebounds from the stop spring 34. The stop spring 34 absorbs the force of slider movement, preventing damage to the door or door holder assembly 10. Of course, conventional compression springs are not required to be fitted into the channel assembly. In alternative embodiments, polymeric or steel blocks can be fitted in the channel assembly to absorb force of the slider, and other mechanisms for engaging the slider can also be attached to the channel assembly.
For example, as best illustrated in FIG. 4, modularization in accordance with the present invention allows simple and easy modification of a the slide assembly for different functions. A hold open stop 128, formed from stamped metal and configured for permanent insertion into the channel assembly 22. The hold open stop 128 has an integrally formed flange 136 that can be snapped into a slot formed in the spring support 124 for locking engagement. At its end opposite from the flange 136, the hold open stop 128 has a stop element 138. The stop element 138 has angled and opposed first and second ramps 139 and 140. The first ramp 139 is typically configured to present a wedge shape surface having a dihedral angle of between about 10 degrees to about 40 degrees, with an angle of 25 to 35 degrees being typical. The dihedral angle presented by the second ramp 140 is much steeper, having a range of between about 50 degrees to about 85 degrees, with angles of 65 degrees to 75 degrees being typical.
The stop element 138 engages slide assembly 126 to hold open door 12. The slide assembly 126 includes an axle pin 143 for pivotally supporting a rocker 142, and an adjustment wedge 146 to permit altering the force exerted by the rocker 142 on the stop element 138 of the hold open stop 128. The adjustment wedge 146 has an internally defined wedge slot 154 through which passes a position pin 156 connected to the slide assembly 126. The position of the adjustment wedge 146 is itself adjusted by an adjustment screw 148 that engages a compression spring 150 situated between a head of the screw 148 and the adjustment wedge 146.
Engagement of the slide assembly 126 and the hold open stop 128 requires a catch 144 of the rocker 142 to contact the stop element 138 of the hold open stop 128. The catch 144 moves upward on the first ramp 139 of the stop element 138 as the slide assembly moves closer to the hold open stop 128, and ultimately slides down the second ramp 140 of the stop element 138 to a position of locked engagement with the second ramp 140 of the stop element 138, holding the door in an open position. Essentially, a reversal of this sequence is required to disengage the door from the hold open position, however, a greater force is required to pull the catch 144 up the steeper angled second ramp 140 compared to that required to push the catch 144 up the gentler angled first ramp 139. This difference in required force ensures that the door will remain in a held open position as long as required, while permitting a nearly normal opening force to temporarily lock the door in the hold open position.
Adjustment of the force needed to impel the catch 144 up the first ramp 139, and pull the catch 144 back up the second ramp 140, is modified with the aid of the adjustment wedge 146. When the rocker 142 rotates about the axle pin 142, a rocker face 145 engages a wedge face 152 of the adjustment wedge 146. The necessary rotation of the rocker 142 to allow movement of the catch 144 up the first ramp 139 is resisted by the adjustment wedge 146, with the adjustment wedge being pushed against the compression spring 150 and increasing the resistance to rotation of the rocker 142. The precise force can be easily adjusted with readily available tools by tightening or loosening the adjustment screw to change the position of the compression spring 150 (and consequently the position of the adjustment wedge 146).
An alternative modular slide assembly that does not require a separate hold open assembly can also be inserted into the channel assembly 22. For example, as best illustrated in FIG. 5, a slide assembly 226 suitable for modular placement in channel assembly 22 can incorporate frictional engaging features for holding open a door. The slide assembly 226 includes a slider 236 having serrations 237 defined on it, first and second springs 242 and 243, first and second friction pads 244 and 245 (formed from brake lining or other wear and heat resistant material), and a friction cam 238 connected to the slider 236 by its shaft 241 and a nut 240, along with additional locking engagement being provided by matched locking of its serrations 239 and serrations 237 of the slider 236. The top surface of the slider 236 has an attached polymeric block 287 constructed from a nylon filled thermoplastic such as Nylatron™ that provides low friction and low wear engagement of the slider 236 with the channel assembly 22 and its channel walls 21.
The springs 242 and 243 have a generally U-shaped cross sectional shape, and are respectively positioned between the centrally located slider 236 and the first and second friction pads 244 and 245. When assembled, the springs 242 and 243 press the pads 244 and 245 against the channel walls 21 of the channel assembly 22, the exact amount of pressure being determined by the angle of rotation of the friction cam 238.
As best seen in FIGS. 6 and 7, the friction cam 238 has an elliptical cross section. As the cam 238 is rotated from a first position with the long axis of the ellipse parallel to the channel to an increasingly angled position with respect to the longitudinal axis of the channel assembly, the springs 242 and 243 are increasingly compressed. This compression of the springs 242 and 243 consequently results in greater static and dynamic frictional force exerted by the pads 243 and 244. Depending on the thickness, type of pad, door resistance, and other appropriate factors, the friction cam 238 cam be adjusted to compress the springs a desired amount by adjusting its rotational angle. When the friction cam 238 is set at the correct rotational angle, it is slightly rocked so that the serrations 237 of the slider and serrations 239 of the friction cam 238 mesh, providing resistance to movement out of position as the nut 240 is tightened on the shaft 241. Using easily available tools, the present invention allows simple and quick adjustment of door hold force.
As those skilled in the art will appreciate, other types of slide mechanism can also be used in conjunction with the standardized channel assembly of the present invention. The examples presented in the present specification are exemplary, and are not intended to limit the particular type of hold open stop, stop block, slider, or other modular mechanism suitable for use in conjunction with the channel assembly. | An overhead door holder assembly, for attachment between a door jamb and a door, to hold the door in an open position includes a jamb bracket attached to the door jamb and a jamb arm pivotally attached to the jamb bracket. A channel assembly having a longitudinally extending channel is attached to the door, and one of a group of modular slide assemblies that interchangeably fit into the channel assembly can be selected for pivotal attachment to the jamb arm. The slide assemblies have attached polymeric blocks that reduce wear caused by sliding components and may have door hold and door stop provisions as well. | 8 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] The present application is a continuation of U.S. patent application Ser. No. 10/999,116, filed Nov. 29, 2004, now U.S. Pat. No. 7,303,334, which is a continuation-in-part of U.S. patent application Ser. No. 10/808,731, filed Mar. 25, 2004, now U.S. Pat. No. 7,099,427, the full disclosures of which are hereby incorporated by reference herein.
BACKGROUND
[0002] The present disclosure relates to a radiation attenuation system. More particularly, the present disclosure relates to a radiation attention system adapted for use with Computed Tomography procedures such as Computed Tomography scanning procedures and Computed Tomography fluoroscopy procedures. The present disclosure further relates to radiation attenuation system that is intended to reduce radiation exposure to at least one of a patient and medical personnel during Computed Tomography procedures.
[0003] Computed Tomography (CT) procedures are commonly used to obtain cross-sectional images of the patient's body, including images of a patient's brain, lungs, heart, liver, bones, blood vessels, etc. CT procedures are often used to diagnose different kinds of diseases such as cancer, to plan radiation treatments and surgeries, and to guide physicians during biopsies and other invasive procedures.
[0004] CT procedures involve the use of CT machines that use x-ray radiation to obtain the cross-sectional images. In conducting a CT procedure, a patient is placed in the CT machine between an x-ray generating source and an x-ray detecting sensor. The CT machine delivers controlled amounts of x-ray radiation from the x-ray generating source to the portion of the patient's body being examined. The x-ray detecting sensor is positioned on the other side of the patient and captures the x-ray radiation passing through the body of the patient. The x-ray detecting sensor sends an output signal to a processor representative of the amount of x-ray radiation absorbed by the patient. The processor receives the output signal from the x-ray detecting sensor and processes the signal to create the cross-sectional images of the patient on a display.
[0005] As presently configured, areas in which CT procedures are conducted (i.e. CT areas) expose not only the patient to radiation, but also the physicians and other medical personnel that may be present during the procedure. In CT procedures, significant amounts of radiation may be scattered to the patient and to the physician, or other medical personnel in the CT area (i.e. scatter radiation). The likelihood of having radiation scattered to the physician or other medical personnel is increased for CT fluoroscopy guided interventional procedures during which the medical personnel is in the CT area during the scan.
[0006] In addition, medical personnel and patients may be exposed to radiation emanating through the body or housing of the CT machine during a CT procedure. CT machines generally include a housing (i.e., gantry) defining an opening in which a patient is placed during a CT procedure. While the x-ray generating source generally concentrates the emitted x-ray radiation to the area defined by the opening, it is possible for at least some x-ray radiation to pass through the housing of the CT machine. Radiation passing through the housing of the CT machine may be received by the patient and/or the medical personnel present during the CT procedure.
[0007] Exposure to radiation may create potential health concerns. Radiation specialists and government agencies recognize the potential health risks caused by ionizing radiation and have developed the principle of ALARA (As Low As Reasonably Achievable). The principle of ALARA requires that radiation levels be reduced to the greatest degree possible taking into account a reasonable cost and physical application.
[0008] Accordingly, it would be advantageous to provide a radiation attenuation system that may be used during CT procedures to minimize a patient's exposure to radiation. It would further be advantageous to provide a radiation attenuation system that reduces the amount of radiation exposure for medical personnel working in a CT area. It would also be advantageous to provide a radiation attenuation system that is relatively flexible and compliant, and adaptable for use with a variety of CT machines and CT procedures. It would also be advantageous to provide a radiation attenuation system that is disposable. It would also be advantageous to provide a radiation attenuation system that is sterilizible before use. It would also be advantageous to provide a radiation attenuation system that may be coupled to CT devices having different configurations. It would further be advantageous to provide a radiation attenuation system for protecting medical personnel that is suitable for use with CT fluoroscopy procedures where medical personnel may need to insert biopsy needles or other instrumentation without hindrance. It would also be advantageous to provide a radiation attenuation system which provides a relatively high degree of comfort to the user. It would further be advantageous to provide a radiation attenuation system that is configured to reduce the amount of radiation exposure realized by a patient and/or medical personnel due to radiation emanating from the body or housing of a CT machine. It would further be advantageous to provide a CT machine having a radiation attenuation system configured to minimize the amount of radiation that passes through the body or housing of the CT machine and into the CT area. It would still further be advantageous to provide a housing for a CT machine configured to minimize the amount of radiation that passes through the substrate or body of the housing into the CT area. It would be desirable to provide for a radiation attenuation system having one or more of these or other advantageous features.
SUMMARY
[0009] An exemplary embodiment relates to a system for the attenuation of radiation during a Computed Tomography procedure using a Computed Tomography machine having a gantry defining an opening configured to receive a patient table. The system includes a shield made of a flexible radiation attenuation material and an interface supporting the shield at the Computed Tomography machine. The interface allows the shield to be selectively added to and removed from the Computed Tomography machine.
[0010] Another exemplary embodiment relates to a method of attenuating radiation during a Computed Tomography procedure preformed by a Computed Tomography machine having a gantry defining an opening. The method includes selectively supporting a flexible radiation attenuation material at least partially in front of the opening defined by the gantry. The flexible radiation attenuation material is selectively addable to and removable from in front of the opening by the medical personnel depending on the Computed Tomography procedure.
[0011] Another exemplary embodiment relates a Computed Tomography machine. The Computed Tomography machine includes a gantry defining an opening through which a patient table is at least partially inserted during a Computed Tomography procedure and a housing enclosing the gantry without substantially covering the opening and remaining fixed relative thereto. The housing is at least partially defined by a front panel that is formed of a substrate and a radiation attenuation material. The radiation attenuation material is in the form of a flexible sheet and is fixed relative to the substrate. The radiation attenuation material attenuates radiation that would otherwise pass through the front panel during the Computed Tomography procedure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a perspective view of a radiation attenuation system for protecting a patient according to an exemplary embodiment.
[0013] FIG. 2 is a perspective view of a radiation attenuation system for protecting at least one of a patient and a medical personnel according to an exemplary embodiment.
[0014] FIG. 3 a is an anterior view of a patient wearing radiation attenuating garment according to exemplary embodiment.
[0015] FIG. 3 b is a posterior view of a patient wearing radiation attenuating garment according to exemplary embodiment.
[0016] FIG. 4 is a perspective view of a radiation attenuation system according to another exemplary embodiment.
[0017] FIG. 5 is a perspective view of a radiation attenuation system according to another exemplary embodiment.
[0018] FIG. 6 is a perspective view of another radiation attenuation system according to another exemplary embodiment.
[0019] FIG. 7 a is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0020] FIG. 7 b is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0021] FIG. 7 c is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0022] FIG. 7 d is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0023] FIG. 7 e is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0024] FIG. 7 f is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0025] FIG. 7 g is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0026] FIG. 7 h is a plan view of a radiation attenuation pad according to an exemplary embodiment.
[0027] FIG. 8 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to one exemplary embodiment.
[0028] FIG. 9 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to another exemplary embodiment.
[0029] FIG. 10 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to another exemplary embodiment.
[0030] FIG. 11 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to another exemplary embodiment.
[0031] FIG. 12 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to another exemplary embodiment.
[0032] FIG. 13 is a partial cross-sectional view of the CT machine of FIG. 1 , taken along line 8 - 8 showing the housing according to another exemplary embodiment.
DETAILED DESCRIPTION
[0033] FIG. 1 shows a Computed Tomography (CT) machine 20 of the type commonly used to create cross-sectional images the body of a patient 10 . CT machines are well known and widely used in the medical field. Accordingly, CT machine 20 , as illustrated, is intended to be representative of all conventionally known CT machines and is not intended to be limited to the exact configuration shown.
[0034] CT machine 20 may be used for both CT scanning procedures and CT fluoroscopy procedures. As used herein, the use of the term “CT scanning procedures” is intended to mean CT procedures conducted as part of a noninvasive examination during which a medical personnel 12 (e.g. a physician, nurse, technician, and the like) administering or otherwise involved with a CT procedure is likely to be outside of the area in which the CT procedure is conducted (i.e., the CT area). The term “CT fluoroscopy procedure”, as used herein, is intended to mean CT procedures conducted as part of an invasive surgical procedure during which the medical personnel 12 is likely to remain in the CT area and substantially near the CT machine during the CT procedure.
[0035] CT machine 20 includes a housing 22 having a front side 23 and a back side 315 . Housing 22 encloses a support structure, commonly referred to as gantry 24 , that is configured to support at least one x-ray emitter 26 and at least one x-ray detector 28 . Gantry 24 may support the x-ray emitter 26 and the x-ray detector 28 in a manner sufficient to allow for the orbital rotation of x-ray emitter 26 and x-ray detector 28 around patient 10 . The gantry 24 defines an opening 30 in which at least a portion of patient 10 is inserted during the CT procedure. In its most common form, opening 30 is a generally circular opening. The illustration of opening 30 as a circular opening is not intended to limit the applicability of the present invention to CT machines having circular openings. As can be appreciated, the present invention is equally applicable with alternative CT machines having openings configured in any of a variety of shapes.
[0036] CT machine 20 further includes a patient table 38 configured to support the body of patient 10 . Patient table 38 is generally positioned perpendicular to the front side 23 of housing 22 and may be movable in the vertical and horizontal directions relative to opening 30 as well as transversely. As can be appreciated, for alternative CT machines, patient table 38 may remain stationary and housing 22 may move relative to patient table 38 .
[0037] To obtain an image, patient 10 is placed on patient table 38 and moved into opening 30 wherein patient 10 is positioned between x-ray emitter 26 and x-ray detector 28 . A primary beam of x-ray radiation emanating from x-ray emitter 26 passes through patient 10 before being captured by x-ray detector 28 . The x-ray radiation beam emanating from x-ray emitter 26 and passing through patient 10 is referred to herein as entrance radiation. During CT fluoroscopy procedures, wherein medical personnel 12 is standing near patient 10 and CT machine 20 , medical personnel 12 may be inadvertently exposed to entrance radiation and radiation leakage from CT machine 20 .
[0038] In addition to entrance radiation and radiation leakage, CT procedures are likely to generate scatter radiation. Scatter radiation refers to radiation emanating from x-ray emitter 26 that reflects off of and through an object such as patient 10 , CT machine 20 , the floor in CT area, etc. and scatters throughout the CT area. During a typical CT scanning procedure, the only person likely to be exposed to scatter radiation is patient 10 . However, during CT fluoroscopy procedures, or any other CT scanning procedure in which medical personnel 12 remain in the CT area, medical personnel 12 may also be exposed to scatter radiation. As explained above, exposure to radiation may create a health risk and should be reduced whenever practicably possible.
[0039] Referring to FIG. 2 , a radiation attenuation system 100 configured to minimize radiation exposure during a CT procedure is shown. Radiation attenuation system 100 includes a first radiation attenuation system 200 that is intended to assist in the protection of patient 10 from unnecessary exposure to radiation during a CT procedure and a second radiation attenuation system 300 that is intended to assist primarily in the protection of medical personnel 12 from exposure to radiation during a CT procedure. According to an exemplary embodiment, radiation attenuation system 100 may further include a third radiation attenuation system 400 that is intended to reduce radiation exposure to at least one of a patient and the medial personnel during a CT procedure. First radiation attenuation system 200 , second radiation system 300 , and third radiation system 400 include at least one radiation barrier article for reducing radiation exposure. Depending on the CT procedure being performed, first radiation attenuation system 200 , second radiation attenuation system 300 , and third radiation system 400 may be used in any of a variety of combinations, or alternatively may be used separately as individual radiation attenuation systems.
[0040] During a CT procedure, patient 10 must be exposed to x-ray radiation (i.e. entrance radiation) in order for cross-sectional images of the patient's body to be obtained. CT procedures are often focused on a specific portion of the patient's body (i.e. the target area). While the target area must be exposed to entrance radiation, the surrounding portions of the patient's body (i.e. secondary areas) do not have to be exposed. Radiation attenuation system 200 is intended to minimize a patient's exposure to entrance radiation, radiation leakage and scatter radiation present during a CT procedure by shielding the secondary areas.
[0041] Referring to FIG. 3 , radiation attenuation system 200 includes a radiation attenuation wrap, shield, cloth, or garment 210 . Garment 210 may be useful in blocking or attenuating radiation, and assisting in the protection of patient 10 . Garment 210 may be made of any radiation attenuation material and preferably is made of a light-weight and flexible radiation attenuation material. Preferably garment 210 is made of a radiation attenuation material that provides a relatively high degree of comfort to the patient. Garment 210 may used to cover the portions of patient 10 during a CT procedure that are not going to be examined.
[0042] Garment 210 preferably includes a body cover portion 212 and a head cover (e.g. hood, hat, helmet, etc.) portion 214 . Body cover portion 212 is not limited covering a patient's torso and may be configured to include leg cover portions, foot cover portions, arm cover portions, and hand cover portions. Preferably, garment 210 wraps around (e.g. underneath) patient 10 and does not simply drape over the top of patient 10 . Head cover portion 214 is intended to protect a patient's head from radiation exposure, and may include portions covering a patient's face, forehead and neck. As can be appreciated, the configuration of garment 210 may vary depending on the application and portion of the patient's body that is to be scanned. For example, it would be anticipated that garment 210 would be configured differently for scanning of the chest as compared to the abdomen or an extremity. Garment 210 may be made in range of sizes to fit adult or adolescent patients as well as infants.
[0043] Garment 210 may include a fenestration area 216 for providing access to the target area (i.e. the portion of the patient's body to be scanned) through an aperture (shown as an rectangular strip 218 ). Fenestration area 216 further provides an opening for allowing medical personnel 12 to access patient 10 for conducting various invasive procedures, such as the fluoroscopic guidance and/or manipulation of instruments during surgical procedures. According to a preferred embodiment, fenestration area 216 may be selectively sealed or opened by coupling a fastener 220 to garment 210 near fenestration area 216 . According to a particularly preferred embodiment, a hook and loop fastener is coupled to garment 210 and allows fenestration area 216 to be selectively sealed or opened depending on the CT procedure being conducted.
[0044] According to a particularly preferred embodiment, garment 210 is configured as a combination of a skirt, a vest, and a helmet. Such a configuration may be particularly suitable for procedures wherein the target area is the patient's abdomen or chest area. During a procedure of a patient's abdomen or chest, medical personnel can access the target area by moving a portion of the vest upwards to expose the desired area. However, the garment 210 is not limited to such a configuration, and such a garment could be used for procedures wherein the target area is not the patient's abdomen or chest.
[0045] While garment 210 is shown as an attenuation system that may be useful during CT procedures to protect a patient from radiation exposure, garment 210 is equally applicable with any procedure that emits ionizing radiation such as, but not limited to, intraoperative use of radiation equipment and implanting radiation therapy devices into patients that emit radiation.
[0046] As stated above, physicians, nurses, technicians, and other health care employees (collectively referred to as medical personnel) present during a CT procedure may be exposed radiation. Medical personnel present for numerous CT procedures may be exposed to significant cumulative radiation doses over time. Radiation attenuation system 300 is intended to reduce radiation exposure to medical personnel 12 present in the CT area during a CT procedure. Radiation attenuation system 300 may be particularly applicable with CT fluoroscopy procedures wherein medical personnel 12 is likely to be near the primary beam of x-ray radiation emanating from the CT machine or at least in an area susceptible to secondary scattered radiation or radiation leakage.
[0047] Radiation attenuation system 300 includes at least one radiation barrier article coupled substantially near or to CT machine 20 configured to reduce radiation exposure to medical personnel 12 . For purposes of this disclosure, the term “coupled” means the joining of two members directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate member being attached to one another. Such joining may be permanent in nature or alternatively may be removable or releasable in nature.
[0048] Referring to FIG. 4 , radiation attenuation system 300 may include a first radiation panel, shield, or pad 320 that may be useful in blocking or attenuating radiation, and assisting in the protection of medical personnel 12 . Pad 320 is made of a radiation attenuation material and is positioned between CT machine 20 and medical personnel 12 . Pad 320 may be coupled near or to the CT machine 20 . Preferably, pad 320 is substantially rectangular shape having an outer edge that includes a top edge 322 and an opposite bottom edge 324 .
[0049] Pad 320 may be coupled near or to CT machine in any position that may protect medical personnel 12 and/or patient 10 from unintentional radiation exposure. According to an exemplary embodiment, pad 320 is coupled to the side of patient table 38 . Pad 320 is coupled near the top surface of patient table 38 and hangs, extends, or drapes over the side of patient table 38 so that bottom edge 324 is near the floor of the CT area. Depending on the size of pad 320 and patient table 38 , multiple pads 320 may be coupled to patient table 38 in order to provide sufficient protection for medical personnel 12 . According to a second exemplary embodiment, pad 320 is coupled to the front side 23 of CT machine 20 . Pad 320 is coupled near gantry 24 substantially tangential to the bottom of opening 30 and extends downward so that bottom edge 324 is near the floor. Bottom edge 324 may be weighted in order to urge bottom edge 324 in the direction of the floor and help maintain pad 320 in a protective position. As can be appreciated, pad 320 is suitable for use anywhere in the CT area so long as pad 320 is between CT machine 20 and medical personnel 12 .
[0050] According to a preferred embodiment, shown in FIG. 5 , pad 320 is a flexible member sized to span across both the areas covered by the first and second exemplary embodiments described above. For such an embodiment, pad 320 may be described as having two portions, a first panel 328 that is integrally formed with a second panel 330 . First panel 328 is coupled to the front side 23 of CT machine 20 near gantry 24 and second panel 330 is coupled to a side portion of patient table 38 that is near opening 30 . Pad 320 is positioned between CT machine 20 and medical personnel 12 . First panel 328 and second panel 330 conform to the contour of CT machine 20 and are substantially perpendicular to each other. As previously stated, bottom edge 324 may be weighted. Such a configuration is intended to reduce the amount of radiation exposure experienced by medical personnel 12 while enabling medical personnel 12 to remain substantially close to opening 30 and patient 10 .
[0051] Referring to FIGS. 4 and 5 , to couple pad 320 to CT machine 20 , pad 320 may include a fastener 326 . According to a preferred embodiment, fastener 26 allows for the detachable coupling of pad 320 to CT machine 20 . According to a particularly preferred embodiment, pad 320 includes a hook and loop fastener coupled to the outer edge of pad 320 for allowing the detachable coupling of pad 320 to CT machine 20 . As shown in FIGURES, fastener 26 is coupled to top edge 322 . In alternative embodiments, fastener 26 may be coupled anywhere along the outer edge of pad 320 , or anywhere else along pad 320 . As can be appreciated, a number of suitable fasteners may provide the detachable coupling of pad 320 to CT machine 20 in addition to hook and loop fasteners such as, snaps, grommets, adhesives, zippers, etc.
[0052] Preferably, pad 320 is coupled to CT machine 20 and patient table 38 on both sides of patient table 38 as shown in FIG. 2 . If pad 320 includes a detachable fastener 26 , a single pad 320 can be utilized by selectively positioning pad 320 along CT machine 20 and patient table 38 to protect medical personnel 12 . As can be appreciated, pad 320 may be dimensioned and shaped in any of a variety of ways depending on the application. For example, pad 320 may be configured in any of a variety of shapes such as a pad having a curvilinear portion to more readily conform to a CT machine.
[0053] Referring to FIG. 6 , radiation attenuation system 300 may also include a second radiation barrier article, shown as radiation curtain, shield, or drape 340 . Drape 340 may be useful in blocking or attenuating radiation, and assisting in the protection of medical personnel 12 . Drape 340 is intended to be positioned between CT machine 20 and medical personnel 12 . Drape 340 is coupled near gantry 24 of CT machine 20 and substantially covers opening 30 . Drape 340 may be made of any attenuation material and is intended to reduce the amount of entrance radiation, radiation leakage and scatter radiation that medical personnel 12 or patient 10 may be exposed to during a CT procedure. In its most preferred form, drape 340 is a made of a flexible attenuation material having an outer edge that includes a bottom edge 344 that hangs downward from a top edge. Preferably, bottom edge 344 drapes around patient 12 and conform to the patient's body and patient table 38 . Similar to pad 320 , drape 340 may include a fastener, such as a hook and loop fastener, along the outer edge and may further be weighted along bottom edge 344 to maintain a desired position.
[0054] According to an exemplary embodiment, drape 340 is a solid shield or member covering opening 30 (shown in FIG. 7 a ). Configuring drape 340 as a solid member may be particularly useful during CT scanning procedures during which medical personnel 12 do not need access to the portion of the patient's body being scanned. Drape 340 may include a viewing panel (shown as a window 346 in FIG. 7 b ) that is relatively clear or translucent for the viewing of patient 12 within CT machine 20 . Window 346 may be of a variety of shapes and sizes, which may be dictated at least in part by the particular application.
[0055] To accommodate CT procedures during which it would be desirable for medical personnel 12 to access the portion of the patient's body being scanned, drape 340 may include a fenestration area 342 for providing access to the portion of the patient that is within CT machine 20 during the CT procedure. Fenestration area 342 may be an aperture (shown as a rectangular opening in FIG. 7 c ) that allows medical personnel 12 to insert medical instrumentation when conducting various invasive procedures, such as the fluoroscopic guidance and/or surgical procedures. According to a preferred embodiment, shown in FIG. 7 d , drape 340 may be configured as a plurality of flaps 348 which do not substantially restrict medical personnel 12 from accessing patient 10 . According to an alternative exemplary embodiment, as shown in FIG. 7 e , drape 340 is a solid member having a slit or cut extending from the bottom edge in a substantially vertical direction to define flaps 348 thereby providing access to patient 10 . According to a particularly preferred embodiment, drape 340 is a solid barrier having a plurality of slits formed in a substantially vertical direction to define flaps 348 (shown in FIG. 7 f ). The use of flaps 348 in combination with drape 340 is intended to reduce the radiation exposure experienced by medical personnel 12 without substantially restricting access to patient 10 .
[0056] As shown in FIGS. 7 a - 7 f , drape 340 is a generally rectangular shield that is disposed across opening 30 . As can be appreciated, drape 340 may be dimensioned and shaped in any of a variety of ways depending on the CT machine and the application. For example, drape 340 may be configured in any of a variety of shapes such as a shield having a curvilinear portion to more readily conform to a CT machine (shown in FIG. 7 g ). Alternatively, drape 340 may be configured as having a circular shape (shown in FIG. 7 h ).
[0057] According to a preferred embodiment, as shown in FIG. 2 , radiation attenuation system 300 includes the use of both pad 320 and drape 340 to assist in the protection of patient 10 and medical personnel 12 . The combination of pad 320 and drape 340 may increase the level of protection relative to the use of any one of the articles alone. The radiation barrier articles of radiation attenuation system 300 (i.e. pad 320 and drape 340 ) may be selectively positionable to allow medical personnel 12 to move an article out of the way if the article is not needed.
[0058] FIGS. 8 through 13 illustrate an attenuation system 400 configured to attenuate radiation emanating through housing 22 of CT machine 20 during a CT procedure. As detailed above, during a CT procedure, radiation is applied to patient 10 by x-ray emitter 26 which is supported by gantry 24 . During the procedure, it is possible for a percentage of radiation being applied by x-ray emitter 26 to inadvertently pass through housing 22 rather than being applied solely to patient 10 . Accordingly, attenuation system 400 is intended to protect patient 10 and/or medical personnel 12 from being undesirably exposed to radiation emanating through housing 22 and into the CT area.
[0059] As can be appreciated, the characteristics of CT machine 20 and housing 22 (e.g., shape, number of components, material, wall thickness, size, etc.) may vary depending on a number of factors including factors relating to the function of CT machine 20 , materials used to build CT machine 20 , and/or the aesthetics of CT machine 20 . It should be clearly understood that attenuation system 400 is suitable for use with any CT machine having a housing through which radiation (e.g., primary beam, scatter, etc.) may undesirably emanate from during a CT procedure. Attenuation system 400 can also be used with other types of radiation systems, such as diagnostic x-ray equipment.
[0060] Housing 22 is shown as being a generally continuous member (e.g., panel, partition, support, etc.), but according other suitable embodiments, may be configured as a plurality of members coupled together to define housing 22 . Housing 22 is defined by a substrate (e.g., body, etc.) having a first surface 23 , shown as being an outer surface (e.g., exposed surface, etc.), and a second surface 25 , shown as being an inner surface (e.g., concealed surface, etc.).
[0061] Attenuation system 400 includes at least one radiation barrier (e.g., member, panel, liner, etc.), shown as radiation shield 410 . Radiation shield 410 may be provided as an inner, outer, or intermediate surface of housing 22 . According to one exemplary embodiment (shown in FIG. 8 ), radiation shield 410 is shown as being supported adjacent to second surface 25 of housing 22 . According to another exemplary embodiment, radiation shield 410 is shown as being supported adjacent to first surface 23 of housing 22 (shown in FIG. 9 ).
[0062] Radiation shield 410 may cover substantially all of second surface 25 and/or first surface 23 of housing 22 , or alternatively, may be selectively provided in areas where radiation is likely to emanate housing 22 (e.g., near gantry 24 , etc.), as shown in FIGS. 11 through 13 . The addition of radiation shield 410 to CT machine 20 reduces the amount of radiation emanating through housing 22 during a CT procedure. Reducing the amount of radiation emanating through housing 22 is intended to reduce the radiation exposure of patient 10 and/or medical personnel 12 present during the CT procedure.
[0063] Radiation shield 410 may be supported relative to housing 22 in a variety of configurations. For example, radiation shield 410 may be coupled (directly or indirectly) to housing 22 . The coupling of radiation shield 410 to housing 22 may be accomplished using a variety of suitable techniques including, but not limited to, adhesives, mechanical fasteners (e.g., clips, snaps, hook and loop fasteners, etc.) any suitable welding process (e.g., ultrasonic welding, etc.), painting, embedding, spraying, etc. Any of the just mentioned coupling techniques may be used alone or in combination to couple radiation shield 410 to housing 22 . According to other suitable embodiments, radiation shield 410 may not be coupled to housing 22 , but instead may be supported by a supplemental member (e.g., a structural component of CT machine 20 , a portion of gantry 24 , etc.) and/or provided as a filler between x-ray emitter 26 and housing 22 .
[0064] FIG. 10 shows attenuation system 400 according to another suitable embodiment. In such an embodiment, housing 22 includes multiple layers and radiation shield 410 is disposed (e.g., sandwiched, etc.) between (e.g., intermediate, etc.) the layers. According to another embodiment, radiation shield 410 is integrally formed with housing 22 . For example, housing 22 may be formed using a molding process in which the material used to form housing 22 is provided around radiation shield 410 . Radiation shield 410 may be provided as a sheet-like member or alternatively may be provided as relatively small particles that is dispersed within the material used to form housing 22 .
[0065] Each of the barrier articles of radiation attenuation system 100 , including shield 410 , described above may be made of any radiation attenuation material including, but not limited to, bismuth, barium, lead, tungsten, antimony, copper, tin, aluminum, iron, iodine, cadmium, mercury, silver, nickel, zinc, thallium, tantalum, tellurium, and uranium. Anyone of the aforementioned attenuation materials alone or in a combination of two or more of the attenuation materials may provide the desired attenuation. According to various exemplary embodiments, the articles of radiation attenuation system 100 can be made of the attenuation material disclosed in U.S. Pat. No. 6,674,087, U.S. Pat. No. 4,938,233, or U.S. Pat. No. 6,310,355 which are hereby incorporated by reference. However, the articles of radiation attenuation system 100 are not limited to such embodiments and may be made of any radiation attenuation material.
[0066] The degree of radiation transmission attenuation factor by the radiation attenuation material may be varied depending upon the specific application. According to an exemplary embodiment, the radiation attenuation material will have a radiation transmission attenuation factor of a percent (%) greater than about 50%, suitably greater than about 90%, suitably greater than about 95% of a 90 kVp beam.
[0067] Preferably, the radiation attenuation material is generally light and flexible, to maximize workability for processing, bending, folding, rolling, shipping, etc. The material may be formable (e.g. deformable) or compliant, and relatively “stretchable” (e.g. elastic). According to alternative embodiments, the material used may be generally rigid and inflexible, and/or substantially weighted.
[0068] According to a preferred embodiment, the articles of radiation attenuation system 100 are generally disposable in whole or in part, thereby minimizing ancillary sources of contamination that may arise from multiple uses. According to another suitable embodiment, the articles of radiation attenuation system 100 are generally non-toxic, recyclable, and/or biodegradable. According to an alternative embodiment, the articles of radiation attenuation system may be reusable (e.g. for attenuation of radiation from atomic/nuclear disaster, clean up, rescue operations, etc.). According to a preferred embodiment, the articles of radiation attenuation system may be sterilized between uses to minimize the likelihood of bacteriological or virus contamination. Sterilization may be performed in any convenient manner, including gas sterilization and irradiation sterilization.
[0069] The construction and arrangement of the articles of the radiation attenuation system as shown in the preferred and other exemplary embodiments is illustrative only. Although only a few embodiments of the present inventions have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g. variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.) without materially departing from the novel teachings and advantages of the subject matter recited in the claims. For example, shield 410 may be configured in a variety of ways (e.g. depending on geometric requirements of housing 22 .) depending on the application. Further, shield 410 may be configured as screens or curtains that are coupled within CT machine 20 .
[0070] Accordingly, all such modifications are intended to be included within the scope of the present invention as defined in the appended claims. The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. In the claims, any means-plus-function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the preferred and other exemplary embodiments without departing from the spirit of the present inventions as expressed in the appended claims. | A radiation attenuation system for use with Computed Tomography procedures and a Computed Tomography having a radiation attenuation system are disclosed. The radiation disclosed attenuation system includes a shield made of a flexible radiation attenuation material and an interface supporting the shield at the Computed Tomography machine. The interface allows the shield to be selectively added to and removed from the Computed Tomography machine. The disclosed Computed Tomography machine includes a gantry defining an opening through which a patient table is at least partially inserted during a Computed Tomography procedure and a housing enclosing the gantry without substantially covering the opening and remaining fixed relative thereto. The housing is at least partially defined by a front panel that is formed of a substrate and a radiation attenuation material. The radiation attenuation material is in the form of a flexible sheet and is fixed relative to the substrate. The radiation attenuation material attenuates radiation that would otherwise pass through the front panel during the Computed Tomography procedure. | 0 |
BACKGROUND OF THE INVENTION
The development of mine roof supporting systems has progressed from the use of wooden braces to roof bolting systems with elongate tensioned steel bolts and, more recently, to the grouting of bore holes.
As a seam of coal or ore is removed in the course of mining, the static vertical and horizontal pressures previously exerted by that seam no longer are available to maintain equilibrium within the surrounding strata. As a consequence, there occurs a slight heaving upward of the floor, an inward bulging at the sides and a drooping of the roof of the shaft. This vertical and horizontal displacement of the roof, sidewalls and floor occurs rapidly until a semi-static equilibrium is reached. However, a slow creep often will continue until the floor or a sidewall collapses.
Traditionally, roof bolting has been carried out by drilling a series of holes into a mine wall or roof strata, following which a steel anchor bolt with an expandable anchor on the upper end is inserted into each bore. A bearing plate is mounted on the lower end of the bolt to abut against the roof or wall surface. Next, the bolt is tightened both to lock the upper anchor and to tension the bolt, thus compressing the strata.
Recent theories describing roof collapse assert that a mere compression of the roof strata may not be adequate. The inadequacy stems from the side-slipping within the strata which may totally negate the support supplied by tensioned bolts. Such side-slipping can shift the direction of overburden pressures to negate the supportive effect of tensioned roof bolts. Thus, investigators have proposed that side-slipping of the overburden can be avoided by completely filling each roof bore with a dowel. As a consequence, as the stratum begins to shift, the incipient motion immediately will be opposed by the dowel surface. By comparison, conventional steel roof bolts are much slimmer than the roof bores in which they are inserted and strata slippage is permitted beyond a critical point leading to failure.
In the average underground coal mine, the seam of coal being excavated is about thirty inches in height. Thus, machines and apparatus used within such mines must be designed to operate under ceilings of that height. Accordingly, the current practice for inserting roof bolts is to flex the steel bolt through an angle of about 90° before it is inserted within a roof bore. Generally, a thirty inch length of the bolt initially is inserted; then the bolt is straightened to the extent possible; the straightened part is inserted next; and this sequence continues until the bolt is completely inserted and the bearing plate and bolt head are in operable position.
SUMMARY OF THE INVENTION
This invention comprises a process for supporting the roof and sidewalls of a mine shaft wherein a length of cable comprising resin bonded glass strands is rotatively inserted into a roof bore simultaneously with a grout or bonding agent. Cable rotation during insertion improves the grouting procedure in three ways. Rotation mixes the grout, wipes the grout against the surface of the bore, and carries the grout to the top of the bore hole. Rotation in a direction to tighten the cable strands tends to push the grout upward due to the natural flow of liquids in the direction of least resistance. For purposes of this invention, suitable grouts are sulfur and polyester, epoxy, polyurethane resins and the like.
An air passage is provided in the cable to allow the escape of entrapped air as the cable advances into the bore hole. Such passages may be provided as one or more hollow filaments or as a passageway formed between the glass strands.
Objects and advantages of this invention will hereinafter become evident from the following description of the preferred embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional elevational view showing a mine shaft with roof bolt holes extending into the roof and apparatus for inserting roof bolts into the holes;
FIG. 2 is a sectional view of apparatus for inserting a roof bolt and the liquid bonding agent with the apparatus being mounted at the entrance of the bolt hole;
FIG. 3 is a sectional view through an inserted and bonded roof bolt taken along lines 3--3 of FIG. 1; and
FIG. 4 is a plan view of the cable rotor shown in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a typical mine shaft 10 includes a floor 12 and a roof 14. Holes 16 are drilled in the roof, the holes having a length of from about 4 to about 12 feet. A cable 18 which includes a plurality of fiberglass strands 20 (FIG. 3) is inserted into the hole 16 by a drive mechanism 22 which includes feed rollers 23. The drawing shows four strands formed of a plurality of resin bonded glass fibers or filaments, but is illustrative only. Cable formed of from three to eight such strands is satisfactory, depending upon acceptable flexibility for operation.
As the cable is being inserted into the hole, the upward push by the drive mechanism 22 is resisted by the frictional back pressure of the surface of the hole 16. Thus, the cable is in slight compression, particularly near the entrance of the hole. Therefore, the cable requires a certain amount of rigidity because the strands must be pushed to near the top of the hole. Rotation of the cable in a direction in which the strands are twisted renders the cable more rigid and thereby makes its insertion into the hole easier. Additionally, outcroppings of rough rock surface within the hole can catch on the top surface of the cable as it is inserted and cause it to buckle or bend. However, with rotation during insertion, the twisting motion of the cable causes it to pass the outcropping and continue its upward movement.
FIG. 3 shows a hollow filament or open duct 24 located in each of the four strands 20. Each such duct extends from one end of the cable to the other to allow air to escape as the cable is inserted.
Simultaneously with the insertion of the cable, a bonding agent 25 is introduced into the annulus shaped cavity defined between surface 16 and cable 18. The bonding agent, which will be described in more detail, is introduced through a plurality of passages 26 in face plate 27. Face plate 27 presses against a sealing gasket 28 positioned against the roof 14 to prevent leakage of the bonding agent.
Beneath face plate 27 is a rotating plate or cable rotor 30 having a patterned opening 32, the profile of which corresponds to the shape of the cable. Thus, plate 30 grips cable 18 as it is inserted and rotates it in the direction of the twist of the strands. The resultant twisting action of the cable serves to urge the bonding agent upwardly into the hole, thus minimizing the pump pressure otherwise necessary to inject the bonding agent, preferably not substantially greater than 15-20 p.s.i. Also, because strands 20 are moving upwardly and rotating, the bonding agent, having a viscosity, preferably of about 100-2,000 c.p.s., clings to and intimately adheres to the strands while being wiped against the surface of hole 16.
The periphery of rotor 30 is formed having gear teeth which are meshed with the associated gears of a drive train shown in FIG. 2. This arrangement represents one of several ways by which rotor 30 can be driven.
For purposes of illustration only, cable 18 is shown mounted on reel 34 from which lengths thereof may be removed as needed.
Bonding agent 25 is injected from a reservoir 36 by one or more pumps 38. The number of such pumps and the exact structure of the storage container 36 depend on the kind of bonding agent used. Suitable bonding agents include sulfur and one or more resins selected from the group consisting of polyester, epoxy and polyurethane resins and the like.
Unsaturated polyester resins having workable viscosities (100-2,000 c.p.s.) at mine temperatures (about 55° F.) represent a preferred bonding agent. From the standpoint of cost economy, water resistance and desirable physical properties, a highly unsaturated maleic orthophthalic/propylene glycol polyester resin is preferred. The curing agent provided with the polyester resin should cause curing in about one minute under mine conditions. A number of such agents are known in the art, one example being benzoyl peroxide/diethyl aniline.
An example of an appropriate epoxy resin for mine bolt grouting is diglycidyl ether of bisphenol A. Suitable curing agents for use therewith are aliphatic polyamines, polyamides and their adducts. The epoxy resins generally have a higher viscosity than the polyester resins and in this sense may be slightly less desirable.
Thermosetting polyurethanes offer several properties well suited for the presently contemplated use. For example, these properties include higher cured strength, rapid rates of curing and potential for chemical bonding with both the cable and the surface of the drilled hole. Two-component urethanes can be formulated for a wide variety of performance parameters including hardness, tensile strength and speed of cure.
Sulfur is another suitable liquid bonding agent. The temperature at which it is inserted into the roof bore must be such that it will not solidify prematurely. It is believed that a temperature of about 135° C. represents an average temperature appropriate for the agent at the position of injection. This temperature is slightly above the melting point of sulfur.
Having described the preferred embodiments, it will be clear to those having ordinary skill in the art that various modifications can be made without departing from the spirit of the invention. Accordingly, it is not intended that the language used to describe the invention herein be in any way limiting. Rather, it is intended that the invention be limited only by the scope of the appended claims. | A process for supporting the roof of a mine shaft includes drilling a hole into the roof and then inserting a multi-stranded cable into the hole. The cable has a duct therein to allow the exit of air during its insertion. During the insertion, the cable is rotated and a bonding agent is introduced into the annulus between it and the surface of the hole. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of inscribing indicia on a surface or gemstones, and more particularly to a system employing a Q-switched pulse laser for forming, markings on a portion of a gemstone
BACKGROUND OF THE INVENTION
[0002] A known system as described in U.S. Pat. No 4,392,476, incorporated herein by reference, for inscribing diamonds includes a Nd.YAG (1.06 μm, frequency doubled) Q-switched laser which marks diamonds by graphitizing the surface at a laser focal point. The beam position is computer controlled to create overlapping treated regions. The accuracy of known embodiments of this system are limited by vibration and laser steering system accuracy.
[0003] U.S. Pat. No. 4,467,172, incorporated herein by reference, describes a laser beam diamond inscribing system, which provides a Q-switched flashlamp pumped YAG laser (1.06 μm, frequency doubled) with the diamond mounted on a computer-controlled positioning table for inscribing alphanumeric characters See also, U.S. Pat. Nos. 2,351,932, 3,407,364, 3,527,198, 3,622,739. 3,775,586 and 4,048,515, and foreign patents JP 00-48,489 and JP 00-77,989.
[0004] U.S. Pat. Nos. 5,410,125 and 5,149,938 describe systems which produce a gemstone marking by employing an excimer laser (193 nm) with a masked marking image Thus, repositioning to form complete characters or graphics is unnecessary The diamond selectively absorbs the excimer laser radiation and undergoes a partial allotropic transformation without losing its diamond crystal lattice configuration See also, U.S. Pat. Nos. 3,527,198 and 4,401,876, 5,410,125 is a continuation-in-part of Ser. No. 595,861, issued as U.S. Pat. No. 5,149,938.
[0005] Gemstone News, Nov. 2, 1995, “Serial Numbers are Laser Inscribed”, and Jeweler's Keystone-Circular, June 1996, pp 76 relate to gemstones inscribed with serial numbers or markings
[0006] U.S. Pat. No. 3,537,198 relates to a method of working diamonds using laser energy U.S. Pat. No. 5,190,024, relates to a diamond sawing process. A laser can be used both to mark and saw the diamond in one operation. See also, U.S. Pat. Nos. 671,830, 671,831, 694,215, 732,118, 732,119, 3,527,198 and 4,392,476, as well as Foreign Preference GB 122,470.
[0007] U.S. Pat. No. 4,401,876 relates to a system for kerfing a gemstone such as a diamond, employing a high energy, high pulse rate, low order mode, laser beam See also, U.S. Pat. Nos. 3,440,388, 3,527,198 and 3,700,850, as well as foreign references BE 877,326, DE 130,138, DE 133,023, GB 1,057,127, GB 1,059,249, GB 1,094,367, GB 1,254,120, GB 1,265,241, GB 1,292,981, GB 1,324,903, GB 1,326,775, GB 1,377,131, GB 1,405,487, GB 1,446,806, GB 2,052,369, Laser Institute of America, “Guide for Material Processing by Lasers” 1978, “Industrial Diamond Review”, March 1980, pp. 90 and 91; “Laser Application Notes”, 1(1) (February 1979); “New Hyperyag”, on Model DLPY 4-System 2000 Yag Laser; and “Diamonds” N.A.G. Press LTD, Chapter Eleven, pp. 235, 239-242.
[0008] U.S. Pat. No. 4,799,786, incorporated herein by reference, relates to a method of diamond identification provides a method for the identification of diamonds in which a sample to be identified is placed in a beam of monochromatic laser radiation of pre-determined wavelength. The scattered Raman radiation emitted from the sample is passed through a filter adapted to pass only scattered Raman radiation of frequency characteristic of a diamond. The filtered radiation is then detected by the human eye or a photocell device See also, U.S. Pat. Nos. 4,397,556 and 4,693,377, and foreign patent GB 2,140,555, Melles Griot, Optics Guide 3, 1985, pp 1,333. 350, 351; and Solin et al., Physical Review B, 1(4) 1687-1698 (Feb. 15, 1970).
[0009] U.S. Pat. No. 4,875,771, incorporated herein by, reference, relates to a method for assessing diamond quality, by assessing diamonds with a laser Raman spectrometer. The system is initially calibrated by use of diamonds with known quality characteristics, the characteristics having been assessed, for example, by a conventional subjective procedure Diamonds of unknown quality characteristics are then placed in the spectrometer and irradiated with laser radiation. The intensity of the scattered Raman signal from the diamond is monitored for one or more orientations of the diamond, the resultant signal being a characteristic of the diamond and believed to indicate a quality level of the diamond See also, U.S. Pat. Nos. 3,414,354, 3,989,379, 4,259,011, 4,394,580, 4,397,556 and 4,620,284, and foreign patents FR 643,142, FR 2,496,888, JP 01-58,544, GB 1,384,813, GB 1,416,568, GB 2,010,474, GB 0,041,348 and GB 2,140,555, S A. Solin and K. A Ramdas, Raman Spectrum of Diamond, Physical Review vol. 1(4), pp. 1687-1698.
[0010] The aforementioned documents detail components, methods and systems which may be applied in the construction and operation of the present invention.
SUMMARY OF THE INVENTION
[0011] The present invention provides a system having a pulse laser, such as a Q-switched laser diode excited Nd:YLF laser, which produces a senes of ablated or graphitized spots on the surface of a workpiece, such as a diamond gemstone. The workpiece is mounted on a translatable stage, for focusing and positioning of the beam.
[0012] The translatable staite is controlled by a computer to produce a complex marking pattern. This computer may also be used for process control and imaging, as well as other functions.
[0013] The process according to the present invention typically achieves a positioning accuracy of about ±1 micron. The laser and translatable mounting stage are compact and are preferably rgidly mounted on a common platform, allowing sufficient common mode vibration immunity so that only standard vibration damping need be employed rather than extraordinary damping. Therefore, simple and small passive vibration isolation mounts for the platform or chassis are employed, rather than requiring active vibration suppression systems as in known systems.
[0014] Optical feedback of the process is possible through one or more video cameras, e g , 2 CCD imagers provided at right angles, which are provided with a field of view including the focal point of the laser. The correct positioning of the gemstone may thus be assured by correct alignment of the imagers on the workpiece. One imager is directed at the work surface along the axis of the laser, and has a focal plane including the focal point of the laser. Optical feedback through the imagers may also be used to monitor the progress of the marking process, and therefore may be used to adjust workpiece positioning as well as inscription speed, number, intensity and/or rate of pulses at a given location, as well as to verify progress of the marking process. One imager is directed to view a top portion of the workpiece, e.g., directed perpendicular to the table surface of a diamond, allowing identification of a girdle profile, while the second imager is directed to view a side portion of the workpiece, e.g., a profile, and also providing a direct view of the girdle of a gemstone. Thus, the second imager may be used to view the marking process in real time.
[0015] The optical feedback system also allows the operator to design an inscription, locate the inscription on the workpiece, verify the marking process and archive or store an image of the workpiece and formed markings.
[0016] The markings themselves may have an invanant inscription, a fully automated inscription, e.g., a serial number, a semiautomated inscription, e.g., having a fixed and variable portion, or a fully custom inscription, including graphics.
[0017] According to one embodiment, an inscription for a gemstone is defined in relation to a bar code which accompanies the packaging for the gemstone or a preprinted sheet. A bar code reader is provided for the operator to input the bar codes into a computer, without having to retype the data and with lower risk of error. Thus, an inscription may include a fixed portion, e.g., a logo or trademark, a semivariable portion, e.g., a gem rating or grading, and a hypervariable portion, e.g., a serial number. In this case, for example, a logo or trademark is preprogrammed, and inscribed on every workpiece in a series. The gem rating or grading can be scanned as a bar code, printed on a sheet associated with that gemstone, such as a receipt or label. The serial number may be automatically determined, and for example, printed on a receipt or label, and employed as a unique identifier to be applied to the stone. The inscribed characters need not be limited to alphanumeric symbols, and in fact may be fonts in any language, line-drawing characters, custom characters or pictorial representations.
[0018] The workpiece may be associated with data, stored in a medium physically associated with the workpiece or in a remote medium accessible through use of an identification of the workpiece For example, the associated memory is a nonvolatile memory, such as a battery-backed random access memory, an electrically erasable read only memory, a ferroelectric memory, or other storage media such as magnetic stripes, rotating magnetic media, optical memories, and printed matter.
[0019] A vanity inscription may be provided on the workpiece as a custom or semicustom inscription, which may be provided as computer text, graphics or a computer-scanned image. The marking system may be employed to mark portions of a gemstone other than the girdle, for example the table. Therefore, in the case of such vanity inscriptions, the intent may be to provide a visible inscription, to enhance the sentimental value of the workpiece, rather than to provide an unobtrusive microscopic identification or authentication marking.
[0020] In many instances, it is desired that each inscribed workplace be separately identifiable. This may be by way of a unique marking, on the stone or a unique combination of marking and easily identified characteristics of the workpiece, such as weight, shape, type, etc,. In one embodiment, the markings themselves form a code, such as an alphanumeric or bar code, Which may be electronically or automatically read or ascertained from an examination of the workpiece.
[0021] An image of the marked work-piece may be formed or printed on a certificate which accompanies the workpiece, allowing verification that the workpiece corresponds to the certificate by studying the image in comparison with the actual workpiece. The image advantageously includes all or a portion of the marking, as well as identifiable features of the workpiece, such as landmarks, edges, facets, etc, Thus, the image may be used as a “fingerprint” identification of the workpiece. The image on the certificate may be formed photographically or electronically. Thus, the image as stored need not be formed through the CCD images or the marking system, and may be produced as a separate step.
[0022] Advantageously, an image of a completed marking or a bitmap of an inscription program is stored in a database, and therefore is available for comparison and later authentication of a workpiece, and to prevent inadvertent or undesired duplicate markings. The storage may be electronic or photographic, and thus the database may reside on magnetic or magnetooptical media, microfilm, paper or film, holographic crystals, magnetic or optical tape, or other known media.
[0023] In accordance with one aspect of the invention, a duplicate-prevention function is provided integral to the marking device which may not be overridden by a user, eg., to prevent inadvertent or intentional misuse of the system. In this case, the laser system may include a lockout circuit which prevents activation of the laser control and positioning systems under unauthorized circumstances. Such a lockout may be provided in the power supply or other critical subsystem of the device.
[0024] Based on the use of the marking system, a report may be generated by the computer/controller. Because the inscription is a raster ablated image, such report may advantageously include either the programmed inscription as a graphic printout or an image received from the optical feedback imaging system, e.g., the video camera. As stated above, the report may also include or be associated with a certificate of authenticity, e.g., including a facsimile of the workpiece image including the marking. A known image authentication scheme is disclosed in U.S. Pat. No. 5,499,294, incorporated herein by reference.
[0025] The entire workpiece is generally mounted on a translatable stage, allowing precise positioning. Thus, fur compact designs, the holder may accommodate workpieces of less than about 30 mm in a largest dimension, although the stage is capable of accurate positioning over a larger distance. The stage is generally translatable along three axes, X, Y, and Z in a Cartesian coordinate system, but may also include other axes, e.g., rotational axes. For example a brilliant cut diamond is radially symmetric. Therefore, where an inscription or marking is desired around the diamond girdle, the diamond may be held in focus by adjusting a Z axial displacement and an inscription defined by translation along the X and Y axes during laser pulsing. Alternately, the diamond may be initially positioned appropriately along the X, Y and Z axes, and rotated about an axis and translated sequentially along a Y axis to define the inscription. In this case, the Z axis and possibly X axis may also be used to retain focus condition. Where X, Y and Z axes are employed for automated control, a manual rotational control is preferably provided with detents at regular intervals.
[0026] The positioning system, for moving the workpiece in relation to the laser focal point may also include or be formed from beam steering systems, such as mirrors, electrooptical elements, spatial light modulators, such as the Texas Instruments Digital Mirror Device (“DMD”, also known as Digital Light Processor, “DLP”), holographic or diffractive elements, or other optical systems. However, a translatable stage is a preferred means for directing the focused laser energy onto a desired portion of the workplace.
[0027] The workpiece generally sits in a holder which detachably mounts to the translatable stage. Thus, a workpiece may be suitably mounted in a holder outside the apparatus while another workpiece is being inscribed. These holders may also increase the versatility of the device by providing adaptation to workpieces or various sizes and shapes. For example, round, oval, heart, marquis and other cut diamonds may each be provided with separately optimized holders; further, diamonds of various size ranges may be accommodated by differing holders, as necessary.
[0028] According to another embodiment, a mounted workpiece, e.g., a diamond in a setting, may be inscribed on portions which are not obscured. For example, in a pronged setting, a portion of the girdle may be exposed, and thus may be available for marking. In this case, a multi-articulated holder or set of holders may be provided to properly position the workpiece within the inscribing chamber of the device. Holders may be provided to accommodate mounted gems in rings, earrings, pendants, and possibly bracelets, brooches, and other common forms.
[0029] The computerized control system provides a user interface making the various functionality accessible to users, and may further limit use and operation to safe and/or desired activities. Therefore, the computerized control system may be programmed to limit activities which would damage the workpiece, circumvent security or authentication procedures, or otherwise be undesired. The computerized control system may therefore require user authentication, employ video pattern recognition of the workpiece, especially markings on the workpiece, and control operation of the laser system to avoid damage to the system components or the particular workpiece. The system may also acquire an image, fingerprint, retinal image or other secure identification of the operator.
[0030] The system may also include a diamond or gemstone analysis system for describing the quality and/or characteristics of the workpiece. This analysis may be employed by the system in order to optimize the marking process, generate data to be marked on the workpiece, and/or to store data identifying the workpiece in relation to the marking. This system may operate automatically or semiautomatically. It is noted that, where gemstone classification automation is employed, a failsafe classification scheme will generally be employed which provides a manual classification or preclassification first. Thus, the risk of mismarking or misclassification will be reduced by the redundancy. The characteristics of the workpiece may be used to control parameters of the marking process.
[0031] Where a diamond having a polishled girdle is to be marked, a single pass inscription is generally sufficient, and all automated optical feedback system may reliably control operation. However, the optical absorption of a smooth girdle on a diamond is low, so that a dye or ink coating is required to be placed on the surface, to ensure absorption of the laser energy. Where the girdle is rough, multiple passes of the inscription device may be necessary to generate a desired marking. The optical absorption of a rough girdle is generally high enough to dispense with the need for optically absorptive dyes or inks. While the execution of retries may be automated, user control may be desirable, and such control is possible through use of the video cameras which are directed at the workpiece, which display a real time image on a computer monitor.
[0032] An optically absorptive dye or ink may be manually applied to the workpiece, such as by a marking pen, or the application process may be automated by applying the dye to a workpiece surface to be marked, such as with a porous marking tip. Advantageously, these inks or optically absorptive dyes remain on the surface of the workpiece, and would not be expected to penetrate. In general, a dye is selected which may be easily removed after marking by use of a solvent, such as alcohol. The dye may be removed manually or through an automated process, such as wiping with a solvent saturated pad.
[0033] In another embodiment, relief inscriptions are possible by modulating the laser pulses or selectively multiply ablating or graphitizing the workpiece at desired positions. Such relief markings are generally not necessary for simple alphanumeric or digital code inscription, but may be useful for logos, pictorial works, antialiasing of raster images, binary or Fresnel-type optics, diffraction optic effects, anti-piracy or anti-copying provisions, or in other circumstances.
[0034] In systems provided with two video cameras, video profiling of the workplace is possible, which may be used to determine an optimal position of the workpiece for marking without requiring focus checking at each location. The dual cameras also allow positioning and viewing on the same video screen, wherein the camera views are each provided as separate image windows. The cameras are useful for determining an appropriate marking location, ensurng laser beam focus, aligning the stone, and monitoring progress of the marking process.
[0035] The computerized control system allows versatility in the design, selection and implementation of graphic and font inscription. In a preferred embodiment, Borland fonts are employed. However, other fonts or combinations of fonts may also be employed, for example, Borland, postscript, TrueType, plotter, or other type fonts or typefaces may be employed. Further, the marking system may be set up to respond to Adobe Postscript, Microsoft Windows GDI, Macintosh QuickDraw, HP-GL, or other graphics standards.
[0036] A preferred laser system is a self-standing diode laser pumped Q-switched Nd:YLF laser with an internal frequency doubler. Such a system avoids the requirements of a relatively large YAG laser with large power supply and strict environmental control, an external frequency doubler, a water cooling system, large size and weight, inherent instability, and long optical path.
[0037] A green filter is provided on the output of the laser to selectively filter laser diode emissions, while allowing the green (530-540 nm) laser emissions to pass. The laser diode illumination is undesirable because it saturates the image on the vertical (Z-axis) camera screen in the laser spot area and prevents convenient viewing of the girdle and inscription.
[0038] The preferred translatable stage arrangement overcomes a typically limited range of optical movement of laser steering systems, requiring inscription operations in multiple segments, and provides good absolute positioning repeatability. However, according to some embodiments of the invention, other types of beam positioning apparatus may be employed, such as beam steering systems.
[0039] A marking may be provided on the stone for a number of reasons. First, it may be desirable to identify a stone if it is lost or mixed with other stones. The marking may also be used to identify source or origin. In this case, the marking may be taken at face value.
[0040] In some instances, however, a risk of forgery or simulation requires further security measures. Therefore, it may be desired to ensure that the stone was marked by an indicated entity, or that the stone corresponds to the marking applied thereto. This requires one of at least two possible schemes. First, that a characteristic of the stone be unique and very, difficult to simulate. For example, certain dimensions or ratios of the gemstone are the subject of somewhat random variations, and thus have a somewhat uncontrolled range of values. Natural flaws and other characteristics are also generally random in nature, and thus also difficult to simulate. It is therefore unlikely that one stone will correspond to another stone, and it is unlikely that another stone can be made to identically correspond to the determined dimensions and ratios through manipulations.
[0041] According to one aspect of the invention, therefore, these difficult to reproduce characteristics are used as an integrity check for an encoded message. These characteristics may be measured or recorded, and stored. Advantageously, these measurements and characteristics may be derived from an image of the stone captured in conjunction with the marking process. In fact, by storing such images and providing a pointer to the image, e.g., a serial number, the measurements or characteristics to be compared need not be determined in advance. Therefore, according to such a scheme, the stone need only include a pointer to a record of a database containing the data relating to the stone to be authenticated. This allows information relating to characteristics of the stone, which may be difficult to repeatably determine or somewhat subjective, to be preserved in conjunction with the stone or an identification of the stone. As stated above, an image of the stone on a certificate of authenticity may be used to verify that the stone is authentic, while providing a tangible record of the identification of the stone.
[0042] Another scheme relies instead on the difficulty in identically copying an inscription, including subtle factors and interactions of the laser marking beam with the stone itself. Thus, the marking itself is self-authenticating. An attempt to copy the marking will likely fail because of the technological limitations on the laser marking techniques, and/or insufficient information to determine all of the encoding information.
[0043] Thus, to authenticate a stone, either the markings alone or the markings in conjunction with the characteristics or physical properties of the stone are analyzed. In one scheme, the markings inscribed on the stone include information which correlates with characteristics of the stone which are hard to duplicate, and which recur with rarity, allowing self-authentication. In other schemes, the marking inscribed on the stone identifies a database record stored in a repository, thus requiring communication with the repository to obtain the authentication information. The hand cutting process for gemstones makes it is difficult or impossible to identically duplicate all measurable aspects of a stone, especially in conjunction with other physical characteristics, such as natural flaws. Such physical properties may include, for example, the girdle width at predetermined locations. The location may be identified, e.g., by an inscribed marking or by an offset from a marking which is not apparent from an examination of the stone alone. For any given gemstone, one or more such locations may be stored, thus increasing the difficulty in simulating the measurement. Further, such measurements are generally easy to obtain or determine from the imaging system of the inscribing system.
[0044] Sophisticated techniques, such as Raman scattering analysis, are known which may provide unique information about a particular natural crystal structure. While the preferred system does not employ Raman scattering analysis, such analysis may be used in conjunction with embodiments of the invention.
[0045] According to a preferred embodiment, the authenticity of a stone is determined may be determined by use of a jeweler's loupe to compare the actual stone to an image of the stone, such as may be provided on or in conjunction with a certificate of authenticity. Because each stone has varying characteristics, including the marking, details of the cut, and the relationship of the marking to the landmarks of the stone, the image serves as a fingerprint, making each stone essentially unique. The certificate, in addition to the image of the stone, may also include other information, such as an encrypted code, as discussed below. Thus, both the stone and the accompanying certificate may include identifying information.
[0046] Thus, the present invention also encompasses secure certificates, i.e, documents which are tamper and copy resistant, bearing an image of a marked stone, security features, and authentication features. Known secure documents and methods for making secure documents and/or markings are disclosed in U.S. Pat. Nos. 5,393,099; 5,380,047; 5,370,763; 5,367,319; 5,243,641, 5,193,853, 5,018,767; 4,514,085; 4,507,349; 4,247,318; 4,199,615; 4,059,471; 4,178,404; and 4,121,003, expressly incorporated herein by reference. U.S. Pat. No. 4,414,967, expressly incorporated herein by reference, discloses a latent image printing technique, which may be used to from an image of a workpiece. U.S. Pat. Nos. 5,464,690 and 4,913,858, expressly incorporated herein by reference, relate to certificate having holographic security devices.
[0047] In another scheme, a stone may be authenticated without the certificate of authenticity, e.g., by a typical jeweler employing simple tools, such as a jeweler's loupe and telephone. Therefore, according to one embodiment of the invention, a jeweler uses a loupe to read an alphanumeric inscription, invisible to the naked eye, on a gemstone. The alphanumeric inscription, or a portion thereof includes identifying information about the gemstone, e.g., a serial number, which is entered into an authentication system, e.g., by a telephone keypad. The characteristics of the stone, determined at or around the time of the marking process, are then retrieved from a database. In general, these stored characteristics may include grading, size, identification and possible location of flaws, and an image of the stone, including unique or quasi-unique features. Thus, for example, an image of the marking and stone or portions of the stone, e.g., surrounding landmarks of the stone may be stored. Some or all of these characteristics may then be provided to the jeweler, such as by voice synthesis, telefacsimile of the image, or otherwise. Where a certificate of authenticity is available, the certificate may be recreated and a facsimile transmitted to the jeweler, allowing verification of all information contained thereon. The jeweler then compares the retrieved metrics and indicia with those of the stone. If the stone corresponds to the stored information, the stone is likely genuine. If, on the other hand, the stone does not correspond to the stored information, it is possible that the stone is a forgery.
[0048] In another embodiment, the authentication system requests a series of measurements from the jeweler, which may be obtained by micrometer or reticle in a loupe, without providing the nominal values to the jeweler, so that no explanation is provided for a failure to authenticate, making forgery more difficult. Of course, the system may also employ more sophisticated equipment for measuring characteristics of the stone and for communications, including a fully automated analysis and communications system.
[0049] In another embodiment, the gemstone is self authenticating. Thus, instead of comparison with metric data stored in a database system, the marking inscribed on the stone itself includes an encrypted message containing data relating to characteristics of the stone. A number of different types of messages may be employed. For example, a so-called public key/private key encryption protocol, such as available Crom RSA, Redwood Calif., may be used to label the workpiece with a “digital signature” See, “A Method for Obtaining Digital Signatures and Public Key Cryptosystems” by R. L. Pivest, A. Shamir and L. Adelmann, Communications of ACM 21(2): 120-126 (February 1978), expressly incorporated herein by reference. In this case, an encoding party codes the data using an appropriate algorithm, with a so-called private key. To decode thed message, one must be in possession of a second code, called a public key because it may be distributed to the public and is associated with the encoding party. Upon use of this public key, the encrypted message is deciphered, and the identity of the encoding, party verified. The data in the deciphered message includes a set of unique or quasi unique characteristics of the gemstone. Therefore, one need only compare the information from the decoded message with the stone to verify the origin of the gemstone and its authenticity. In this scheme, the encoding party need not be informed of the verification procedure. Known variations on this scheme allow private communications between parties or escrowed keys to ensure security of the data except under exceptional authentication procedures.
[0050] Typical encryption and document encoding schemes which may be incorporated, in whole or in part, in the system and method according to the invention, to produce secure certificates and/or markings, are disclosed in U.S. Pat. Nos. 5,426,700 (and 07/979,081), 5,422,954; 5,420,924, 5,388,158; 5,384,846; 5,375,170; 5,337,362; 5,263,085; 5,191,613; 5,166,978; 5,163,091; 5,142,577; 5,113,445; 5,073,935; 4,981,370; 4,853,961, 4,893,338; 4,995,081; 4,879,747; 4,868,877; 4,853,961; 4,816,655, 4,812,965; 4,637,051; 4,507,744; and 4,405,829, expressly incorporated herein by reference See also, W. Diffie and M. E. Hellman, “New directions in cryptography”, IEEE Trans information Theory, Vol IT-22, pp 644-654, November 1976, R C Merkle and M E Hellman, “Hiding information and signatures in trapdoor knapsacks”, IEEE Trans Information Theory, Vol IT-24, pp. 525-530, September 1978, Fiat and Shamir, “How to prove yourself practical solutions to identification and signature problems”, Proc. Crypto 86, pp 186b-194 (August 1986), “DSS specifications of a digital signature algorithum”, National Institute of Standards and Technology, Draft, August 1991; and H. Fell and W Diflie, “Analysis of a public key approach based on polynomial substitution”, Proc. Crypto. (1985), pp 340-349, expressly incorporated herein by reference.
[0051] Another encoding scheme uses a DES-type encryption system, which does not allow decoding of the message by the public, but only by authorized persons in possession of the codes. This therefore requires involvement of the encoding party, who decodes the message and assists in stone authentication.
[0052] In order to provide enduring authentication, it may be desired that multiple codes, containing different information in different schemes, be encoded on the gemstone, so that if the security of one code is breached or threatened to be breached, another, generally more complex code, is available for use in authentication. For example, a primary code may be provided as an alphanumeric string of 14 digits. In addition, a linear bar code may be inscribed with 128-512 symbols. A further 2-D array of points may be inscribed, e.g., as a pattern superimposed on the alphanumeric string by slight modifications of the placement of ablation centers, double ablations, laser power modulation, and other subtle schemes which have potential to encode up to about 1 k-4 k symbols, or higher, using multivalued modulation. Each of these increasingly complex codes is, in turn more difficult to read and decipher.
[0053] The ablation pattern of the marking is subject to random perturbations due to both system limitations and surface variations of the stone. Thus, even with a self authenticating code, it is generally desired to store image information relating to the stone in a database after the marking process is completed. This database may then be used for further verification or authentication by image comparison or feature extraction.
[0054] Thus, a number of authentication schemes may be simultaneously available. Preferably, different information is encoded by each method, with the more rudimentary information encoded in the less complex encoding schemes. Complex information may include spectrophotometric data, image information, and geometric dimensional topology. Thus, based on the presumption that deciphering of more complex codes will generally be required at later time periods, equipment for verifying the information may be made available only as necessary
[0055] Known techniques for using LD numbers and/or encryption techniques to preventing counterfeiting of secure certificates or markings are disclosed in U.S. Pat. Nos. 5,367,148, 5,283,422; 4,494,381; 4,814,589, 4,630,201 and 4,463,250, expressly incorporated herein by reference.
[0056] It is also noted that information may also be stored holographically in crystalline matter. Therefore, in accordance with the present invention, authentication holographic data may be stored within a crystal. The techniques for forming and reading such holographically encoded messages are known, and the use of such encoded messages to authenticate gemstones is a part of the present invention. Thus, the information may be stored as a hologram within the crystalline structure of the stone, or as a relief or phase hologram on a certificate. Therefore, a hologram may be formed directly from the gemstone, preferably optically enlarged. Since the laser markings comprise ablation spots, these will be apparent in the hologram. Further, since the marking process includes a laser, this same laser may be used to expose the hologram, using a modified optical system. For example, a pair of chromate holograms may be individually formed for each gemstone, one placed on the certificate and the other stored with the originator of the marking. The certificate may also include known secunty features.
[0057] Where an original hologram of the workpiece is available, authentication may be automated by optically correlating the hologram and the workpiece. This method will be very sensitive to subtle changes in the workpiece, and thus particularly tamper proof. Preferably the optical correlation pattern of the hologram and the workpiece is stored after generation or developing the final hologram, in order to compensate for any changes during processing. This optical correlation pattern may be stored photographically or digitally.
[0058] Therefore, it is a characteristic of this aspect of the invention that, in order to identify a gemstone, the information stored thereon identifies a database record relating to the stone, and including information relating thereto, or the stored information itself relates to characteristics of the stone.
[0059] In one aspect of the invention, the imaging system is ordinarily disposed to view both a portion of the girdle of the stone and a profile thereof. Therefore, it is generally desirable to derive the required information relating to the stone from the imaging system while the gemstone is mounted in the apparatus. Where the inscription itself includes encoded characteristics, these may be applied by the apparatus by imaging the stone through the imaging system, and applying an inscription based on the imaging system output, i.e., by using feedback positioning. An image of the inscribed stone may also be obtained and stored. As stated above, the inscription may be explicitly encoded with readily apparent information, such as an inscribed alphanumeric code, or may include covert information, such as ablation spot placement with respect to stone landmarks, beam modulation, spacing between distant ablation spots, and pseudorandom ablation markings. The markings may also include indicia made at critical portions to allow repeatable measurements, such as edge margins of the girdle.
[0060] According to one method of the invention, a gemstone to be marked is imaged, with the image analyzed and extracted information compared to information in a database. Preferably, the database is a central database, remote from the marking apparatus, and the stored information is in digital form. The image is compared to data relating to at least a subset of images of comparable gemstones. An encoded marking is then proposed for a location on the girdle of the stone which, is either absolutely unique, or unique when taken with an easily defined characteristic of the stone. The database system is employed to prevent identical markings on comparable gemstones, and thus fails to approve a proposed marking if it is too similar to any other stone in the database. Thus, according to this aspect of the invention, each stone has a unique coding, and only rarely will a stone be found which is capable of receiving an identical marking to a previously inscribed stone while meeting the same coding criteria. In a simple embodiment, the database assigns a unique serial number to each stone and prevents use of duplicate serial numbers. On the other hand, in a more complex scheme, serial numbers need not be unique if other characteristics of the stone may be used to distinguish candidates.
[0061] According to another aspect of the invention, the inherent limitations on the accuracy and repeatability of the marking process are employed to provide a unique encoding of a gemstone. Thus, the surface imperfections of the girdle and the ablation process itself interact to prevent a theoretically ideal marking. Because these effects may be due to vibration, power line fluctuations, laser instability and the like, they will tend to be random over a number of marking operations. These effects will also result from characteristics of the stone. Thus, an attempt to recreate a marking to a high level of detail, even with advanced equipment, will invariably be met with difficulty. Thus, by storing high resolution images of the actual marking, possibly including off axis images or defocused images to gain ablation depth infomation, authentication of the markings is possible.
[0062] In like manner, intentional or “pseudorandom” irregularities (seemingly random, but carrying information in a data pattern) may be imposed on the marking, in order to encode additional information on top of an a marking pattern. Such irregularities in the marking process may include beam modulation, double ablations, fine changes in ablation position, varying degrees of overlap of ablation locations, varying laser focus during pulses. Without knowledge of the encoding pattern, the positional irregularities will appear as random jitter and the intensity irregularities will appear random. Because a pseudorandom pattern is superimposed on a random noise pattern, it may be desirable to differentially encode the pseudorandom noise with respect to an actual encoding position or intensity of previously formed markings, with forward and/or backward error correcting codes. Thus, by using feedback of the actual marking pattern rather than the theoretical pattern, the amplitude of the pseudorandom signal may be reduced closer to the actual noise amplitude while allowing reliable information retrieval. By reducing the pseudorandom signal levels and modulating the pseudorandom signal on the actual noise, it becomes more difficult to duplicate the markings, and more difficult to detect the code without a priori knowledge of the encoding scheme.
[0063] While alphanumeric codes and other readily visible codes may be read by common jewelers, subtle encoding methods may require specialized equipment for reading. Therefore, another aspect of the invention provides an automated system for reading codes inscribed on a gemstone. Such a system operates as a video microscope with image analysis capability. The image analysis capability will generally be tuned or adapted for the types of coding employed, reducing the analysis to relevant details. Therefore, where a pseudorandom code appears in the ablation pattern, the individual ablation locations and their interrelations are analyzed. Likewise, where ablation depth or amplitude is relevant, confocal microscopy may be employed.
[0064] In like manner, a certificate of authenticity may be provided with authentication and security coding, to prevent forgery or counterfeiting. In addition to the techniques discussed above, a number of other known techniques are available for the tamper and copy protection of documents. In this case, the certificate adds an additional level to the security of the marking process. Therefore, while the workpiece preferably includes a secure marking which does not require a certificate of authenticity for authentication, the addition of the certificate eases the authentication process while making forgery more difficult.
[0065] A typical electronic reading device for a gemstone inscription will include a CCD imaging device with a high magnification lens, e.g., about 200 times magnification, and an illumination device. Apparent resolution of the CCD may be increased by multiframe averaging with slight shifts of the gemstone with respect to the CCD optical system. A computer system with a frame grabber or a tele-video system (e.g., a videoconferencing system) may be used to obtain the data and analyze it. In general, known image processing schemes may be used to extract the encoded information.
[0066] In addition to being analyzed for information content, i.e., the markings, the workpiece image may also be compared with an image stored in a database. Therefore, based on a presumptive identification of a gemstone, an image record in a database is retrieved. The image of the presumptive gemstone is then compared with the stored image, and any differences then analyzed for significance. These differences may be analyzed manually or automatically. Where a serial number or other code appears, this is used to retrieve a database record corresponding to the stone which was properly inscribed With the serial number or code. Where the code corresponds to characteristics of the stone and markings, more than one record may be retrieved for possible matching with the unauthenticated stone. In this case, the information in the database records should unambiguously authenticate or fail to authenticate the stone.
[0067] According to another aspect of the invention, the laser energy microinscribing system includes a semiconductor excited Q-switched solid state laser energy source, a cut gemstone mounting system, having an aperture, an optical system for focusing laser energy from the laser energy source, through said aperture onto a cut gemstone, a displaceable stage for moving said gemstone mounting system with respect to said optical system so that said focused laser energy is presented to desired positions on said gemstone, having a control input, an imaging system for viewing the gemstone from a plurality of vantage points, and a rigid frame supporting said laser, said optical system and said stage in fixed relation, to resist differential movements of said laser, said optical system and said stage and increase immunity to vibrational misalignments. By employing a laser system with low cooling and power requirements, the device may be made self contained and compact. By minimizing the size of the apparatus, and enclosing the device in a rigid frame or chassis, vibration immunity is improved. Thus, as compared to systems employing flashlamp excited lasers, substantial vibration isolation apparatus is eliminated.
[0068] According to another aspect of the invention, prior to any marking operation, the proposed marking and/or the presumed resulting image are compared to database records to determine if the proposed marking and/or resulting marked gemstone are too close to any previously marked gemstone to be easily distinguished. If so, the marking or proposed marking may be altered. In addition, as an automatic feature of the machine, this comparison may prevent use of an authorized machine to counterfeit a previously marked gemstone, and will insure the integrity of the database.
[0069] According to another aspect of the invention, a pattern marking is inscribed on a portion of the gemstone, such as a girdle. Because it is difficult to recreate a particular girdle pattern exactly, the pattern will allow, for example with a loupe, quantification of girdle characteristics, including width contour and size. Thus, the pattern assists in providing a metric for gemstone authentication.
[0070] The database may be stored locally to the marking apparatus but preferably a central database is maintained, receiving identification and/or image information from many remote marking locations, and allowing central control and retrieval of records. This also facilitates a separation of function to maintain the integrity of the system and long term authentication procedures.
OBJECTS OF THE INVENTION
[0071] It is therefore an object of the invention to provide a laser energy microinscribing system, comprising a pulse laser energy source; a workpiece mounting system, having an optical aperture; an optical system for focusing laser energy from the laser energy source, through said optical aperture onto a workpiece, means for directing said focused laser energy onto a desired portion of the workpiece, having a control input; an imaging system for viewing the workpiece from a plurality of vantage points; an input for receiving marking instructions; a processor for controlling said directing means based on said marking instructions and information received from said imaging system, to generate a marking in accordance with said instructions; and a storage system for electronically storing information relating to images of markings on a plurality of workpieces
[0072] It is also an object of the invention to provide a method of microinscribing a workpiece with laser energy front a pulse laser energy source, focused by an optical system on the workpiece, comprising the steps of mounting a workpiece in a mounting system, directing the focused laser energy onto a desired portion of the workpiece, electronically imaging the workpiece from a plurality of vantage points, receiving marking instructions from an input; controlling the directing of the focused laser energy based on the marking instructions and the electronic imaging, to generate a marking in accordance with said instructions; and storing electronic information relating to images of markings on a plurality of workpieces.
[0073] It is a still further object of the invention to provide a laser energy microinscribing system, comprising a semiconductor excited Q-switched solid state laser energy source, a cut gemstone mounting system, leaving an aperture, an optical system for focusing laser energy from the laser energy source, through said aperture onto a cut gemstone, a displacable stage for moving said gemstone mounting system with respect to said optical system so that said focused laser energy is presented to desired positions on said gemstone, having a control input; an imaging system for viewing the gemstone from a plurality of vantage points, and a rigid frame supporting said laser, said optical system and said stage in fixed relation, to resist differential movements of said laser, said optical system and said stage and increase immunity to vibrational misalignments.
[0074] These and other objects will become apparent. For a fuller understanding of the present invention, reference should now be made to the following detailed description of the preferred embodiments of the invention as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0075] The invention will now be described with respect to the drawings of the Figures, in which
[0076] [0076]FIG. 1 is a diagram of the laser optical path of the system according to the present invention,
[0077] [0077]FIG. 2 is a diagram of the top illumination and imaging systems according to the present invention;
[0078] [0078]FIG. 3 is a diagram of a side illumination and imaging systems according to the present invention,
[0079] [0079]FIG. 4 is a diagram of a bottom illumination system according to the present invention;
[0080] [0080]FIG. 5 is a block diagram of the stage positioning system and control according to the present invention;
[0081] [0081]FIG. 6 is a diagram of a prior art beam steering system,
[0082] [0082]FIGS. 7A, 7B, 7 C, 7 D, and 7 E are various views of a workpiece mounting system according to the present invention,
[0083] [0083]FIG. 8 is a flow chart depicting operation of a system according to a first embodiment of the present invention;
[0084] [0084]FIG. 9 is a block diagram of an apparatus according to the first embodiment of the present invention;
[0085] [0085]FIG. 10 is a block diagram of an apparatus according to a second embodiment of the present invention;
[0086] [0086]FIG. 11 is a flow chart depicting an automatic marking generating routine according to the present invention;
[0087] [0087]FIG. 12 is a flow chart depicting an authentication sequence according to the present invention,
[0088] [0088]FIGS. 13A, 13B, 13 C and 13 D show details of a marked diamond, a two dimensional marking pattern a modulated dot placement encoding scheme, and a detail of the marked diamond, according to the present invention, and
[0089] [0089]FIG. 14 is a semischematic view of the mounting frame, showing vibration dampers the corners thereof.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0090] The detailed preferred embodiments of the invention will now be described with respect to the drawings. Like features of the drawings are indicated with the same reference numerals.
[0091] The system according to the present invention may be used to micro-inscribe alpha/numeric characters on the girdle of diamonds 13 . It is based on a pulse laser 1 , and preferably a Q-switched laser diode pumped solid state laser, to provide minimum volume and installation requirements, and optimum compatibility with any office environment.
[0092] A preferred laser based inscribing system according to the present invention thus contains the following primary elements.
[0093] In a vibration isolated frame 140 with shock absorbers 141 , at the positions of support
[0094] (1) Laser diode pumped laser 1 and programmable power supply 14 , with a Beam Expander 5 .
[0095] (2) Optical assembly containing guiding 8 and focusing optics 10 , miniature CCD cameras 28 , 32 and illumination system.
[0096] (3) XYZ motion stages 50 (with Z elevator stage) including encoders 145 , limits and DC brushless motors.
[0097] (4) Diamond holder 144 and accessories
[0098] (5) Enclosure 142 with safety interlock 143 to prevent operation with open cabinet and to prevent stray or scattered laser energy from posing a safety hazard.
[0099] (6) Computer system 52 for control:
[0100] (a) PC (Pentium 100 Mhz), PCI bus, 1024 by 768 VGA monitor
[0101] (b) Frame grabber 56 (Matrox, videographic card)
[0102] (c) 3-axis motion controller card 60
[0103] (d) Cables, Power Supplies
[0104] (e) System operation software (Windows)
[0105] (f) Application Software
[0106] Apparatus
[0107] As shown in FIG. 1, a Nd:YLF 2 nd harmonic laser 1 (QD 321 q) is provided, which emits a beam 2 having about 525 nm wavelength. A 1047 nm filter 3 is provided to attenuate any residual fundamental laser output energy, to produce a filtered laser beam 4 . The filtered beam is then expanded in a ten-times beam expander 5 to reduce energy density. In the path of the expanded beam 6 , a 780 nm filter 7 is provided to eliminate energy from the diode pumps. A dichroic mirror 8 refects the expanded, filtered beam 9 toward a ten-times microscope objective 10 The microscope objective 10 focuses the beam onto the workpiece 11 , which is for example a girdle 12 of a cut diamond 13 .
[0108] [0108]FIG. 2 shows the top illumination and imaging systems. An LED 20 or array of LEDs having emission at about 650 nm projects through a collimating lens 21 to produce a collimated illumination beam 22 . The collimated illumination beam 22 projects on a beam splitter 23 , which reflects the collimated illumination beam 22 toward a reflecting mirror 24 . The reflected collimated illumination beam 25 passes through the dichroic mirror 8 , parallel to the filtered beam 9 , and through the microscope objective 10 onto the workpiece 11 . The workpiece 11 reflects a portion of the illumination beam back through the microscope objective 10 and through the dichroic mirror 8 , onto the reflecting mirror 24 , tracing an opposite path from the collimated illumination beam 25 . A portion of the reflected illumination beam 27 , however, passes through the beam splitter 23 , toward a top CCD camera 28 . Thus, the top CCD camera 28 views the workpiece 11 with the 650 nm illumination. When displayed on a 14 inch video monitor 159 , the resulting magnification of the image 29 is about 200 times.
[0109] The side illumination and imaging systems, shown in FIG. 3 is somewhat simpler than the top illumination and imaging systems shown in FIG. 2. A set of spaced 650 nm LEDs 30 produce illumination 31 at angles generally converging from the top toward the workpiece 11 . A side CCD camera 32 , views the workpiece 11 through a doublet lens 33 and window 34 , at right angles to the top CCD camera 28 . The resulting image 35 of the side CCD camera 32 on a 14 inch video monitor is also about 200 times magnification. Where the workpiece 11 is a cut diamond 13 having a girdle 12 , the side image 35 includes the profile of the girdle 12 ′.
[0110] The bottom illumination system, shown in FIG. 4 includes a set of spaced miniature are lamps 40 below the workpiece 11 , producing illumination along paths 41 which are upwardly converging.
[0111] The stage positioning and control system is shown in FIG. 5. The workpiece is mounted on a three axis stage 50 , with encoder feedback in a workpiece mount assembly 144 . The drivers 51 for the three axis stage are provided within the laser system enclosure 142 , separate from the computer control 52 . The computer control 52 communicates through a positioning control system 53 (Galil), which is an ISA bus card. A breakout box 54 is provided within the laser system enclosure 142 , which is connected by a set of cables 55 to the positioning control system 53 .
[0112] As shown in FIG. 6 (prior art), a known system described in U.S. Pat. No. 4,392,476 includes an X scanner 61 and a Z scanner 63 , which steer the laser beam onto the diamond 13 . This known system has limited repeatability. Further, the system is relatively large, and subject to vibrational influences.
[0113] FIGS. 7 A- 7 E show the diamond holder in top, side, side detail, mounted stone holder, and unmounted stone holder, respectively. A slide 116 allows precise positioning with respect to a slot, within the cabinet. The slide 116 is positioned by a set of hardened steel balls and spring loaded balls which positions the holder 116 as it is inserted into the slot. A set of manual adjustments allow control over coarse 106 and fine 104 rotation, with a lock/release chuck 107 provided. The workpiece 11 is set in a pot 108 mounted in a chuck 109 , with two round rods positioning the workpiece, held in place by a finger 110 .
[0114] As shown in FIG. 7D, a mounted workpiece holder allows a mounted workpiece 111 to be held precisely. A spring loaded trigger 112 is provided to allow mounting and unmounting of the mounted workpiece.
[0115] Mode of Operation
[0116] The system includes a static laser beam, e.g., a laser beam generation apparatus which does not move. The XYZ positioning system 50 moves the workpiece 11 and generates the inscription with repeatability and resolution of about 1.0 microns. The beam size at the focal point is greater than about 1 micron, so that the positioning system 50 accuracy is not the limiting factor in the placement of the marking.
[0117] With the axis of symmetry of the workpiece 11 , which is for example a diamond 13 , horizontally disposed, the diamond girdle 12 is viewed horizontally (profile mode) and vertically (inscription mode) by two CCD cameras 28 , 32 . The vertical axis also corresponds to the axis of laser 1 . A third camera may also be provided, for example having an optical path facing generally upward toward the laser. Of course, an imagining device facing the laser beam is provided in a manner to prevent damage during operation. Due to the focus of the laser 1 , as well as filtering optics 8 , 23 , 34 there is low risk of damage to the CCDs 28 , 32 due to laser energy. The user can choose to view one or more cameras. Where multiple images are present, they may be tiled at reduced size on the computer monitor screen 159 . Using a mouse 161 as a pointing device, the girdle 12 is centered and focused by viewing, the screen 159 , using particularly a profile view. The diamond 13 can be manually rofated in its mounting 144 to bring the correct part of the girdle 12 to the center of a display window on the screen 159 . The images are provided with a magnification of about 200 times, although other magnifications or variable magnifications are possible. Magnification is defined herein as the ratio of the inscription size as measured on screen 159 and that of the actual inscription size. In general, a 14 or 15 inch diagonal video monitor is employed, with a resolution of 1024 by 768 pixels.
[0118] The user-entered portion of the content of the inscription is typed on a keyboard 148 or entered by a bar-code reader 149 into the computer. Of course, the data entry may also be by voice through a microphone 150 for speech recognition, magnetic strip through reader 151 , or through point-and-click operations using a computer mouse 161 . The entered inscription and logo are shown on the video screen 159 superimposed on an area corresponding to the girdle 12 of the diamond 13 . Using the mouse 161 and keyboard 160 , the user can change all inscription characteristics in order to fit it correctly in the girdle 12 . While the preferred user interface is a graphic user interface with pointing device (mouse 161 ), keyboard 160 and display screen 159 , where the user's hands may be occupied, a voice-command recognition system may be used, e.g., through microphone 150 , with verification of all input information and commencement of operational sequence by a specific sequence of actions by the user in fail-safe manner, so that, e.g., stray noises do not cause catastrophic interference.
[0119] In the horizontal camera 32 screen the user can measure the girdle 12 profile, using a mouse input device 161 to mark the critical dimensions. This data is then used to keep the focal point of the laser output on the surface of the girdle 12 at all times. The profile data and girdle 12 outline may be automatically extracted from the images, or a manual entry, step employed to outline the profile and/or girdle boundaries. In general, the inscription positioning on the girdle will be manually assisted, although full automation, especially for low value small stones, known as mellee, may be employed. When these procedures are complete a so-called G-code file is generated containing all inscription data. This file is transferred to the positioning stage controller 51 for performance of the actual inscription.
[0120] The inscription code file may optionally be automatically generated and authorized based on an algorithm to prevent unauthorized or fraudulent inscriptions, as depicted in FIG. 11. The authorization process according to one embodiment of the invention includes the steps of obtaining or retrieving an image of the workpiece 171 , analyzing the image to determine characteristics of the workpiece 172 , transmission of the characteristics in conjunction with data relating to the stone to an authenticator, through, for example, a telecommunications link 152 , which may be at a different location, determining whether the characteristics and proposed marking are unique 173 , which may be performed remotely, or locally, and if the characteristics and marking are not unique, proposing a change in the marking 174 and then reverifying the modified proposed marking with the authenticator. After a marking is approved, the marking is encrypted 175 , and the encrypted code transmitted to the marking control 176 . Thus, only if the authenticator approves a marking does the system commence marking.
[0121] The characteristics of the workpiece may be determined by eye 146 , and may also be determined by a sensor 147 of appropriate type. For example, dimensions, weight, optical transmission characteristics, facet angles and the like may be measured. During the initial marking process, the characteristics are determined, and are preferably stored in conjunction with the marking information in a database 156 . For example, this database may store images, compressed images or aspects of images derived from the CCD imagers 28 , 32 . Preferably, after the marking has occurred, the top CCD imager 28 is used to capture an image of the marking, which is then stored. According to one embodiment of the invention, information stored in the database or marked on the stone may be encrypted using a secure encryption method by means of an encryption processor 157 , reducing the risk of fraud. Further, the marking may be, in part, self authenticating by including identification of characteristics of the marked workpiece. Of course, the encryption processor may be the same as the control system 155 , and need not be a separate physical device.
[0122] The controller executes all I/O operations such as laser on/off, laser power out of range, limit switches, mouse, etc., as well as performing the motion itself. Thus, the control system may easily be upgraded as desired separately from the marking system hardware.
[0123] The operator can observe the diamond before, during and after the inscription marking process. In case the inscription is not complete, the operator can choose to repeat all or selected parts of this inscription in a second or subsequent marking operation.
[0124] [0124]FIG. 8 shows a flow diagram of the operation of the control system for the laser inscription process. A software module in the control system generates interrupts which sense laser system conditions, and may also initiate action automatically based on those conditions 121 . The inputs to the laser system sensing module 121 include emergency stop 122 , laser ready 123 , mechanical limit reached 124 , and door open 125 . Of course, other conditions may be sensed and controlled by this sensing module 121 .
[0125] A main interface screen 126 is provided allowing the operator to access and control the main functionality of the laser inscription system. This interface screen 126 initially controls laser warm up and positioning at a home position 127 . After a gemstone is inserted into the laser inscription system, it is jogged into alignment 128 with reference to the top and side views, displayed on the video monitor. Next, the inscription is entered or edited by an input device such as a keyboard 148 or bar code reader 149 , and the inscription positioned with respect to the workpiece in the top view 129 . If the workpiece has a rough surface, such as a brutted girdle of a diamond, the inscription positioning is verified in the side view 130 . The host computer 52 sends commands to the laser inscription controller 60 defining the inscription pattern, by defining XYZ positioning of the workpiece 131 and a pattern of laser modulation 132 , in order to define the inscription pattern, e.g., the font or logo structure. After all or a segment of the inscription is made, the inscription is verified to ensure complete inscription, and all or a portion of the inscription may be repeated as necessary 133 . The inscription is then complete, and a new inscription process may be commenced 134 .
[0126] In addition, a maintenance mode of operation is available, which allows adjustment of system parameters 135 , motion system diagnostics 136 , and a summary report of inscription data 137 .
[0127] Inscription Specification
[0128] The length of inscription depends on size of characters and spacing. Below is a table representing appropriate dimensions
HEIGHT WIDTH SPACING (microns) (microns) (microns) Large characters 80 60 30 Medium characters 60 45 25 Small characters 40 30 20 Ex Small chars 20 15 10
[0129] The total length of inscription=number of characters X (width+spacing)+logo length
[0130] The system accommodates maximum single inscription lengths of approximately 2 mm. At an average of 80 microns per character (including spacing) this gives 25 characters which covers requirements for logo+14 characters. Longer inscriptions can be implemented by consecutive inscriptions without dismounting diamond. In this case there is no limit on number of characters, except by the available surface area. Each logo+14 characters is accounted for as a single inscription process. Inscribing more characters would normally present no problem. It is noted that the characters may be alphanumeric, line-drawing, multi-lingual fonts, custom bitmaps, or other pictorial representations, and may be fully programmable.
[0131] The software of the control system also allows any number of inscribed symbols. It is also easy to rotate the stone and position a section of the inscription so that it is or seems to be continuous with the first one. Any symbol size may be produced, within the limits of the line width and surface to be inscribed. For example, with a red beam, the lower limit of symbol size is around 30 microns. With a green beam the lower limit of symbol size is about 15-20 microns.
[0132] The depth of inscription is less than about 10 microns.
[0133] The line width (green beam) is less than about 9 microns on a polished girdle and less than about 12 microns on a brutted girdle. The system employs a green laser to provide a finer inscription line width than is possible with a standard-type red laser. Start up time for the system is about 15 minutes, mostly accounted for by laser stabilization time, after which the instrument is fully operational, an advantage over other laser types. In a preferred marking method, the irradiated areas overlap, to provide an appearance of continuity of marking.
[0134] The laser output is provided as a Q-switched laser, which may be provided in a range of about 1200 to 200 nm, with a frequency doubler or harmonic generator as necessary to provide an output wavelength of less than about 600 nm. A preferred laser 1 is a Q-switched solid state neodynium laser, e.g., a laser diode pumped Nd:YLF laser, operating at 106 μm, with a frequency doubler to provide in output of 530 nm.
[0135] Operating according to the system heretofore described, net inscription times (laser time) are estimated to be less than 20 seconds for polished girdles and about less than 35 seconds for brutted girdles.
[0136] On polished girdles, inscriptions are generally satisfactory after a first pass. Brutted girdles, on the other hand, may require multiple passes, depending on surface quality, to achieve a desired marking. For time efficiency, multiple runs are executed only on those characters requiring additional runs. These characters can be marked with the mouse. Of course, the reruns may be automatically performed based on a predetermined criteria or based on optical feedback from the video cameras.
[0137] Mounting and dismounting the stone is performed using a modular holder 144 with a quick connect socket, and therefore may be accomplished in about 20-30 seconds, The rest of the operations, e.g., locating optimal place for inscription, painting, etc., depend on the manual skill of the operator, and may take about 30-40 seconds. Consequently, 40 stones per hour throughput is possible using the apparatus according to the present invention.
[0138] DC brushless motors are employed in the translatable stage system 50 . These are driven by a standard-type motor driver system. The X, Y stage employs linear encoders for feedback of stage position, while the Z stage employs a rotary encoder for a helical positioning mechanism.
[0139] Font and Symbol Capabilities
[0140] An assortment of characters may be provided with each system, such as an ASCII font set containing 26 letters and 10 numerals, business characters as follows (TM), (SM), ® and a logo. These font sets are, e.g., available from Borland Additional fonts, e.g , Japanese and/or Hebrew, and logos may, of course, be employed, e.g., added to the system using removable magnetic media, smart cards, or by digital telecommunication. The font may also include custom or editable characters, allowing full freedom to define a raster bitmap represented by a character identification code. Thus, any figure which can be rendered in lines or a bitmap may be included as a marking.
[0141] Inspection data can be entered in three ways.
[0142] Manually-alphanumeric symbols entered from the keyboard 148 and logo selected from the logo library.
[0143] Semi-automatic—part of the alphanumeric symbols from bar-code 149 or from a keyboard 148 and part of the symbols selected automatically by a serialization counter.
[0144] Fully automatic—a complete inscription is generated by the device, after inputting an identification from bar code or similar system.
[0145] Using a graphic video overlay, the inscription position and dimensions can be easily adjusted.
[0146] The system controller also provides over/under power protection. In case laser power exceeds set limits the system will stop working and issue a warning, thus ensuring that no damage is caused to the diamond or a workpiece.
[0147] Vibration dampers 141 are provided at the base of the laser system frame 140 . Thus, due to the compact size of the system and relatively small components, the frame 140 may have sufficient rigidity to provide isolation from vibrational effects. Operation is therefore possible in any normal office environment at normal room temperature, without extraordinary measures, such as strict environmental control, or active vibration damping.
[0148] The computer 52 is a “PC” type, and is generally provided as a separate enclosure from the laser inscribing system enclosure 142 . Generally, two cables 55 connect the computer controller 55 to the laser system enclosure 142 , a motion controller and laser control cable and a frame grabber cable. The user may therefore position the screen 159 and keyboard 160 with mouse 161 at the most convenient position.
[0149] Inscription Observation
[0150] The system includes two high resolution miniature CCD cameras with illumination and filter systems for efficient viewing of entire inscription process on a video screen as follows:
[0151] The complete inscription with logo is projected on an image from a vertically oriented camera 28 of the girdle 12 providing the user with the ability to interactively change length of inscription, height of characters remove and align the whole inscription. The girdle 12 area may be outlined by the user with a mouse 161 or automatically determined by image analysis in the computer system 52 .
[0152] The operator can thus observe the inscription before marking, observe the marking process itself, and then observe the result and decide if the inscription is complete or not. A protective enclosure 142 prevents scattered radiation from reaching operator eyes. Filters or the like may also be provided to prevent damage to the video cameras from reflected laser energy
[0153] The operator is provided with complete control of positioning, and inscription allowing approval of the inscription before laser operation. Cursors on the screen help in centering the inscription. The system also has a side camera 32 for girdle 11 profile mapping and table viewing.
[0154] The operator marks as many points that are needed on the profile allowing the system to then automatically adjust (Z-axis focal location) to conform to the girdle profile during marking. A manual override is also provided where the automated inscription depth control is not desired.
[0155] The side camera 32 allows precise determination of the position of the girdle 12 of the gemstone 11 , so that the laser 1 may be focused onto the gemstone 11 surface with high precision. In order to effectively ablate a small surface portion of the gemstone 11 , without damaging deeper portions, or producing significant undesired thermal stress effects around the inscription, the laser 1 is provided with a very narrow depth of field, e.g , about 30 μm. In addition, the small depth of field is required in order to obtain maximum power density from a relatively low power laser 1 . Thus, by attempting to focus using a top view only, without a profile view, to achieve focus by maximizing contrast and edge sharpness, user discretion is required and accuracy is limited. In contrast, by providing a side view, the profile of the stone is aligned with a predetermined focal plane, assuring accuracy of about ±7 μm. In practice, at 200 times magnification, the ±7 μm corresponds to ±2 pixels of the video imaging camera. Thus, after determining the exact focal plane of the laser 1 empirically, this plane may be provided as a reference in the control system, and the workpiece moved manually or automatically with relative ease to the desired location(s) The reference may appear, for example, as a line on a computer monitor displaying a Z-axis video image of the workpiece. The operator jogs the Z-axis control until the profile of the workpiece 11 in the image is tangent to the reference line.
[0156] Vibration and/or impact during, e.g., shipping, may alter the focal plane of the laser with respect to the workpiece mount 144 In this case, a simple “trial and error” or empirical study is conducted to redetermine the exact focal plane, which is then used to provide the correct reference in the control. This calibration study may be conducted, for example, on a relatively inexpensive diamond or other material test piece, in which successive ablations are conducted under differing conditions, e.g., differing Z-axis positions at successive positions in the X-Y plane. After the series of ablations, the test piece is examined to determine the optimial conditions of orientation, e.g., smallest spot size. The conditions of the optimal orentation are then used to determine the focal plane and hence the calibrated reference plane.
[0157] The user has complete control over character sizing. Once the cursors are placed on the girdle (according to girdle dimensions) the computer will display a first choice which the user can change.
[0158] A motorized Z-axis is provided for focusing the laser onto the workpiece surface. This Z-axis is computer controlled, and enables the operator to focus onto the girdle 12 of the diamond 13 by means of the computer keyboard controls, with direct position input to computerized numeric control (CNC). The girdle profile is determined by reference to an orthogonal view to the girdle surface, and therefore the Z-axis may be controlled for each coordinate. A system may also be provided which uses hand operated micrometer screws for focusing, for example where long inscriptions on fancy shaped stones necessitates the use of segmented inscriptions.
[0159] The parameters of the inscription process, including laser power, Q-switch frequency and inscription speed, may be controlled for optimization of the laser-maternal interaction when switching between substrates and differing surface qualities. Thus, the present invention allows the implementation of varying ablation sequences based on the desired inscription and the characteristics of the workpiece. Often, the characteristics of the workpiece are known and input into the control system, i.e, by a bar code, magnetic strip manual keying, database retrieval, or other method. However, the system according to the present invention may also include a system for itself determining a characteristic or set of characteristics off the workpiece and implement an inscription process based on the input or determined characteristics and the desired resulting inscription. Likewise, where an inscription is preexisting, the system according, to the present invention may analyze the existing inscription and produce a modified inscription. Thus, where features according to the present inscription method are desired, they may be superimposed on or added to existing inscriptions. Further, an old inscription may be analyzed and stored according to the present methods without any modifications thereto, e.g., for security and authentication purposes.
[0160] Software
[0161] The computer controller preferably operates in a Windows environment, although Windows 95 or NT, Macintosh, UNIX derivatives, X-terminal or other operating system which supports the various system components may be employed. The optical feedback system and preview of inscription functions advantageously employ a graphic user interface.
[0162] All machine features are generally controlled by the software, with the exception of laser pulse power and pulse frequency, which are set from power supply panel. Of course, the laser control system may be completely automated with a computer control, allowing software control over pulse power, Q-switch frequency, and inscription speed.
[0163] User control and input for interaction with the software, which is preferably a graphic user interface system, is generally performed via mouse 161 and keyboard 160 . Data entry of workpiece information may employ other input devices, such as a microphone, optical or bar code scanner, gemstone characteristic sensor, magnetic disk or stripe, or other known input devices.
[0164] The software can generate various reports according to specifications and formats as desired, based on an individual inscription procedure or a number of inscriptions. The software may also be used to generate a certificate of authenticity with anti-forgery and anti-tamper features, with an image of the workpiece.
[0165] Images obtained through the CCD images can be stored, for example, on magnetic disks or optical media, and may be stored locally or remotely. Such storage may be useful in order to identify and inventory workpieces, or to ensure system operation.
[0166] The computer may also be provided with standard computer networking and communications systems. For example, an Ethernet communication link, IEEE 802 3 may be used to communicate over a local area network. Communications with a central database may occur over telephone lines using a standard analog modem, e.g., v 34 , ISDN, Frame Relay, the Internet (using TCP/IP), or through other types of private networks. Data is preferably encrypted, especially when in transit over unsecure public channels.
[0167] Logo and graphic editors are also provided for the creation of logos and graphics. A font editor is provided to edit character raster images of fonts. Because the raster image corresponding to each code is programmable or modifiable, complex symbols may be inscribed with the same ease as letters and numbers, once the symbol is defined as a font character. According to one aspect of the invention, a graphic pictorial image is engraved onto the stone, thereby making the stone an artwork. The pictorial image may be identical or different for each stone, and may also include encoded information. A logo may differ from a character by being larger, with potentially a higher dot density. Thus, characters are generally defined as raster bitmaps, while logos may be further optimized or the laser controlled to obtain a desired appearance.
[0168] Stone Mount
[0169] The mount includes a fixed base, held in fixed position with respect to the frame 140 , with a removable holder 118 , as shown in FIGS. 7 A- 7 E The holder 118 can be easily removed or taken out from the fixed base without changing the diamond's orientation. A holder 118 is selected based on the diamond size to be processed in the machine, with various holders available for differing sized stones. The diamond can be easily placed in or removed from the holder and can be externally adjusted to bring the correct part of the girdle to face the camera.
[0170] The diamond holder is based on a standard holder known in the diamond industry. The diamond center sits in a concave depression suited to the diamond size. A spring loaded metal strip 110 pushes against the table to hold the diamond securely into the pot 108 , while making sure that the table is parallel to the holder 118 axis. If the girdle plane is not parallel to the table or the girdle surface is not parallel to the diamond axis of symmetry, the holder provides two adjustments knobs 105 , 117 to correct for those cases so that, when viewed through the video camera 28 on a video screen 159 the girdle 12 is horizontal and the entire relevant surface is in focus. In addition, there are adjustments for rough 106 and precise 104 rotation of the diamond 13 in the holder 118 . Rotation about the center axis of the diamond 13 is therefore achieved manually, although an automated or mechanized rotation is also possible. The rough adjustment 106 has 16 rotational steps, while the tine adjustment 104 is continuous.
[0171] All of the above adjustments of the diamond in the holder 118 can be performed outside of the inscribing apparatus and the diamond 13 can therefore be pre-aligned before insertion into the machine. The holder 118 is designed in a manner enabling access to all the adjustment knobs with one hand, while the holder 118 is inserted into he machine. Correction through visual on screen feedback 159 can be easily achieved.
[0172] The user is provided with a range of controllable-intertsity illumination aids. The laser axis, for example, is illuminated with a red LED 20 , which is useful for viewing polished girdles 12 in the vertical (Z-axis) camera 28 . In order to provide high contrast between the workpiece 11 profile and the background, three groups of LEDs 30 are provided around the microscope objective 10 , illuminating the workpiece 11 from three sides. Each side-illumination group 30 may have, e.g., three LEDs. Further, two miniature are lamps 40 are provided to illuminate the workpiece 11 from the bottom. This lower illumination is useful, e.g., for observing brutted girdles 12 of diamonds 13 in the vertical (Z-axis) camera 28 .
[0173] The complete holder 118 is very easily inserted into the machine. In the machine there is a fixed base with a slot. The slide 116 of the holder 18 slides in the slot, in the manner of a credit card or cassette tape, and comes to a precise halt. Spring based ball-tipped plungers facilitate the sliding action and prevent the holder from making any movement when the machine is operating, by engaging countersunk recesses 103 . The holder 118 can be taken out and inserted back again with the diamond 13 coming to the same place as before.
[0174] The general structure of the holder 118 is shown in FIGS. 7 A- 7 E. The operator can hold the unit with one hand, normally the left hand, and insert the holder into the slot. With the same hand the operator can make all the adjustments while monitoring the video screen and operating the mouse or keyboard with his right hand. The holder 18 position in the slot is very well-defined and the holder can be taken out and reinserted with the diamond 13 and holder 118 regaining the same position. When taken out, the holder 118 has an “out” position where it is still supported by the slide 116 and the stone is 40 mm out of the machine. In this position, the stone can be inked, inspected, cleaned, etc., without need for the user to support the unit with one hand.
[0175] The stone 11 is positioned by the holder 118 and mount so that the center axis is horizontal and is perpendicular to the laser beam. The holder 118 is made of steel. The contact points are the concave cup 108 which supports the center of the diamond, and a strip 110 which presses on the table toward the cup 108 in a manner that assures parallelism of the table to the symmetry axis of the holder 118 , and assures correct positioning with respect to the laser beam. In a preferred arrangement, three sizes of holders 118 are provided to cover a range of diamond 13 sizes. The holder 118 can support any stone which has a center and a table. In addition, holders 118 may also be designed to accommodate special fancy shapes.
[0176] In general, it is desired to make the set-up and inscribing times approximately equal, so that the machine is always busy inscribing. Thus, further improvements in set-up time will not improve throughput. Therefore, a set of stone holders is provided. The user is provided with enough holders ready for inscribing, and that means the machine is inscribing almost continuously. The procedure is as follows:
[0177] Stones are prealigned on holders. The operator, on completing the inscription, removes the holder with an inscribed stone and inserts a prepared holder with a stone to be inscribed. Minor adjustments may be required of the diamond or the holder, which may be accomplished under guidance of the video imaging system. In addition, the operator must also input or define the inscription. The inscription process is then commenced. During the inscription, the operator can remove the stone from the previously used holder, allowing reuse. Generally, a large number of holders will not be required to ensure that the inscribing system is always busy, i.e., there is always a holder readily when the inscribing operation is complete. Where single operator productivity is maximum, a second operator may assist in mounting stones in holders and/or defining the inscription process.
[0178] Mounted stones are held by a holder 119 which has a design which depends on the fact that some of the girdle 12 must be exposed for the inscription process to take place. Thus, the holder 119 is provided with three fine “claws” 120 which can be opened and closed by pressing a “trigger” 112 . The claws 120 are spring loaded in the closed position. The claws 120 grasp around the girdle 12 (between prongs of the setting) and press the table against a flat surface 138 upon release of the trigger 121 . The flat surface 138 is perpendicular to the gemstone central axis. The holder 119 design thus assures that the gemstone 11 is centered and held firmly, and allows the stone to be rotated to a desired location for an inscription.
[0179] Since a mounted stone is held in an opposite manner from an unmounted stone, the inscription direction is preferably reversed. This reversal is accomplished, for example, within the control software. In this case, the inscription may be inverted, with the inscription process commencing from the “beginning”, or the inscription made in reverse order. In order to facilitate the following of the inscription process by the human operator, the inscription preferably proceeds from the “beginning”, and the reversal is selected as a screen “button” of the graphic user interface system. In addition, the processed video image of the stone may also be selectively inverted, so that the apparent orientation of the stone in a processed image during mounted and unmounted inscription operations is the same.
[0180] The operator will always “OK” the process before laser operation. He will either see the complete inscription on the text screen, or on the video directly on the girdle.
[0181] When the inscription is completed the operator can judge (even before cleaning) whether the inscription is successful. Even after cleaning, so long as the stone remains seated in the holder, will return to exactly the same position. The operator can choose to repeat the whole inscription or parts thereof any number of times he wishes to. Verification of the inscription is performed prior to removal of the diamond from the holder, so that the process may be repeated if necessary. The inscription is clearly visible on the video screen even before cleaning the ink/graphite from the stone. Even with the preferred 200 times magnification, an inscription will eave to be extremely long in order not to be wholly visible on the screen.
[0182] Authentication
[0183] Where a workpiece bears a marking, it may be desired to determine whether the marking is authentic, for example according to the flow chart depicted in FIG. 12. The workpiece is viewed under magnification to read markings present thereon 181 . The authentication process provides at least two options. First, the markings may be encrypted, and are thus processed with a key 183 , e.g., a public key. Where the actual characteristics of the stone form the encrypted message, the decrypted message is compared to the actual characteristics of the workpiece 184 . Thus, the authenticity may be determined. Alternately, the markings may include a code which identifies the workpiece, allowing retrieval of information relating to the workpiece from a database. The database thus stores the characterizing information.
[0184] In a second embodiment, also shown in FIG. 12, the authentication process involves a remote system. Therefore, the markings are transmitted to a central system 182 . The characteristics of the workpiece are read or extracted 185 and also transmitted to the central system 186 . The central system then authenticates the marking and the characteristics 187 , for example against a stored database of characteristics of marked workpieces. The authentication result is then transmitted to the remote site 189 .
[0185] Encryption
[0186] A diamond 200 , as shown in FIG. 13A, with further detail, enlarged in FIG. 13D, is provided with a number of identification and security features. The diamond 200 , for example, is a color F stone weighing 0.78 Carats, grade VS2 with two identified flaws 207 . The diamond 200 has a set of markings inscribed on the girdle 201 . The markings include an “LKI” logo 202 , formed as characters, a trademark registration symbol 203 , a serial number in Arabic numerals 204 , a one dimensional bar code 205 , a two dimensional code 206 , a set of visible dimensional references 209 , and single ablation spots 208 , 210 having defined locations. For most purposes, the logo identifies the series of marking, while the serial number is used to identify the diamond 200 . In order to encode further information, a visible bar code 205 allows, for example, binary information to be encoded and retrieved from the diamond 200 . The two dimensional code generally requires a machine for reading, and allows high density data encoding. The visible dimensional references 209 allow use of a reticle to measure distances, providing additional characteristics of the diamond 200 which may be used to uniquely define the diamond 200 . The single ablation spots 208 , 210 are less visible, and may thus require a key for searching. In other words, authentication of these spots may require transmission of their location, with confirmation by inspection of the diamond 200 . The marking 210 , for example, has a defined physical relation to one or both flaws 207 , making copying very difficult.
[0187] [0187]FIG. 13B shows, in more detail, a typical two dimensional code, with simple binary modulation. Thus, the presence 213 or absence 214 of an ablation at a coordinate 211 , 212 location defines the data pattern. On the other hand, FIG. 13C shows a more complex code. In this case, ablations are spaced discontinuously or partially overlapping, so that an outline or partial outline of each spot 223 may be identified. Due to stochastic processes, the actual placement of the center 224 of an ablation, or its outline may vary. However, the modulation pattern imposed may be greater in amplitude than the noise, or a differential encoding technique employed so that the noise is compensated. Thus, an array of spots 223 on generally coordinate 221 , 222 positions, with the exact positions 225 modulated according to a pattern 225 . In this case, without knowledge of the modulation scheme, it would be difficult to read the code, thus making it difficult to copy the code. Further, to the extent that the noise amplitude is near the apparent signal amplitude, a copying system may require very high precision.
[0188] There has thus been shown and described novel receptacles and novel aspects of laser workpiece marking systems and related databases, which fulfill all the objects and advantages sought therefor. Many changes, modifications, variations, combinations, subcombinations and other uses and applications of the subject invention will, however, become apparent to those skilled in the art are considering this specification and the accompanying drawings which disclose the preferred embodiments thereof. All such changes, modifications. variations and other uses and applications which do not depart from the spirit and scope of the invention are deemed to be covered by the invention, which is to be limited only by the claims which follow | A laser energy microinscribing system, comprising a semiconductor excited Q-switched solid state laser energy source, a cut gemstone mounting system, allowing optical access to a mounted work-piece, an optical system for focusing laser energy from the laser energy source onto a cut gemstone, a displaceable stage for moving said gemstone mounting system with respect to said optical system so that said focused laser energy is presented to desired positions on said gemstone, having a control input, an imaging system for viewing the gemstone from a plurality of vantage points, and a rigid frame supporting said laser, said optical system and said stage in fixed relation, to resist differential movements of said laser, said optical system and said stage and increase immunity to vibrational misalignment. The laser energy source is preferably a semiconductor diode excited Q-switched Nd:YLF laser with a harmonic converter having an output of about 530 nm The system may further comprise an input for receiving marking instructions, a processor for controlling said displaceable stage based on said marking instructions and said imaging system, to selectively generate a marking based on said instructions and a predetermined program, and a storage system for electronically storing information relating to images of a plurality of workpieces. A secure certificate of authenticity of a marked workpiece is also provided | 1 |
BACKGROUND OF THE INVENTION
The invention relates to a device for connecting structural components, with a base part, which is disposed at the one structural component, a spacer, which is in threaded engagement with the base part and is supported with one end at the other structural component, and a connecting screw, which is inserted frictionally engaged through the spacer.
A known device of this type is described in EP-B-0 176 663 and is used to connect two structural components, which are disposed at a particular distance from one another, with the help of the connecting screw without distorting the structural components as the connecting screw is tightened. The connecting screw is inserted, for example, through the structural component, which is to be supported at the spacer, and is then screwed into an internal thread of the other structural component, which is connected with the base part. During this screwing-in motion, the spacer is taken along by friction. The thread between the spacer and the base part is a left-handed thread, so that the spacer is screwed further out of the base part and approaches the structural component, which is held by the head of the connecting screw, until this component finally lies in contact with the front surface of the spacer.
However, if the distance between the structural components, which are to be connected, is greater than the maximum adjusting path of the spacer, it may happen that, as the connecting screw is screwed in, the spacer is screwed completely out of the base part. Since the spacer in this case is accessible only with difficulty, if at all, it is difficult to restore the threaded engagement between the spacer and the base part.
In the state of the connecting device as delivered, the spacer normally is screwed completely into the base part. From practice, a connecting device is known, for which the spacer in this position is in contact with a stop and, in addition is held in position by a spring-mounted latch. However, it must be possible to overcome the resistance of the latch when the connecting screw is being screwed in. Accordingly, it is not impossible that, because of improper handling or jarring, the spacer, before use of the connecting device, becomes detached completely from the base part, so that the parts of the connecting device fall apart and are lost.
For stability reasons, the base part and the spacer should consist of metal. In that case, however, the danger exists that the structural components, which are to be connected to one another, are scratched during the assembly by the spacer, which protrudes from the base part. This problem occurs, for example, in vehicle construction, when a cross member is to be fastened with the help of two such connecting devices between two body parts of the vehicle, which have already been painted.
SUMMARY OF THE INVENTION
It is therefore an object of the invention, to provide a device of the type mentioned above, with which damage by the spacer to one of the structural parts, which is to be connected, is avoided.
Pursuant to the invention, this objective is accomplished owing to the fact that the spacer is surrounded by a jacket of a softer material, preferably of plastic, and that the jacket, at least in the state, in which the spacer and the base part together have the smallest axial dimension, is flush with the front surface of the spacer or of the harder core of the latter or protrudes relative to this front surface.
Advantageous developments of the invention arise from the dependent claims.
A possible embodiment is characterized in that the spacer has a jacket, which overlaps the base part and in that stops are disposed at this jacket and at the base part, which limit the unscrewing movement of the base part and the spacer. In that case, the protective jacket is part of the spacer.
In the case of a different embodiment, the jacket is seated on the base part. Since the device, in the original state, before the start of the assembly work, is adjusted to the smallest possible axial dimension, the spacer lies protected in the jacket until the structural components, which are to be connected, are brought into position and the connecting screw is screwed in.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following, an example of the invention is described in greater detail by means of the drawings, in which
FIG. 1 shows an axial section through a connecting device and two structural components, which are to be connected,
FIG. 2 shows two jackets, which belong to the connecting device, in a section in the plane II—II of FIG. 1,
FIG. 3 shows a side view of one of the jackets,
FIG. 4 shows the connecting device of FIG. 1 in the state during the establishment of the connection,
FIG. 5 shows a side view of the connecting device without the structural components, which are to be connected, in the state with the maximum axial dimension,
FIG. 6 shows an axial section through a connecting device of a different embodiment,
FIG. 7 shows a connecting device of a further embodiment and
FIG. 8 shows a part of the connecting device of FIG. 7 in a front view.
DETAILED DESCRIPTION
In FIG. 1, two plate-shaped structural components 10 , 12 are shown, which are to be connected to one another at a distance from one another by a connecting device 14 . The connecting device 14 is formed by a base part 16 , which is held at the structural component 10 , a spacer 18 , which is screwed into the base part 16 , and a connecting screw 20 , which is inserted through the structural component 12 and inserted into a central borehole of the spacer 18 and, during the establishment of the connection, is screwed into a threaded borehole 22 of the structural component 10 .
The base part 16 has a metal core 24 , which is supported at the structural component 10 and, at the outer periphery, has a knurled collar, onto which the plastic jacket 26 is pressed. The jacket 26 forms two claws 28 , with which the base part 16 is clipped non-rotationally to the structural component 10 .
The spacer 18 also has a metal core 30 , which is surrounded by a plastic jacket 32 . The jacket 32 is pressed onto a knurled collar 34 of the core 30 and grips into an annular space between the core 24 and the jacket 26 of the base part 16 .
The cores 24 , 30 of the base part and of the spacer engage one another by means of a left-handed thread 36 . In the central bore hole of the spacer 18 , a lock washer 38 is pressed, which brings about a non-positive connecting with the outer thread of the connecting screw 20 .
When the connecting screw 20 is screwed into the threaded borehole 22 of the structural component 10 , the spacer 18 is carried along in the direction of rotation, while the base part 16 is held non-rotationally by the claws 28 . Therefore, because of the left-handed thread 36 , the spacer 18 is screwed out of the base part 16 , so that it moves axially towards the structural component 12 which, in turn, is pressed by the head of the connecting screw 20 against the spacer.
At the opposite ends of the outer jacket 26 of the base part 16 , two cog-shaped stops 40 , 42 are formed, which are offset by 180°, protrude towards the inside from the jacket 26 and, together with a further stop, which is formed by a rib 44 on the outer periphery of the jacket 32 of the spacer 18 , limit the adjusting path of this spacer in the screwing-in as well as in the screwing-out direction. As can be seen clearly in FIGS. 2 and 3, the rib 44 has the shape of a left-handed helix which, at the free end of the jacket 32 , runs almost completely around the jacket. The pitch of this helix is identical with the pitch of the left-handed thread 36 . The opposite ends 46 , 48 of the rib 44 are opposite to one another at a distance, which is slightly larger than the peripheral length of the stops 40 and 42 .
In the state shown in FIGS. 1 and 2, the end 46 of the rib 44 lies against the stop 40 and thus prevents further rotation to the left of the spacer 18 . In this way, the screwing-in motion of the spacer is limited. However, if the spacer 18 is rotated to the right with the help of the connecting screw 20 , the opposite end 48 of the rib can move past the stop 40 . After a full revolution, the spacer 18 emerges from the base part 16 by the length of a thread pitch of the left-handed thread 36 , so that the end 46 of the rib 44 can then move past the stop 40 .
As the connecting screw 20 is screwed in further, the state, shown in FIG. 4, is then reached as an intermediate state, in which the spacer 18 has already moved some distance out of the base part 16 . If the connecting screw 20 is screwed in further, the structural component 12 is clamped tightly between the head of the connecting screw and the end of the spacer 18 and, with that, a stable connection is established between the structural components 10 and 12 .
If the distance between the structural components were larger and the connecting screw 20 were longer, the spacer 18 could be moved out further. The screwing-out movement of the spacer is, however, limited owing to the fact that the end 48 of the rib 44 comes up against the stop 42 , as shown in FIG. 5 . In this way, it is prevented that the spacer 18 can be screwed out completely from the base part 16 .
As can be seen in FIGS. 1 and 4, the jacket 32 of the spacer projects somewhat beyond the core 30 with its end facing the structural component 12 . Therefore, when the spacer comes up against the structural component 12 , there is frictional contact between the jacket 32 and the structural component 12 . Since the jacket 32 consists of plastic, damage to the surface of the structural component 12 is avoided. However, if a more stable support of the spacer 18 at the structural component 12 is desired, the end of the jacket 32 can also be offset back into a flush position, so that the spacer 18 is also supported with its metal core 30 at the structural component 12 .
The procedure for producing the connecting device, described above, may be as follows. The core 30 of the spacer is screwed into the core 24 of the base part 16 , before these metal parts are connected with the associated plastic jackets. The screwing in therefore is not impeded by the stops 40 , 42 and the rib 44 . The screwing-in depth can be adjusted to a particular value by inserting a suitable gauge in the space between the collar 34 of the spacer and the front surface of the core 24 of the base part.
The jacket 32 is then pushed from the left in FIG. 1 over the core 24 of the base past and pressed onto the collar 34 of the spacer. Subsequently, the jacket 26 of the base part is pushed, once again from the left in FIG. 1, over the jacket 32 . At the same time, the jacket 26 is held in an angular position, in which the stop 40 can enter the space between the ends 46 , 48 of the rib 44 . In this position, the jacket 26 is then pushed onto the core 24 , until its front surface is a flush with the front surface of the core 24 .
The end position of the spacer 18 , in the screwed-in position shown in FIG. 1, can be defined precisely in this way. The adjusting path of the spacer is defined by the position of the stops 40 and 42 . Since these stops are diametrically opposite to one another in the example shown, the adjusting path of the spacer corresponds to (n+½) revolutions and accordingly amounts to (n+½) times the pitch of the left-handed thread 36 (n is a whole number). This adjusting path can also be varied infinitely by changing the angular offset between the stops 40 and 42 .
The end position of the spacer 18 in the screwed-in position preferably is selected so that the front surface of the spacer 18 , facing the structural component 10 , is recessed slightly from the front surface of the base part 16 . By these means, it is prevented that the spacer 18 becomes jammed, when the base part 16 is pressed against the structural component 10 .
FIG. 6 shows a connecting device 114 of a different embodiment. The connecting device 114 is formed by a base part 116 , which is held at the structural component 10 , a spacer 118 , which is screwed into the base part 116 , and the connecting screw 20 , which is inserted through the structural component 12 and into the central borehole of the spacer 118 and, during the establishment of the connection, is screwed into the threaded borehole 22 of the structural component 10 .
The base part 116 has a threaded metal bushing 124 , which is supported at the structural component 10 and, at the outer periphery, has a milled edge, onto which a plastic jacket 126 is pressed. The jacket 126 forms two claws 128 , with which the base part 116 is clipped non-rotationally to the structural component 10 .
The spacer 118 consists completely of metal. The threaded bushing 124 of the base part and the spacer engage one another by means of a left-handed thread 130 . A lock washer 132 , which establishes a non-positive connection with the external thread of the connecting screw 20 , is pressed into the central borehole of the spacer 118 .
When the connecting screw 20 is screwed into the threaded borehole 22 of the structural component 10 , the spacer 118 is carried along in the direction of rotation, while the base part 116 is held non-rotationally by the claws 128 . Therefore, because of the left-handed thread, the spacer 118 is screwed out of the base part 116 , so that it moves axially onto the structural component 12 which, in turn, is pressed by the head of the connecting screw 20 against the spacer.
The left-handed thread 130 of the spacer 118 is bounded at one end, on the right hand side in FIG. 6, by a shoulder 134 . At the inner peripheral edge, the jacket 126 forms a circulating collar 136 , at which one end of the threaded bushing 124 is supported. An elastic latch 138 protrudes inwards at least at one place on the periphery from this collar 136 . This latch 138 forms a stop, which interacts with the shoulder 134 and, in this way, limits the maximum extension path of the spacer 118 .
At the end facing the structural component 12 , the spacer 118 has a radially protruding flange 140 , which forms a stop surface for the structural component 12 , when the structural components 10 and 12 are clamped together by the connecting screw 20 . In the state shown in FIG. 6, in which the spacer 118 still is retracted completely in the base part 116 , the outer surface of the flange 140 concludes flush with the front surface of the jacket 126 . A projection 142 , starting out radially from the edge of the flange 140 , lies at an inwardly protruding stop 144 of the base part 116 . The stop 144 thus prevents the spacer 118 being rotated to the left in the screwing-in direction of the connecting screw 20 . Accordingly, the spacer 118 cannot be shifted beyond the position, shown in FIG. 6, in the direction of the structural component 10 . However, when the connecting screw 20 is screwed to the right into the threaded bushing 124 , the spacer 118 can rotate along to the right, since then the projection 142 is freed from the stop 144 . After a complete revolution of the spacer 118 , the projection 142 has already emerged to such an extent from the base part 116 , that it can move outside of the base part past the stop 144 .
In the case of the example shown, it is thus ensured that the spacer 118 cannot be screwed out of the base part 116 in the one or the other direction.
However, for assembling the connecting device, the spacer 118 can be screwed from the right side in FIG. 6 into the threaded bushing 124 of the base part. In so doing, the elastic latch 138 initially is bent towards the inside, so that it gives way to the spacer 118 . As the spacer is screwed in further, the latch 138 then slides along the outer threads of the spacer and finally slides over the shoulder 134 , so that it can spring back once again into its original position, in which it acts as a stop for the shoulder 134 .
FIGS. 7 and 8 show a further example of a connecting device 146 , for which the connecting screw 20 is screwed in from the opposite end. In this case, the structural component 10 has a keyhole-shaped opening 148 with two diametrically opposed protuberances 150 for accommodating the claws 128 . The circular inner part of the opening 148 is covered by a disc 152 , at which the head of the connecting screw 20 and the threaded bushing 124 of the base part 116 are supported.
The threaded bushing 124 and the spacer 118 in this case have a right-handed thread, so that the spacer 118 moves to the right in FIG. 7 in the direction of the structural component 12 , when the connecting screw 20 is turned to the right.
FIG. 7 shows the spacer 118 already in the extended state, in which the shoulder 134 has already almost reached the stop position. In this case however, the stop at the jacket 126 is formed by a rigid projection 154 and not by a spring-mounted latch. The flange 140 , which is formed at the spacer 118 and in this case has a smaller diameter, has a recess 156 , through which the projection 154 can pass axially, at one place of its periphery.
During the assembly of the connecting device 146 , initially the threaded bushing 124 and the spacer are screwed together, before the threaded bushing 124 is pressed into the jacket 126 . The spacer 118 can therefore be screwed from the right in FIG. 7 into the threaded bushing 124 , until it has reached approximately the screwed-in position shown in FIG. 7 . Subsequently, the spacer 118 and in the threaded bushing 114 are inserted jointly from the left side in FIG. 7 into the jacket 126 . In so doing, the spacer 118 is held at an angular position, in which the projection 154 can pass through the recess 156 . In the end phase of the insertion movement, the threaded bushing 124 is then pressed with its milled outer circumferential edge into the jacket 126 . Finally, the spacer 118 is screwed deeper into the threaded bushing 124 , until its opposite end faces are flush with the corresponding surfaces of the base part 116 and the jacket 126 , respectively.
In the state, in which the connecting device has the smallest possible axial dimension, the base part 116 is then clipped to the structural component 10 and the connecting screw 20 is inserted and screwed in, so that the spacer 118 can then be extended once again.
FIG. 8 shows a part of the front surface of the flange 140 , as well as a part of the collar 158 , which is formed at the jacket 126 and surrounds this flange 140 . In this state shown in FIG. 8, the recess 156 , which is formed at the edge of the flange 140 , is twisted with respect to the projection 154 of the base part. At the left flank of the recess 156 in the view of FIG. 8, a projection 160 is formed, which protrudes radially towards the outside from the edge of the flange 140 . A stop 162 , which protrudes towards the inside, and a bridge-like stop spring 164 are integrally molded to the inner peripheral surface of the collar 158 . As long as the flange 140 lies axially outside of the base part, as shown in FIG. 7, the spacer 118 can be turned to the right and, with that, screwed deeper into the base part 116 . During the last revolution, immediately before the minimum axial dimension is attained, the flange 140 enters the collar 158 . The projection 160 initially, overcoming a certain resistance, slides over the lock spring 164 and then comes into contact with the stop 162 . The further screwing-in movement of the spacer 118 is limited in this manner. The spacer is held by the stop spring 164 in the position attained with the minimum axial dimension and prevented from shifting because of vibrations. However, the force of the stop spring 164 is dimensioned, so that it can be overcome by the frictional resistance between the connecting screw 20 and the spacer, when the connecting screw 20 is being screwed in. During the screwing-in movement, the spacer 118 rotates to the left in the view of FIG. 8, so that the projection 160 distances itself from the stop 162 . | A device for connecting structural components ( 10, 12 ), with a base part ( 16; 116 ), which is disposed at the one structural component ( 10 ), a spacer ( 18; on 118 ), which is in threaded engagement with the base part ( 16; 116 ) and is supported with one end at the other ( 12 ) structural component, and a connecting screw ( 20 ), which is inserted frictionally engaged through the spacer ( 18; 118 ), wherein the spacer ( 18; 118 ) is surrounded by any jacket ( 32; 126 ) of a softer material, preferably of a plastic which, at least in the state, in which the spacer and the base part together have the smallest axial dimension, is flush with the front surface of the spacer ( 118 ) or of the hard core ( 50 ) of the same or protrudes with respect to this front surface. | 5 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/833,738, filed Jul. 27, 2006 the disclosure of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
Virtually all bacteria are host to viruses known as bacteriophages (hereinafter known as “phages”). These phages are species-specific, to the extent that a phage associated with the bacterium Enterococcus faecalis will be capable of infecting only Enterococcus faecalis , and a phage associated with Escherichia coli will infect only Escherichia coli . Viruses are non-cellular entities known as obligate parasites, which means they reproduce only within the cells of their specific hosts and they cannot replicate independently.
During lytic infection, phages will utilize the metabolic ‘machinery’ of the host and in the process multiply within the host cell to a point known as the “burst size”, at which point the host cell ruptures and releases the newly formed phages into the environment. The host cell is killed in the process. The newly formed phage particles may persist in the environment where they are ready to infect additional suitable host cells that they encounter. Because certain phages are excreted or egested by warm-blooded animals including humans, their presence in the environment may be interpreted as an indication of fecal contamination.
Because phages and enteric viruses are generally considered more resistant than bacteria to antagonistic environmental factors, phages may exhibit longer survival times than the bacteria currently used to determine the extent of fecal contamination in the environment. If that is the case, then it follows that testing the environment (water, food, etc.) for the presence of phages may yield more useful correlative evidence of viral contamination than would be the case when bacterial indicators are used.
Unfortunately, until now no simple, accurate method of testing for phages as environmental indicators has been available. In food and water testing, one of the most important indicator bacteria is Escherichia coli and various phages specific to it have been well described and documented. Since E. coli is by definition a “coliform” bacterium, the phages associated with it are known as “coliphages”. This bacterium and its viruses are well documented, the following discussion will be based on them. It should, however, be recognized that any microbial species and its phages might be used.
By minor changes in the nutrient formula and the use of different host bacteria, the methodology can be employed to detect any other bacteriophage specific to the host bacteria that can be propagated on a medium.
Currently, the approved methods for coliphage detection are detailed in Standard Methods for the Examination of Water and Wastewater, 20th edition as Method 9211 D., ISO Method 10705-2, ASTM Method 4201-96, and EPA Methods 1601/1602. These methods involve the use of agar based media which necessitates difficult and time-consuming temperature control procedures to maintain the integrity of samples and bacterial cultures. Because of the cumbersome, technique-specific nature of the Old Method(s), achievement of reproducible results is difficult for those laboratory technicians who lack experience with the methods or those who do not pay meticulous attention to detail, particularly as it relates to the temperature of the agar.
The approved enumerative methods are based upon the use of a semisolid matrix that functions to immobilize the host bacteria and the infecting phages. The medium must gel so that the bacteria grow within the gel-solid matrix, where they are attacked (infected) by phages present in the sample. When a bacterial host cell is infected with the virus, the virus reproduces within the host until the host cell is engorged with virus particles at which point it bursts and releases the viruses into the environment where they are free to infect new host cells. The consistency of the gel may affect the migration of phage particles in the medium. Those bacteria that are infected release many more phage particles which infect surrounding bacteria so that a clear zone of dead host cells appears in the “lawn” of dense living bacterial growth which covers most of the plate. This clear zone of necrosis is known as a viral “plaque” and the number of visible plaques is used to quantify the number of viruses originally present in the sample.
The use of coliphage qualitative and quantitative test methods are somewhat analogous to the testing for coliform bacteria in a given sample. Neither the coliphages nor the coliform bacteria are generally considered primary pathogens (disease-causing agents); rather, they are considered “indicators” of pathogenic contaminants that may be found in the same environment and their presence is generally assumed to indicate the potential presence of disease-causing microorganisms. Typical bacterial pathogens include species of genera such as Salmonella (typhoid and paratyphoid) or Vibrio (cholera). The absence of coliform bacteria is generally considered to reflect a likely absence of these and other bacterial pathogens because the indicator organisms are typically more numerous than pathogen bacteria in the environment and indicator and pathogenic bacteria generally exhibit similar survival times in the environment.
Because viral pathogens such as hepatitis A virus, the poliovirus group, noroviruses, and others tend to exhibit appreciable resilience in the environment and are characterized by extended survival times and in general to a high degree of resistance of antagonistic forces such as heat, freezing, and desiccation, for example, these viruses may be present even when the bacterial indicators are completely absent. Therefore, if a virus indicator such as a coliphage is used, there is an increased probability of capturing an actual virus contamination event when it occurs. Moreover, exclusive reliance upon bacterial indicators may result in the incorrect conclusion that pathogenic viruses are absent from the environmental sample.
SUMMARY OF THE INVENTION
Some of the basic materials suggested in the new invention are similar to those of the traditional agar based methods, but there are several very important and unique differences. Instead of the incorporation of agar into the media as the gelling agent, the gelling in this invention is accomplished by incorporating materials other than agar which convey very different properties and constraints to the method.
This invention has a purpose and is designed to produce a more accurate enumeration of the number of bacteriophages present in a sample by reducing the number of labile viruses inactivated by contact with materials at an elevated temperature.
DESCRIPTION OF THE INVENTION
The invention incorporates specific ingredient(s) that, when combined, result in the formation of a semi-solid or gelled matrix. The change in the physical state of these ingredients from a liquid to a semi-solid state is temperature-independent.
The ingredients consist of two types of materials, the first being one or more of a class of agents commonly referenced as “gums”. These “gums” may include but not be limited to pectins, carrageenans, alginates, gellans, gelatins, xanthans, and guar. At least one of this ingredient type which has the property of combining with the second material type must be included in the invention composition. The second type of material consists of divalent metallic salts, with the preferred material being calcium chloride.
The combination of these two types of materials results in a gel which is an improved alternative to agar for the propagation of host bacteria and the detection and enumeration of bacteriophages that infect the host bacteria. One preferred choice of the invention incorporates pectin as the primary gelling agent, and the mechanism is similar to that of the Pectin Gel Method that is used and marketed by Micrology Laboratories of Goshen, Ind. and disclosed in U.S. Pat. No. 4,241,186, incorporated by reference herein.
The modification and application of Pectin Gel technology makes this invention novel and unique from the traditional agar based method, improving the ability to detect and enumerate bacteriophages that are present and viable in a sample, including those that are currently inactivated by the molten, hot (minimum 45° C.) agar medium.
Even small temperature increases well below the minimum 45° C. temperature of molten agar medium, such as seen when a human hosts spikes a fever to 39° C. is understood to inactivate viruses. However, the fact that some bacteriophages can be recovered and form plaques when a molten agar medium method is used may hide the non-obvious fact that other bacteriophages may have been present in the sample which are capable of infecting host bacteria but were not detected because they were inactivated by the heat and therefore cannot form plaques. These uncounted bacteriophages are not enumerated because they become damaged by the elevated temperature of the molten agar medium or because they attach to host bacteria that are damaged and inactivated by the elevated temperature of the molten agar medium.)
While the use of temperature independent gelling materials improves on the enumeration of bacteriophages by eliminating the temperature induced inactivation of labile viruses, this invention further incorporates other improvements over currently available, existing methods. For example:
1. The appearance of the plaque is generally apparent after 6 hrs. incubation time for coliform type bacteriophages.
2. The ease of seeing and counting the plaques present on the dish is greatly enhanced by the combination of a chromogenic substrate such as 5-Br-4-Cl-3-indolyl-â-Dgalactoside (X-Gal) and a bacterial stain such as 2, 3, 5 Triphenyl-2H-Tetrazolium Chloride (TCC). The mechanisms for these two compounds in the mix need to be explained and understood in order to comprehend the uniqueness of the method.
First, the presence of the X-Gal is important to the coloration of the plaque as the X-Gal is a chromogenic enzyme substrate which is cleaved by interaction with the enzyme galactosidase, resulting in an insoluble chemical dimer that assumes a teal blue-green color. Also a fluorogenic enzyme substrate such as 4-methylumbelliferyl-B-D-galactoside could be used as a color producing agent.
Therefore, when the bacteria (in the case of this example the bacteria are E. coli or coliform introduced into the mix grow, they produce the enzyme galactosidase and the bacterial cells and aggregates of those cells assume the teal coloration. This coloration stays with the bacterial cells whether they are dead or alive. Therefore, without any other colorizing agent in the mix, the lawn of bacteria will turn a teal color, and even areas of plaque will be teal from the fact that the insoluble pigment was present before the bacteria were killed by the bacteriophage. The bacteriophage infects bacterial cells and replicates within the bacterial cells until the cells burst and release quantities of newly formed bacteriophage which can infect and kill other bacterial cells in the vicinity, thus forming a zone, or plaque, consisting of dead bacteria. This plaque forms an irregularly edged circular area which is what must be discerned and counted to determine the presence and quantity of bacteriophage in the original sample. Each circular plaque zone is considered the result of an original host bacterium being infected by a single bacteriophage. The use of the X-Gal alone may not result in easily seen plaques.
Therefore, an additional colorizer to increase and contrast the plaques from the rest of the bacterial lawn may be needed. This is where the TCC or some other similar oxidation reduction compound (Redox) becomes important. The TCC in the mix remains colorless in its oxidized state until the bacteria grow actively and cause it to be reduced, whereupon it becomes a red color. This reduction only occurs where there are living bacterial cells or aggregates and so the living portion of the bacterial lawn assumes a red color which is combined with the teal of the X-Gal and the red becomes dominant in the lighting conditions described.
The circular \plaque areas do contain only dead bacterial cells and therefore no reduction of the TCC occurs in the plaque and it stands out as a teal circular area in a deep red background lawn, so that it becomes very simple and easy to see and enumerate the Plaque. Therefore, the contrasting color that causes the circular Plaque to stand out will only occur if there is a colorizing agent activated by living cells. This explains one of the unique features of the method.
It should be understood that the X-Gal and TCC combination used in the example is not limiting.
One should be aware that there are many potential variations in the combinations of Redox reagents, antibiotics and chromogenic compounds that may be used successfully for this method. For example, there are various tetrazolium salts available which may give different colors when reduced, such as blue. The combination of a blue-producing T-salt with a pink or red chromogenic galactoside or glucuronide enzyme substrate would result in the phage plaque appearing pink or red with the background being blue or purple. Also redox reagents such as methylene blue or reazurin might be used. Regardless of the combinations chosen, the principles of the method are realized and achieved. Many variations of host bacteria, bacteriophages, temperature-independent gelling agents, chromogenic and fluorogenic substrates for various enzymes, and inhibitors of non-target bacteria can be described to produce an analogous testing capability, but the instructions for the general method are presented below.
3. Another advantage of the invention is that the likelihood of confusing small air bubbles in the medium with bacteriophage plaques is eliminated. When no chromogen is used in the medium (other methods) both the plaque and air bubbles appear as clear circular spots and are easily confused. With the new invention, air bubbles still appear as clear circular spots, but plaques appear as colored circular spots.
4. The size of the plaque areas produced by the new invention also are generally significantly larger and therefore more obvious and easily seen than those of other existing methodology. This is due to the unique properties of the gel that is produced by the pectin or other gum(s) used in the method versus the agar-based gel of other methods.
5. This invention also allows a large (up to 10 mL) sample to be tested in one standard sized petri dish. It is feasible that through the use of larger dishes, larger single samples could be run. Larger samples are advantageous when sample (test) materials contain very low numbers of bacteriophage. For example, if a water sample contains 20 bacteriophage/100 mL, a 1-4 mL sample will likely show as negative, while a 10 mL sample will contain 2 plaques.
6. The invention does not require the use of an overlay of the sample mix on the top of a prepoured plate or container. This makes the procedure much more energy and time effective.
7. The invention also takes advantage of antibiotics and antibiotic-resistant hosts for the suppression of interfering microorganisms that may obscure viral plaques. For example, conferring ampicillin, nalidixic acid and streptomycin resistance in the E. coli (or other bacterial type) strain used would eliminate most interference by extraneous organisms and eliminate the necessity of using other means of controlling that potential problem.
Example
Bacteriophage Quantitation from a Water Sample
The following are materials and formulations suggested for a generic set-up and procedure constituting the new invention. The final pH of the sterile Medium should be around 6.0-6.2 and may need to be adjusted with an appropriate solution such as 10% aqueous Potassium Carbonate. The need for this depends on whether the only gelling agent in the Nutrient Medium is the Low Methoxyl Pectin or if a mix of pectin with other gums such as alginate, carageenan, etc. are used.
Reagents and Supplies Needed:
1. A sterile Nutrient Medium with the following formulation is provided in a container.
FORMULATION (ingredients for one Liter):
Proteose Peptone #3
30
gm.
Soy Peptone
10
gm.
Potassium Phosphate (dibasic)
4
gm.
Sodium Chloride
6
gm.
Low Methoxyl Pectin
25
gm.
X-Gal (5Br4Cl3IndolylBDgalactoside)
180
mg.
IPTG (IsopropylBDthiogalactoside)
180
mg.
2. Tryptic Soy Broth (TSB) such as manufactured by Difco or BBL
3. Sterile reagent water
4. Bacterial Stain (sterile 5% 2,3,5 Triphenyl-2H-Tetrazolium Chloride, abbreviated TCC)
5. Bacterial Host Cells specific for Bacteriophage
6. Specific Bacteriophage for use as positive control.
7. Sterile Pretreated Petri Dishes containing semi-dry layer holding 225 mg of Calcium Chloride
Procedure:
1. All materials and solutions are equalized to room temperature (22-35 C.—exact temp. not crucial)
2. To a bottle containing 10 mL of sterile Nutrient Medium, add test water sample or test sample concentrate or instead, to create a control, add a solution containing a known concentration of Specific Bacteriophage. If needed add TSB or sterile reagent water to bring total volume to 18-20 mL. Also, then add 70 uL of Bacterial Stain, and 0.3 mL log phase Bacterial Host Cells.
3. Mix the combined solution by swirling several times (do not vortex to avoid creating excessive bubbles) and pour the entire mixture into a sterile Pretreated Petri Dish.
TABLE 1
Various combinations of sample and TSB or sterile reagent water
volumes capable of producing acceptable plaque formation.
Various combinations of sample and TSB or sterile reagent water volumes
capable of producing acceptable plaque formation.
Sample
Sterile TSB or
Nutrient
Bacterial
Bacterial
Volume
Sterile water
Medium
Stain
Host
(mL)
(mL)
(mL)
(uL)
(mL)
1
7
10
70
0.3
2
6
10
70
0.3
3
5
10
70
0.3
4
4
10
70
0.3
5
3
10
70
0.3
6
2
10
70
0.3
7
1
10
70
0.3
3. Swirl the dish gently several times and place the dish (upright) on a level shelf of an incubator. If the test is for coliform bacterial types, the incubator should be set at 35° C. The mixture in the dish will gel within 1 hour. Incubate the dishes for 12-16 hours.
4. Remove the dish from the incubator and count the circular teal plaques on the red bacterial lawn. Examination of the dish for the plaques is best done with the dish placed on a light box or colony counter and a light source from the top of the dish may also be helpful. The plaque color will be more intense when the light shines from the top of the dish.
The invention herein described eliminates the difficulties of previously described approachs and offers an effective and easy way to accomplish the stated goals, not only saving time and energy, but increasing the accuracy and recovery of the target phages.
The described example for the new invention allows the rapid assessment of coliphages in/on virtually any substrate including water, food and environmental surfaces. It therefore has great utility for the testing of water, food and other materials where convenient, accurate and precise coliphage results are useful. The invention is simple to use, and results are precise and reproducible. It requires minimal equipment and technician time to obtain accurate and useful information with minimal chance of error. The components are inexpensive and it requires little time and energy to operate. | A method to propagate, enumerate and quantify bacteriophage(s) in a water sample or other aqueous sample was designed which contains ingredients to stimulate the growth of select bacterial species which are susceptible to infection by specific bacteriophage(s), in which interfering background organisms are either inhibited or inconsequential. Important features of the medium include oxidation-reduction compounds producing colored and/or fluorescent products, chromogenic and/or fluorogenic enzyme substrates, and temperature-independent gelling agent(s). A preferred combination is the growth medium containing 2,3,5-triphenyl tetrazolium chloride, 5-bromo-4-chloro-3-indolyl-B-D-galactoside, and appropriate gelling agents, which (when properly used) produces a dark red bacterial lawn containing teal blue-green, irregularly circular spots representing individual phage plaque, all discernible to the eye in visible light. The procedure can also be readily applied towards automatic counting systems under artificial illumination. The procedure can be employed with water samples and with elution buffers that can retain bacteriophages in suspension following contact by the buffer with foods, soils, hard surfaces and other solids that may be contaminated by bacteriophages. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 60/942,379, filed Jun. 6, 2007, the entire contents of which are hereby incorporated by reference.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The present invention is directed toward an alignment device for positioning masonry elements when forming a masonry joint and toward a method of using same, and more, specifically, toward an alignment device having first and second arms for guiding a masonry string away from a first location to define a level line for building a masonry wall and toward a method of using same.
[0004] 2. Description of Related Art
[0005] Using traditional methods, building structural joints, such as the corners of a building or similar structure, can be quite time consuming. To create a joint, an experienced or lead mason must use a level to build the corners (inside or outside) on the structure before other masons can build the walls between the corners. An eight block corner typically takes a lead mason about 45 minutes to an hour to build. Thus for a 4-man crew made up of a lead mason and three less senior masons, the less senior masons cannot begin work until at least two corners have been constructed by the lead mason. It would therefore be desirable to provide a method and apparatus that would allow masons of having less skill than a master mason to construct structural joints.
SUMMARY OF THE INVENTION
[0006] This and other problems are addressed by embodiments of the present invention, a first aspect of which comprises an alignment device for assembling a masonry joint that includes a main body configured to slidably engage a generally vertical support pole. The main body includes a first arm and a second arm projecting away from the main body, and the first arm defines a predetermined angle relative to the second arm. A reel assembly is mounted on the main body for supporting a reel of string, and the main body has a string guide between the reel assembly and the first arm for guiding a string from the reel to the first arm.
[0007] Another aspect of the invention comprises an alignment system that includes first and second support poles and an alignment device on each of the support poles. Each of the alignment devices includes a main body configured to slidably engage the first or second support pole. Each main body has a first arm and a second arm projecting away from the main body, and the first arm defines a predetermined angle relative to the second arm. A reel assembly is mounted on the main body to support a reel of string. The main body also has a string guide between the reel assembly and the first arm for guiding a string from the reel to the first arm. The string extends from the reel of string of the alignment device on the first support pole over the string guide, along the first arm of the alignment device on the first support pole and connects to the alignment device on the second Support pole.
[0008] A further aspect of the invention comprises a method of building a wall that includes steps of inserting first and second poles vertically into the ground at a first location and placing a first alignment device over the first pole and placing a second alignment device over the second pole. A reel of string is placed on the first alignment device, and the string is pulled from the reel of string along the first arm and to the second alignment device where it is attached. A masonry block corner is then built at each of the first and second poles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Example embodiments of the present invention will be more fully understood from the detailed description given hereinbelow and the accompanying drawings, wherein like elements are represented by like reference numerals, which are given by way of illustration only and are not intended to limit the example embodiments.
[0010] FIG. 1 illustrates a system including a pole and an alignment device for assembling a structural joint in accordance with an embodiment of the present invention.
[0011] FIG. 2 is a perspective view of the alignment device of FIG. 1 .
[0012] FIG. 3 is a top plan view of the alignment device of FIG. 2 .
[0013] FIG. 4 is an exploded perspective view of a reel assembly of the alignment device of FIG. 2 .
[0014] FIG. 5 is a perspective view of the pole the system of FIG. 1 .
[0015] FIG. 6 is a perspective view of a pole brace collar for the corner pole of FIG. 5 .
[0016] FIG. 7 is a perspective view of a pole brace for supporting the corner pole of FIG. 5 .
[0017] FIG. 8 is a perspective view of a second embodiment of an alignment device according to the present invention.
[0018] FIG. 9 is a top plan view of the alignment device of FIG. 8 .
[0019] FIG. 10 is a perspective view of a building foundation having several types of corner joints and schematically showing different alignment devices that could be used to build each type of corner joint.
[0020] FIG. 11 is a perspective view of a third embodiment of an alignment device usable in the system of FIG. 1 .
[0021] FIG. 12 is a top plan view of the alignment device of FIG. 11 .
DETAILED DESCRIPTION
[0022] FIG. 1 illustrates a system for assembling a structural joint of a structure in accordance with an example embodiment. System 1000 includes at least two alignment devices 100 (only one is shown) separated by a distance along a structure such as a residential or commercial building. As will be seen in more detail below, each alignment device 100 has an alignment guide with at least one alignment arm attached to a main body 101 of the device. The main body 101 includes a reel assembly 150 for paying out masonry string 75 and a string guide 120 thereon.
[0023] The system 1000 includes a corner pole assembly 200 provided for each device 100 . The corner pole assembly 200 includes a corner pole 21 0 on which the alignment device 100 is movably secured so as to slide up and down the pole 210 to build up the structural joint, and a pair of pole braces 230 attached to a corner pole brace 220 to secure the corner pole 210 in a vertical orientation at the corner of the building structure. The masonry string 75 is payed out from the reel assembly 150 of one alignment device 100 through alignment channels on the main body 100 and alignment arm 111 , then is tightened and secured at the other alignment device 100 so as to provide a level line for building up the structural joint with masonry products 50 , which can be brick or block products, for example. Of note, there is no need to actually build a corner as in the prior art before laying rows of masonry products; the system is installed and the masonry products can be laid immediately
[0024] FIG. 2 is a perspective view of a alignment device for assembling a structural joint of a structure in accordance with an example embodiment that is usable in the system of FIG. 1 . Referring to FIGS. 2 and 3 , the alignment device 100 , also called a corner mount assembly, is shown in this embodiment as being applicable to an ‘outside’ corner, i.e., it is used to build up an outside corner of a building structure with masonry product. Accordingly, the device 100 of FIG. 2 is employed where the structural joint to be built up is an outside corner, such as a 45° or 90° outside corner, for example.
[0025] Device 100 includes a main body 101 to which a string reel assembly 150 is attached thereto for paying out masonry string used in preparing a level line. The main body 101 may be composed of a resilient material such as polyvinyl carbonate (PVC), although other materials may be used, such as a medium or heavy gauge impact plastic like acrylonitrile butadiene styrene (ABS). ABS is an easily machined, tough, low-cost, rigid thermoplastic material with medium to high impact strength, and is a desirable material for turning, drilling, sawing, die-cutting, shearing, etc. PVC and ABS are merely two examples. Alternatively, main body 101 could be composed of other thermoplastic and thermoset materials that have characteristics similar to PVC or ABS, such as, for example, polypropylene, high-strength polycarbonates such as GE Lexan, and/or blended plastics.
[0026] Device 100 includes a masonry alignment guide 110 attached to the main body 101 at an upper end thereof. The masonry alignment guide 110 is provided to keep masonry products 50 such as concrete block and brick level and straight as the device 100 is moved up the corner pole 210 to build up the structural joint.
[0027] The alignment guide 110 comprises alignment arms 111 that extend at an angle from each other to mate to the building corner. Each alignment arm 111 includes one or more string guide alignment supports 112 extending above arm 111 along a top surface thereof. The alignment arm 111 may be composed of PVC plastic of another material such as ABS, polypropylene, GE Lexan, etc. The string guide alignment support 112 includes a groove or alignment channel 113 therein that receives and aligns the masonry string 75 as it is paid out from the reel assembly 150 . Each alignment arm 111 additionally includes one or more viewing notches 114 between string guide alignment supports 112 to enable a user of the device to verify that the masonry product 50 is aligned with the masonry string 75 .
[0028] The alignment guide 110 also includes an offset guide 115 at the intersection of the two arms 111 . The offset guide 115 can be employed when using brick for job such as building a corner accent (sometimes referred to as a “Cowen corner”) and bands that encircle a residential building. Each alignment arm 111 includes a Support brace 116 which has a string keeper 117 therein. The string keeper is embodied as a notch or slot and is designed to hold the masonry string 75 secure; the string 75 is fed through the keeper 117 and a knot is tied such that the knot cannot pass through the slotted string keeper 117 . The string keeper 117 is thus employed when a alignment device 100 is receiving the string 75 from another alignment device 100 at the adjacent corner of the building structure. Further, all of the string guide alignment supports 112 and offset guide include a pair of wear pins 118 on the top corners thereof. The wear pins 118 are formed from metal or a harder plastic material prevent the masonry string 75 from cutting into the PVC material of the alignment arms 111 .
[0029] The main body 101 further includes a string guide alignment support assembly, shown generally at 130 . Assembly 130 includes a string guide alignment support 132 and a string feed guide 135 . The string guide alignment support 132 extends above the top of main body 101 and includes a string holder 134 to prevent the string from shifting out of position. The top ends of the string guide alignment support 132 also include a wear pin 118 thereon. The string feed guide 135 controls the string alignment as it comes off a string reel 155 of the reel assembly 150 . In an example, the string feed guide 135 is configured to hold the string in a 4″ offset for a step out work evolution in shifting from setting an 8″ concrete block to a 12″ block. The string feed guide 135 includes a channel or recess 137 which aligns the string as it comes off the reel 155 , and has a cross-wise string holder 139 to prevent the string 75 from shifting out of position.
[0030] The alignment device 100 includes at least one bottom support guide 140 attached to the main body 101 which provides support for the alignment guide 110 above it. Each bottom support guide 140 has brace supports 142 for additional support. The main body 101 also includes an alignment block 145 that maintains the masonry product (such as a concrete block) in the plumb position, so as to prevent shouldering. The alignment block 145 is provided on two sides of the main body 101 , each below a corresponding alignment arm 111 of the alignment guide 110 . Further, a thumb screw 148 is provided through the main body 101 for securing the alignment device 101 to the corner pole 210 of the system 1000 .
[0031] As shown in FIG. 3 , the dotted line 146 indicates the path of the string 75 from the reel assembly and out from device 100 so as to provide a level line for building up the structural joint with masonry products 50 . Following dotted line 146 , string 75 rolls off of the string reel 155 , up through the string feed guide 135 , along offset guide 115 and across a viewing notch 114 , along one side of a string guide alignment support 112 (within a channel 113 not shown), across another viewing notch 114 and then along through a channel 113 (not shown) on an opposite side of another string guide alignment support 112 , and then over to a alignment device 100 on an adjacent corner. The string 75 is tightened in a keeper 117 at the other device 100 so as to provide a level line for building up the structural joint with masonry products 50 .
[0032] FIG. 4 is an exploded perspective view of a reel assembly the alignment device of FIG. 2 . The reel assembly 150 includes a spacer block 151 which provides support for the string reel 155 and also provides additional thread depth for the reel support bolt 153 . A notched locking wheel 152 is provided between spacer block 151 and string reel 155 . The locking wheel 152 is secured to the string reel 155 and holds the reel 155 in the desired position when the masonry string 75 is being tightened. The reel assembly 150 includes a handle 156 to reel-in loose masonry string 75 .
[0033] The tightening of the string 75 should be done by hand-pull, with the slack taken in by actuating handle 156 . The spacer block 151 includes a pawl 158 ( FIG. 2 ) that engages the locking wheel 152 to secure it in the desired position when the string is tightened. The handle 156 includes a handle extension 157 that improves leverage for reeling.
[0034] FIGS. 5-7 describe the corner pole assembly 200 of FIG. 1 in further detail. As shown in FIG. 5 , the corner pole 210 supports the alignment device thereon against a building structure. In an example, corner pole 210 may be constructed of 2″ square tubing, 16 gauge steel, although it is evident that other materials could be used, such as an alloy, aluminum, a hard plastic, etc. At the corner pole bottom is provided a pair of different sized flange 212 , 214 . Flange 212 is employed when the alignment device is employed to lay masonry products 50 and includes a small offset from the corner post to accommodate the alignment device. In an example, flange 212 is welded to the corner pole 210 and may be 4′ long×1½″ wide. Flange 214 is employed when the alignment device is not used to lay masonry products 50 . In an example, flange 214 is welded to the corner pole 210 and may be 2′ long×1½″ wide. Flange 214 does not have an offset from the corner pole and can be used as a corner marker at the location where the corner of the structure will be formed.
[0035] As shown in FIG. 6 , the corner pole brace collar 220 includes a recess 222 to receive the thumb screw 148 that extends there through and into the main body 101 of the alignment device 101 . The brace collar 220 can be secured to the corner pole 210 via a suitable fastener such as a thumb screw. In an example, brace collar 220 can be made from 2″ flat stock steel.
[0036] The brace collar 220 includes a pair of flange brace supports 224 that may be composed of 1½″ flat stock steel. Each flange brace support 224 includes a drilled hole 226 for receiving the corner braces 230 . As shown in FIG. 7 , each brace 230 may be composed of two brace arms of different width and thickness such that the lower arm 231 fits within the upper arm 232 and is secured by a suitable fastener 233 to form the brace 230 . The end of the upper arm 232 includes a flat bar 234 welded thereto which includes a drilled hole 236 that mates which the drilled hole 226 of the flange brace support 224 so that the brace 230 can be secured to the brace collar 220 with a suitable fastener. At the lower end of brace 230 , the lower arm 231 includes a flat bar 235 with a drilled hole 237 to receive a threaded fastener (bolt) end 239 from a piece of steel pipe 238 . The pipe 238 has a hollow interior configured to receive a piece of rebar 240 ( FIG. 1 ) for securing the brace 230 into the ground. The bolt end 239 of pipe 238 may be secured to the flat bar 235 via a suitable fastener such as a wing nut 241 .
[0037] Installation of the system 1000 is explained as follows. Initially the corner pole 210 is set up and braced with braces 230 to hold the corner pole 210 in a vertical position. Then the corner pole 210 is scored every 8″ or brick, or every 12′ for block. The alignment device 100 is then installed on the corner pole 210 via the thumb screw 148 , noting that the device 100 is slid down the corner pole 210 to the proper elevation for laying the first row of bricks, and then secured.
[0038] To create the level line, the reel 155 is release by unlocking pawl 158 , and string 75 is paid out from the reel assembly 150 through alignment channels on the main body and alignment arms (i.e., as described in FIG. 3 , through the string feed guide 135 , along offset guide 115 , across viewing notch 114 and along one side of a first string guide alignment support 112 , across another viewing notch 114 and along an opposite side of a second string guide alignment support 112 , and then out to be pulled over to another alignment device 100 on an adjacent corner. The payed-out string 75 is tightened and secured in a string keeper 117 at the other alignment device 100 , and then the string reel 115 is locked at the first device 100 via pawl 158 . Accordingly, a level line has been created for building up the structural joint with masonry products 50 at a fraction of the time it would take a lead mason using conventional level line techniques.
[0039] The lead mason can then begin building the first row of masonry products 50 along the level line formed between the alignment devices 100 . Once complete, the alignment devices 100 are raised to the next score line on the corner pole 210 and secured to building the next row off of the structural joint. The corner pole 210 is typically about eight (8) feet in length. In building structures above 8′, the pole 210 can be eliminated as the level line has already been achieved and the top length of the structure is plumb.
[0040] FIG. 8 is a perspective view of a alignment device for assembling a structural joint of a structure in accordance with another example embodiment that is usable in the system of FIG. 1 . As many of the components of device 100 ′ have already been described with regard to alignment device 100 in FIGS. 2-7 , only the differences are discussed in detail. Like reference numerals are used for like elements where applicable.
[0041] Referring to FIGS. 8 and 9 , alignment device 100 ′, also called a corner mount assembly, is shown in this embodiment as being applicable to an “inside corner,” i.e., it is used to build up an inside corner of a building structure with masonry product 50 . Accordingly, the device 100 ′ is employed where the structural joint to be built up is an inside corner, such as a 45° inside corner, for example.
[0042] Like the alignment device 100 of FIG. 1 , alignment device includes a main body 101 with an alignment guide 110 attached thereto. The alignment guide 110 includes a pair of alignment arms 111 with a viewing notch provided 114 between a pair of string guide alignment supports 112 extending above the alignment 111 along a top surface thereof. The abutting ends of the interior string guide alignment supports 112 each include a wear pin 118 thereon. The wear pins 118 prevent the masonry string 75 from cutting into the PVC material of the alignment arms 111 .
[0043] Each alignment arm 111 of alignment guide 110 is supported by a support brace 116 having a string keeper 117 to hold the masonry string 75 secure when alignment device 100 ′ receives the string 75 from another alignment device 100 or 100 ′ at the adjacent corner of the building structure. The support brace 116 also includes a string feed hole 119 to maintain the masonry string 75 aligned with the string reel 155 . The support brace 116 includes wear pins 118 that extend out the rear facing to prevent the masonry string 75 from cutting into the PVC material of the support brace 116 .
[0044] Unlike device 100 of FIGS. 2 and 3 , device 100 ′ has no guide alignment support assembly 130 . Instead, as string 75 comes off the string reel 155 , it travels over a wear pin 118 and up through feed hole 119 , which serves as a string guide. From there, the string passes around a wear pin 118 on an interior string guide alignment support 112 of one alignment arm 111 , across viewing notch 114 and through an alignment channel 113 of the exterior string guide alignment support 112 on arm 111 , to be received at an alignment arm 111 of another alignment device 100 / 100 ′ at an adjacent corner.
[0045] The components and functions of the reel assembly 150 are the same as described in FIG. 4 , thus a detailed explanation is omitted for purposes of brevity. The alignment device 100 ′ is attached to the corner pole 210 as previously described. The method for assembling a structural joint of a structure using system 1000 configured with alignment device 100 ′ is also similar to as previously described, with the exception of the different string alignment off of reel 155 as described above.
[0046] FIG. 10 illustrates locations on a building structure where different alignment devices can be employed to build Lip structural joints. As shown in FIG. 10 , a masonry structure (footwall) on the outside of a building 170 has several structural joints that need to built up to lay the masonry products in building up the structure 170 . Accordingly, different alignment devices 100 , 100 ′ can be used depending on the corner angle. As shown alignment device 100 A is used for building up a 90° inside corner joint, device 100 B for a 45° inside corner joint (for structures below one side of a bay window) and device 100 C for a 45° outside corner joint can be employed in system 1000 .
[0047] FIG. 11 is a perspective view of a alignment device for assembling a structural joint of a structure in accordance with another example embodiment that is usable in the system of FIG. 1 . As many of the components of device 100 ″ have already been described with regard to alignment devices 100 and 100 ′, certain differences are discussed in detail. Like reference numerals are used for like elements where applicable.
[0048] Referring to FIGS. 11 and 12 , alignment device 100 ″ is applicable to expansion or control joints for long expanses of a structure. For example, in building a 400 foot wall, a control joint is employed at 50 foot intervals for structural strength and to maintain the level-line so as to have a plumb, level structure. Thus, control joints can be built between two alignment devices 100 ″ at a distance of 50 feet apart. Pulling the masonry string 75 at 50 foot intervals reduces string bow; building up sectional parts of the wall between control joints maintains the top of the wall level and flat.
[0049] Referring to FIGS. 11 and 12 , the alignment guide 110 is flat so as to be flush across the control joint. The alignment guide 110 includes three viewing notches 114 provided between four string guide alignment supports 112 extending above the alignment guide 110 along a top surface thereof. Each string guide alignment support 112 has an alignment channel (not shown) grooved therein along its length.
[0050] Unlike the alignment device 100 of FIGS. 2 and 3 , alignment device 100 ″ has no guide alignment support assembly 130 . Instead, as string 75 comes off the string reel 155 , it is pulled over a wear pin 118 on brace support 116 and up through feed hole 119 that serves as a string guide. The string passes along the channels in the guide alignment supports 112 and viewing notches 114 , to be received at an alignment guide 110 of another device 100 ″ (another control joint) or at an alignment arm 111 of another alignment device 100 / 100 ′ at a corner, for example.
[0051] The components and functions of the reel assembly 150 are the same as described in FIG. 4 , thus a detailed explanation is omitted for purposes of brevity. The alignment device 100 ″ is attached to the pole similar to corner pole 210 , but without flanges 212 and 214 . The method for assembling a structural joint of a structure using system 1000 configured with alignment device 100 ″ is similar to as previously described in FIG. 3 , with the exception of the different string alignment off of reel 155 as described above.
[0052] The example alignment device, system and method for assembling structural joints can enable less-skilled masons to perform the level-line evolution. There is no need to actually build a corner before laying rows of masonry products; the system can be installed and the masonry products can be laid immediately. The use of the alignment devices removes the human error from manual sighting so as to build plumb structural joints for both residential and commercial structures. Additionally, the system facilitates the ability of the mason to check the job for squareness. Building up masonry products around bay windows becomes much simpler with the example system and device, and cowan corners may be built only with trig pins and other tools.
[0053] The example embodiments being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as departure from the exemplary embodiments of the present invention. All such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | An alignment device for assembling a masonry joint includes a main body configured to slidably engage a generally vertical support pole, the main body including a first arm and a second arm projecting away from the main body, the first arm defining a predetermined angle relative to the second arm, and a reel assembly on the main body for supporting a reel of string, the main body further including a string guide between the reel assembly and the first arm for guiding a string from the reel to the first arm. Also a method of building a wall using the alignment device. | 4 |
GOVERNMENT INTEREST
The invention described herein may be manufactured, used, sold, imported, and/or licensed by or for the Government of the United States of America.
FIELD OF INTEREST
This invention relates to laser range finders and laser designators.
BACKGROUND OF THE INVENTION
Laser range finders and laser designators are becoming an increasingly vital component in high precision targeting engagements. The precise and accurate range to target information is an essential variable to the fire control equation of all future soldier weapons. This information is easily, and timely, provided by laser range finders. The laser designator operator surgically selects a target by placing the high-energy laser beam onto the target.
Unfortunately, current fielded laser systems are bulky, heavy and expensive. These laser systems were developed with twenty year old laser technology.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide an end pumped slab laser cavity for a laser range finder and laser designator that minimizes the size, weight, performance and production costs of the laser range finder and laser designator. To meet this object, a laser diode pump produces laser outputs into an Nd:YAG folded cavity. The output from Nd:YAG folded cavity 101 passes through a passive/active Q-switch 102 and then, through an optical parametric oscillator 103 . The components of this laser range finder or laser designator are optically fused together into a single block. The end result is an eye safe 1.5 μ output for laser designation or range finding.
This invention proposes a new concept, the End Pumped Slab Laser Cavity, which makes the development/fabrication of a very compact laser range finder or designator feasible.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects of the invention will become readily apparent in light of the Detailed Description Of The Invention and the attached drawings wherein:
FIG. 1 is a block diagram of the present invention having an end-pumped Nd:YAG—OPO micro-slab design.
FIG. 2 is a block diagram of the present invention giving more details of the end-pumped Nd:YAG—OPO micro-slab design.
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes several optical components fused into one ‘block’ or pseudo-monolithic laser cavity. It is termed “pseudo-monolithic” since many components are incorporated into the structure. The proposed invention is named ‘End Pumped Slab’ because of its design is intended for laser diode pumping from the end, even though for higher energy diode pumping from the sides is possible. FIG. 1 depicts the components of the End Pumped Slab Laser Cavity. As shown in FIG. 1 a laser diode pump 100 produces laser outputs to an Nd:YAG folded cavity 101 . The output from Nd:YAG folded cavity 101 passes through a passive/active Q-switch 102 and then, through an optical parametric oscillator 103 . The end result is an eye safe 1.5 μ output.
The optical components described above are bonded (diffusion or optical epoxy) to form one optical ‘block’. All components are pre-aligned during the crystal manufacturing process to form the optical laser cavity. The polarization coating at one of the turn angles is required only if linearly polarized output is required for pumping an external optical parametric oscillator (OPO) cavity 103 (e.g. to the 1.5 micron eye safe wavelength) or if an active, polarization dependent, Q-switch is used for precise timing of the laser output pulse. This polarization is essential for effective OPO conversion and active Q-switch 102 operation. The active material is Nd:YAG. The Q-switch 102 can be an optical passive device made from chromium YAG if critical pulse firing timing is not required. This component can also be coated with the proper optical layers for the laser cavity's output coupler.
All the optical components previously described have been fabricated in YAG-base materials. This is not necessary but desired in that the End Pumped Slab Laser Cavity has a uniform coefficient of thermal expansion and the Nd:YAG material is relatively inexpensive and available. This leads to robust/dependable operation over the wide range of thermal conditions the laser must operate. Other materials may be used in the End Pumped Slab Laser Cavity if conditions allow. For example, Nd:YVO4, Nd:YLF, Nd:YAP, etc. are all candidate materials that may be used in End Pumped Slab laser cavity configuration of the present invention.
The present invention simplifies the producibility of a laser range finder system. The fabrication of the End Pumped Slab Laser Cavity can be done using batch processing. Large rectangular, pre-coated optical components can be joined together, optically aligned to form the laser cavity and then sliced to produce modules. This batch process can greatly reduce the overall fabrication costs of the End Pumped Slab Laser Cavity module. The End Pumped Slab module is ultra-compact. Its overall size is approximately 15 mm (L)×10 mm (W)×5 mm (H) as depicted in FIG. 2 . This extremely small size of a laser cavity allows for construction of a very compact, and lightweight, laser range finder. FIG. 2 also shows the High-Reflection Coating (HR), the Polarized High-Reflection Coating (Pol-HR), and the Anti-Reflection Coating (AR) specifications for one example of the present invention. A standard Nd:YAG Crystal has the following properties. Such crystals can be found from such companies as Casix™.
1. Basic Properties (1.0 atm % Nd doped)
Chemical Formula
Nd: Y 3 Al 5 O 12
Crystal Structure
Cubic
Lattice Constants
12.01 Å
Concentration
~1.2 × 10 20 cm −3
Melting Point
1970° C.
Density
4.56 g/cm 3
Mohs Hardness
8.5
Refractive Index
1.82
Thermal Expansion Coefficient
7.8 × 10 −6 /K [111], 0–250° C.
Thermal Conductivity
14 W/m /K @ 20° C.,
10.5 W /m /K @ 100° C.
Lasing Wavelength
1064 nm
Stimulated Emission Cross Section
2.8 × 10 −19 cm −2
Relaxation Time of Terminal Lasing
30 ns
Level
Radiative Lifetime
550 μs
Spontaneous Fluorescence
230 μs
Loss Coefficient
0.003 cm −1 @ 1064 nm
Effective Emission Cross Section
2.8 × 10 −19 cm 2
Pump Wavelength
807.5 nm
Absorption band at pump wavelength
1 nm
Linewidth
0.6 nm
Polarized Emission
Unpolarized
Thermal Birefringence
High
2. Standard Products specification
Dopant Concentration (atomic %): 0.9%~1.1%
Orientation: <111> crystalline direction ( i À5 i ã)
Wavefront distortion: λ/8 per inch,
measured by a double-pass interferometer @
633 nm
Extinction Ratio:
Rods with diameter from 3 mm to 6.35 mm and with length to 100 mm: >
30 dB
Rods with diameter from 7 mm to 10 mm and with length to 100 mm: >
28 dB
Dimension Tolerances
Diameter: i À0.025 mm ( i À0.001″), Length: i À0.5 mm ( i À0.02″)
Barrel Finish: 50 80 micro-inch (RMS), grooved rod barrel are also
available
Ends Finish:
Surface Figure:
<λ/10 @ 633 nm
Parallelism:
<10 arc seconds
Surface quality:
<5 arc minutes
Clear Aperture:
>10/5 Scratch / Digper MIL-O-1380A
Chamfer:
<0.1 mm @ 45 i ã
Clear Aperture:
extend over the entire faces to the chambered
edges
Anti-Reflection Coating:
Single layer MgF2 coating with high damage
threshold for high power laser
operation. Reflectivity R < 0.25% @ 1064 nm per surface.
Damage threshold
over 750 MW/cm2 @ 1064 nm, 10 ns and 10 HZ.
High-Reflection Coating:
Standard HR coating with R > 99.8% @ 1064 nm and
R < 5% @ 808 nm can
be performed. Other HR coatings, such as HR @ 1064/532 nm,
HR @ 946 nm,
HR 1319 nm and other wavelengths are also available.
Standard products in-stock:
The standard Nd: YAG laser rod has dimensions
of ?3 × 5 mm and ?4 × 50
mm with AR or HR- coating for Diode Pumped Solid State Lasers (DPSS)
Of course for the present invention, these standard performance specifications would have to be changed in accordance with the sample specifications given in FIG. 2 . However, such crystals are available and may be adapted to accommodate the present invention.
The End Pumped Slab Laser Cavity is a module that requires none of the labor extensive alignment procedures as current laser range finders/designators. No optical holders have to be fabricated, no complex engineering is required to design the optical cavity, and no precise laser cavity alignment(s) are required. Therefore, production labor and material costs are greatly reduced.
The End Pumped Slab Laser Cavity is a modular component. The modularity lends to ease of design for different pump sources. It can be incorporated in a flash lamp pumped or laser diode pumped system. The energy of the pump source (e.g. drive electronics) can be tailored for the specific mission (e.g. long range vs. medium range performance) without forcing all of the systems to meet the high demand requirements of the few.
In particular, the cavity is configured for optimal absorbtion for diode laser pumping over broad temperature ranges. The End Pumped Slab cavity is designed to be pumped by laser diode arrays on either side of the “plate.” The width of the cavity has been designed to absorb nearly all of the laser diode pump output.
The present invention may be used as the laser source in very compact laser range finders or laser designators. It can be coupled with an OPO cavity for generation of eye safe laser output for eye safe laser range finding. These laser range finders have both military and commercial applications. The compact design of the End Pumped Slab Laser Cavity also lends itself to placement in other laser-based portable/hand-held devices. These may be medical devices, industrial tools or scientific equipment that would benefit from the size/weight reduction, dependable performance, and low cost of the End Pumped Slab Laser Cavity. | The End Pumped Slab Laser Cavity incorporates all optical components required for a short-pulse laser. These optical components are ‘locked’ into alignment forming an optical laser cavity for diode laser or flash lamp pumping. The optical laser cavity never needs optical alignment after it is fabricated. The cavity is configured for optimal absorbtion for diode laser end-pumping over broad temperature ranges. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a §371 of International PCT Application PCT/FR2013/050720, filed Apr. 2, 2013, which claims the benefit of FR1253464, filed Apr. 16, 2012, both of which are herein incorporated by reference in their entireties.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a plant for compressing a gas stream comprising at least 0.1% water, typically at least 0.1% water and at least 20% CO 2 , and to a compression process using such a plant.
BACKGROUND
In order to reduce emissions of CO 2 of human origin into the atmosphere, processes for capturing the CO 2 generated in a given process have been developed. It is a question of extracting the CO 2 from a gas generated by the process, optionally purifying it and finally, in general, compressing it in order to transport it in a pipeline.
One of the routes for treating CO 2 consists in distilling the CO 2 -rich gas stream in a cryogenic purification unit.
In such a unit, it is necessary to compress the incoming gas: it being possible for the incoming gas to be flue gases resulting from a process such as an adsorption purification process or a blast furnace process.
For applications that treat wet CO 2 , that is to say comprising at least 0.1% water, the use of stainless steel compressors is recommended since the condensation of the wet CO 2 forms carbonic acid which is highly corrosive for carbon steels. However, the use of stainless steel compressors leads to a plant that has a high cost.
Furthermore, document FR-A-1412608 teaches a plant for intermediate cooling of compressed gas comprising compressors associated with exchangers and a cooling water circuit. The consecutive exchangers are connected in series to the cooling water circuit. Similar teaching is given by documents WO-A-2011/088527, US-A-2011/000227 and U.S. Pat. No. 7,269,956.
SUMMARY OF THE INVENTION
Hence, one problem that is faced is to provide a plant for supplying a cryogenic distillation column that has a lower cost.
One solution of the invention is a plant for compressing a gas stream comprising at least 0.1% by volume of water, comprising a compressor having N compression stages, wherein:
each compression stage comprises a compression means and an exchanger connected directly or indirectly to a cooling water circuit C; and at least a first exchanger IC 2 and a second exchanger IC 3 of a first and of a second consecutive or non-consecutive compression stages are connected in series to the cooling water circuit C,
characterized in that the exchangers not connected in series to the cooling water circuit comprise, at their cooling water outlet, a device that makes it possible to create a pressure drop.
Depending on the case, the plant according to the invention may have one or more of the following characteristics:
the shells of the exchangers of the n first compression stages, located on the feed side of the compressor, consist of a steel having a chromium content of less than 11% by weight and no stainless coating, with n≦N−1; the shells of the exchangers of the n first compression stages, located on the feed side of the compressor, are made of carbon steel, with n≦N−1; the second exchanger IC 3 is also connected directly to the water cooling circuit C and a temperature regulation system makes it possible to control the mixing of the cooling water resulting from the first exchanger and of the cooling water resulting directly from the cooling water circuit C (cf. FIG. 4 ); the exchangers not connected in series to the cooling water circuit comprise, at their cooling water outlet, a device that makes it possible to create a pressure drop corresponding to the pressure drop caused by the exchangers being connected in series; the exchanger of the last compression stage, located on the production side of the compressor, is made of stainless steel; within the context of the invention, preferably n=N−1. the device that makes it possible to create a pressure drop comprises an orifice or a valve, typically a pressure drop of the order of 1 bar (or more if necessary); the feed plant feeds a cryogenic distillation column with a gas stream.
Another subject of the present invention is a process for compressing a gas stream comprising at least 0.1% water and at least 20% CO 2 using a compression plant according to the invention.
Preferably, the compression process according to the invention is characterized in that:
the temperature of the cooling water T w of the cooling circuit C is measured; T w is compared to the dew point T d of the gas stream entering a second exchanger IC 3 belonging to one of the N−1 compression stages located on the feed side of the compressor;
and, if the temperature of the water of the cooling circuit T w is such that T w −T d <10° C.:
the cooling water inlet of said exchanger is connected to the cooling water outlet of a first exchanger IC 2 belonging to said N−1 compression stages, located on the feed side of the compressor, and/or water external to said compression plant and having a temperature T s >T w is introduced directly into the cooling water circuit C or directly into said exchanger,
so that the temperature T exch of the water entering said exchanger is such that
T exch −T d ≧10° C.
Preferably, the gas stream is a stream produced by an H 2 PSA (pressure swing adsorption), a CO 2 PSA, a membrane separation process, a combustion turbine, an oxy-fuel combustion process, a cement production process, a blast furnace, a hydrogen production process or a refining process.
The solution proposed by certain embodiments of the present invention make it possible to reduce the price of the machine by avoiding the condensation of the wet CO 2 (that is to say comprising at least 0.1% water) in the compressor, making it possible to choose much less expensive materials, typically carbon steel.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the invention and are therefore not to be considered limiting of the invention's scope as it can admit to other equally effective embodiments.
FIG. 1 gives an example of the composition of a gas stream resulting from a PSA in the production phase.
FIG. 2 gives dew point curves for the various temperatures of the gas stream.
FIG. 3 shows an embodiment of the invention.
FIG. 4 shows an alternate embodiment of the invention.
DETAILED DESCRIPTION
The plant and the process according to the invention will be described in greater detail with the aid of FIGS. 1 to 3 .
It should be noted firstly that the composition of the gas stream to be compressed is not constant and varies as a function of the operating phases of the PSA or blast furnace, which modifies the value of the dew point.
The minimum temperature of the gases in an exchanger is considered to be equal to the cooling water inlet temperature, corresponding to the skin temperature of the tubes of the exchanger in which the cooling water circulates. In other words, the minimum temperature of the gas stream in the exchanger will be able to be controlled by the cooling water inlet temperature.
Hence, in order to avoid the risk of condensation in the heat exchangers, a margin will be able to be constantly maintained between the conditions of the gas stream and its dew point. In order to maintain this margin, the plant according to the invention is used.
The invention will now be described in detail by taking the example of a compression plant comprising four compression stages (cf. FIG. 3 ) that feeds a cryogenic distillation column with a compressed gas stream.
The exchangers IC 2 and IC 3 of the second and of the third compression stage are connected in series ( FIG. 3 ). The exchanger IC 3 of the third compression stage will be referred to as “second exchanger” according to the invention while the exchanger IC 2 of the second compression stage will be referred to as “first exchanger” according to the invention. In other words, the exchanger of the third compression stage is fed by the return of hot water (cooling water heated in the exchanger of the second compression stage) originating from the exchanger of the second compression stage thus allowing a sufficient margin at the dew point in the exchanger of the third compression stage and thus avoiding the risks of condensation. The temperature difference of the water between the inlet and outlet of the exchanger is generally 10° C.
The exchangers IC 2 and IC 3 of the second and of the third compression stage must be designed for an identical cooling water flow. A device (an orifice or a valve for example) must be installed at the outlet of the exchangers IC 1 and cooler of the first and of the fourth compression stage in order to create an additional pressure drop (typically of 1 bar) corresponding to the pressure drop induced by assembling the exchangers IC 2 and IC 3 of the second and of the third compression stage in series.
Means for measuring the temperature, pressure and water content of the gas flow and the temperature of the water of the cooling circuit at the inlet of the exchanger of the third compression stage may be installed in order to calculate the difference between the temperature of the gas flow and its dew point.
Other arrangements are also possible for feeding the exchanger of the third compression stage with hotter water such as for example a mixture of cold and hot water through a thermostatic valve, in particular when the margin observed is not sufficient.
It should be noted that in general the first exchanger or exchangers of the first compression stages located on the feed side of the compressor do not need to receive hotter water and are connected directly to the cooling water circuit. Indeed, since the gas flow is at lower pressure, its dew point is colder and therefore further away from the nominal temperature of the cooling water. When the pressure of the gas stream increases, its dew point approaches that of the cooling water and in order to maintain a sufficient margin, the invention proposes to circulate the cooling water at least partially in series in at least two exchangers.
Regarding the means for compressing the first three compression stages, the volute casings of the compressor are made of carbon steel as for standard compressors. The impellers are made from a material made of martensitic stainless steel as for standard compressors. The exact grade is selected in order to meet the criterion of API617 (American code for machines) for applications with hydrogen-containing gas.
The exchangers of the first three compression stages are preferably shell and tube exchangers. Their shells are made of carbon steel as standard. The tubes are generally made of a copper-based material. For such an application with a closed cooling water circuit (containing corrosion inhibitors) and wet gas, the tubes are made of carbon steel. For an open or semi-open cooling water circuit, tubes made of stainless steel or copper are necessary to prevent corrosion of the water side.
Preferably, aluminum fins are installed on the tubes to improve the heat transfer and thus reduce the size of the exchanger. The tube sheet is made of forged carbon. To avoid any risk of leakage from the cooling water side to the process side which would lead to condensation and then to corrosion of the process side, a strength weld of the tube/tube sheet connection is recommended. These welds are then tested by a helium leakage test with an acceptance criterion based on a low leakage level. In order to reduce the velocity of the gas entering the exchanger, a “velocity limiter” plate is added. All the other gas side parts of the exchanger are made of carbon steel. These may be galvanized.
Drains are installed at a low point in case of condensation (in case of rupture of the tube for example). A level detector in these low points makes it possible to detect the presence of liquid in the exchanger. A water separator is installed at the outlet of each exchanger in order to prevent any drop from going to the impeller in case of condensation (in case of rupture of the tube for example). Automatic condensate traps are not necessary. Only manual valves are installed in the drain when the liquid is detected. A temperature probe in the intake pipes of the stages makes it possible to detect condensation and stop the machine.
The exchanger of the fourth compression stage (cooler) is entirely made of stainless steel (the grade 304L is a good compromise) because it is subject to much condensation. A water separator and an automatic condensate trap make it possible to remove the condensed water (having a high content of carbonic acid) from the gas. These devices must be suitable for carbonic acid.
Another subject of the present invention is a process for starting-up the compression plant according to the invention, wherein:
a dry gas at a temperature T g above the dew point T d of the gas stream to be compressed is compressed in the compressor having N compression stages until the skin temperature of the n first compression means and of the n first exchangers in contact with the gas stream, located on the feed side of the compressor with n≦N−1, and the temperature of the water from the cooling water circuit C are above the dew point T d of the gas stream to be compressed, the dry gas is replaced by said gas stream to be compressed.
Preferably, the gas stream comprises at least 0.1% water and at least 20% CO 2 , and the dry gas is nitrogen or carbon dioxide.
This start-up procedure makes it possible to heat the parts of the compressor (volute casings, pipes, exchangers, etc.) in contact with the gas stream in order to avoid condensation of the CO 2 and therefore corrosion of these parts.
During winter, the cooling water may be too cold and could cause condensation in the exchangers. The nitrogen start-up phase also makes it possible to heat the temperature of the cooling water to a sufficient level. The temperature of the cooling water is monitored and comes under the conditions necessary for replacing nitrogen with the process gas and also for controlling and optimizing the cooling capacity of the water system (operation/shutdown of the cooling system fans). The power of the cooling water of the cooling fan is reduced when the water is too cold with respect to the water content in the process gas.
Lastly, another subject of the present invention is a process for shutting down the feed plant according to the invention, wherein the compressor is flushed and purged with a dry gas.
While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step. The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
“Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
“Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary a range is expressed, it is to be understood that another embodiment is from the one.
Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such particular value and/or to the other particular value, along with all combinations within said range.
All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited. | A method and apparatus for compressing a gas flowing comprising at least 0.1 vol % water, include a compressor containing N compression stages, in which each compression stage includes a compressing means and an exchanger directly or indirectly connected to a water-coolant circuit; and in which at least a first exchanger and a second exchanger, in first and second consecutive or non-consecutive compression stages, are connected in series to the water-coolant circuit. The exchangers, which are not connected in series to the water-coolant circuit, include at their water-coolant output a pressure drop device. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] N/A
FIELD OF THE INVENTION
[0002] The present invention relates generally to the field of ladders and devices for ladders. More particularly, the present invention relates to a protective ladder guard for hunting stands to prevent unauthorized persons from ascending the ladder to reach the hunting stand platform in the owner's absence.
BACKGROUND OF THE INVENTION
[0003] The use of ladder hunting stands, which provide an elevated platform above the ground while hunting wild game animals, is well documented. There are numerous commercially available ladder tree stands, tri-pod stands, elevated modular stands, automated game feeder systems and the like, which provide access to an elevated platform or enclosure relative to the ground, using an integral ladder for climbing. While tree stand manufacturers produce a wide variety of ladder stands, they do not provide devices designed to prevent unauthorized persons from climbing the ladder to reach the hunting platform in the owner's absence. Such a device would prevent trespassing, the poaching of wild game animals, and the theft or vandalism of the tree stand or the tree stand accessories. As a result, demand exists for a simple, portable, convenient, inexpensive protective device, designed to prevent unauthorized persons from ascending the ladder to reach a hunting platform above.
[0004] The unauthorized climbing of ladder hunting stands is a problem many hunters face. This unwelcome behavior may often result in the theft of the hunting stand, hunting stand accessories or other valuable personal property, and facilitates the poaching of wild game animals. Many tri-pod, elevated modular stands and automated game feeder systems have further refinements of value also posing a risk of theft or vandalism. The aftermath of such trespassing activity continues to be a source of great frustration to honest and ethical hunters.
[0005] Ladder guards, which deter unauthorized ladder climbing are well known. U.S. Pat. Nos. 7,793,759 to Aiken, 7,717,231 to Horton, 5,441,126 to Orrick, 4,126,206 to Becnel, and 3,968,857 to Bryan are examples representing endeavors to block access to a plurality of rungs to prevent unauthorized climbing of ladders. While such devices and methods suit their intended purpose well for use with commercial ladders, step ladders, swimming pool ladders and the like, or for ladders of a type permanently secured to tall buildings, radio towers, storage tanks and the like, they are not satisfactory for use with modern ladder hunting stands, and do not effectively solve many specific problems faced by hunters.
[0006] One solution, the Vital-Security™ slide/lock by Vital Zone™, requires permanent structural modifications be made to the lower bottom two sections from the original tree stand ladder, which incorporate a set of sleeves and hinges now integral to the intersecting ladder columns, locking pin mechanisms and padlocks. In use, both hinge mechanisms are first unlocked and then the protective sleeves are raised to allow the bottom section of the ladder to be folded upward to connect with a receiver housing integral to the next uppermost section of the ladder, allowing the hinge mechanism to be secured using a locking pin, and then be finally secured using a padlock. To lower the ladder section and return it to ground level, the process is reversed, thus allowing access to the ladder.
[0007] Another solution, manufactured by Primal Vantage™, requires permanent replacement of the lower bottom section from the original tree stand ladder, with a new section of ladder, having a removable square framed insert having two rungs welded horizontally inside the frame, requiring four long threaded bolts to be passed through the column from the outside and secured into four threaded receiver holes integral to the square framed insert. To prevent climbing the ladder, the four long bolts must be removed and retained for later use, the insert section must be removed, and transported to and from the hunting stand each time. The process is reversed to reinstall the section, thereby allowing access to the ladder.
[0008] Many hunters reject such solutions because of the many potential safety problems and mechanical difficulties encountered while attempting to retrofit a ladder hunting stand that has already been installed. In the case of ladder tree stands, the ladder supplied by the manufacturer is an integral component of the product's design, thus any post installation modifications could affect the tree stand's structural integrity. Once connected and installed, each section of the ladder serves to support the next section sequentially supporting the ladder structure and the tree stand platform. Removing a section of the ladder is risky and difficult post installation due to the difficulty of separating the reverse interconnecting sections, and compounded by the total combined weight of downward forces being applied by the mass of the ladder and tree stand platform. Any attempt to remove the ladder or to rotate a section of the ladder out of the way could negate the structural support element designed for the ladder thus affecting platform sturdiness, allowing other ladder sections to separate or allowing the hunting platform itself to shift position on the tree. Undermining the safety and stability of the tree stand platform in this manner could lead to a potentially unsafe or dangerous situation, especially if the ladder or platform becomes loosened or dislodged from the tree while in use. Should an unfortunate accident or injury occur, the hunter also bears risk of liability should an insurance claim ensue. Potential remedies could also be found limited simply because structural modifications were made to the tree stand after purchase.
[0009] Another problem encountered is that these solutions require several time consuming, intricate, multi-step tasks, which must be completed with a certain degree of precision, and which must be performed safely every time the hunter enters or leaves the area. In addition, it is highly desirable to occupy the hunting stand well before sunrise and depart the area after sunset, thereby increasing the difficulty in performance of these tasks in darkness, thus reducing the safety margin required to perform such tasks. In addition, maintaining total quiet of the surrounding area is also an essential element for successful game hunting. It is doubtful these tasks can be accomplished consistently, quickly, and safely in the dark, without making unwanted metallic noises, which undoubtedly will disturb the wild game animals in the surrounding area. In the case of tri-pod hunting stands or elevated modular houses, the problem encountered is that attempting to retrofit the ladder is likely not a practical solution, because the entire ladder is typically welded to the tri-pod frame or modular structure.
[0010] As such, considering the foregoing, it may be appreciated that there continues to be a need for novel and improved devices and methods for preventing access to ladder hunting stands, which solves the aforementioned problems, protects the private property of hunters and prevents poaching of wild game animals.
SUMMARY OF THE INVENTION
[0011] The foregoing needs are met, to a great extent, by the present invention, wherein in aspects of this invention, enhancements are provided to the existing model of ladder guards.
[0012] Aspects of the present invention relate to a hunting ladder guard for hunting ladder stands, tri-pod stands, modular hunting stands and the like.
[0013] In related aspects, the hunting ladder guard provides a simple yet effective protective ladder guard device to prevent unauthorized persons from ascending the ladder to reach the hunting stand platform in the owner's absence, thereby preventing trespassing, theft, vandalism and poaching of wild game animals.
[0014] In related aspects, the hunting ladder guard is designed to secure most hunting ladder stands and tri-pod ladder stand designs.
[0015] In an aspect, a hunting ladder guard, can include:
a. a ladder guard plate, further including
i. a plate hook, which is connected to an upper end of the ladder guard plate; is configured as an inward protruding hook that attaches on to an upper rung of a hunting ladder;
ii. two or more bracket apertures; and
b. a bracket;
such that a lower end of the ladder guard can be attached to a lower rung, and the bracket inserted through two consecutive bracket apertures, which are positioned such that an upper leg of the bracket reaches behind and over the lower rung, and a lower leg of the bracket reaches behind and under the lower rung, such that a pad lock can be inserted through pad lock apertures in the upper and lower legs of the bracket, thereby locking the ladder guard plate in place on the hunting ladder.
[0021] In related aspects, the hunting ladder guard is designed to be inexpensive, lightweight, sturdy, weatherproof, convenient, easy to transport, and easy to use. In further related aspects, it reduces risk of potential serious injury by not requiring the hunter to retro fit, disassemble or reassemble the ladder stand sections because the ladder or hunting platform is never retracted, replaced or moved, and thus does not undermine the hunting stand structural integrity.
[0022] In other related aspects, the hunting ladder guard requires no special tools, or installation or removal of nuts and bolts, and complex repetitive installation and removal tasks are reduced to a minimum.
[0023] In other related aspects, the hunting ladder guard allows hunters to quickly and quietly unlock the device with a minimum of effort, while standing on the ground, while working in darkness and without disturbing nearby game animals, place the accessory on the ground while hunting, and quickly, easily and quietly reinstall and secure the device before departing the area. Further, in related aspects, the hunting ladder guard provides year round protection, should a hunter decide to leave the hunting stand in place during the off-season.
[0024] There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
[0025] In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. In addition, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
[0026] As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 illustrates a perspective view of a ladder guard installed on a hunting ladder, according to an embodiment of the invention.
[0028] FIG. 2 illustrates a perspective view of a ladder guard before installation on a ladder, according to an embodiment of the invention.
[0029] FIG. 3 illustrates a rear perspective view of a ladder guard installed on a ladder, according to an embodiment of the invention.
[0030] FIG. 4 illustrates a front perspective view of a ladder guard plate, according to an embodiment of the invention.
[0031] FIG. 5 illustrates a rear perspective view of a ladder guard plate, according to an embodiment of the invention.
[0032] FIG. 6 illustrates a perspective view of a bracket of a ladder guard, according to an embodiment of the invention.
[0033] FIG. 7 illustrates a side, partially center-cut view of a section of a hunting ladder guard, according to an embodiment of the invention.
[0034] FIG. 8 illustrates a perspective view of a ladder guard, according to an embodiment of the invention.
DETAILED DESCRIPTION
[0035] Before describing the invention in detail, it should be observed that the present invention resides primarily in a novel and non-obvious combination of elements and process steps. So as not to obscure the disclosure with details that will readily be apparent to those skilled in the art, certain conventional elements and steps have been presented with lesser detail, while the drawings and specification describe in greater detail other elements and steps pertinent to understanding the invention.
[0036] The following embodiments are not intended to define limits as to the structure or method of the invention, but only to provide exemplary constructions. The embodiments are permissive rather than mandatory and illustrative rather than exhaustive.
[0037] In the following, we describe the structure of an embodiment of a hunting ladder guard 100 with reference to FIG. 1 , in such manner that like reference numerals refer to like components throughout; a convention that we shall employ for the remainder of this specification.
[0038] In an embodiment, as illustrated in FIG. 1 , a hunting ladder guard 100 can be installed on a hunting ladder 150 , such that it prevents a person who is not authorized to use the hunting ladder 150 from climbing up the hunting ladder, by covering a plurality of rungs of the ladder 150 . FIG. 1 shows the hunting ladder guard 100 installed on a conventional hunting ladder 150 , wherein the hunting ladder is installed on a tree 170 , with a chair 160 positioned at the end of the hunting ladder 150 , such that the chair 160 is resting against and secured to the tree.
[0039] In a related embodiment, as illustrated in FIG. 2 , a hunting ladder guard 100 , can include:
a. a ladder guard plate 210 , further including
i. a plate hook 216 , which is connected to an upper end of the ladder guard plate 210 ; such that the plate hook 216 is configured as an inward protruding hook that can attach on to a rung 152 of the hunting ladder 150 ; ii. at least two bracket apertures 212 ; and
b. a bracket 204 ;
[0044] such that the upper end of ladder guard plate can be attached to an upper rung 152 of a ladder 150 using the plate hook 216 , and a lower end of the ladder guard 100 can be securely attached to a lower rung 152 of the hunting ladder 150 , such that the bracket is inserted through two consecutive bracket apertures 212 , which are positioned such that an upper leg of the bracket 204 reaches behind and over the lower rung 152 , and a lower leg of the bracket 204 reaches behind and under the lower rung 152 , such that a pad lock 206 can be inserted through pad lock apertures in the upper and lower legs of the bracket 204 , thereby locking the bracket in place around the lower rung, and thereby locking the lower end of the hunting ladder guard 100 in place, attached to the lower rung 152 .
[0045] In a related embodiment, FIG. 3 shows a rear view of a hunting ladder guard 100 installed on a ladder 150 .
[0046] In related embodiments, as shown in FIG. 3 , the ladder guard plate 210 when attached to a ladder 150 , can be configured to be inside vertical side columns 302 of the ladder such that a gap width between a column 302 and a vertical side of the ladder guard plate 210 is no more than 1-2 inches. A ladder guard plate 210 can thereby fit to ladders of varying width, with some variation of the gap between the vertical sides of the ladder guard plate 210 and the columns 302 of the ladder.
[0047] In further related alternative embodiments, a hunting ladder guard 100 can be configured such that a main surface of the ladder guard plate 210 covers the vertical side columns 302 .
[0048] In a related embodiment, FIG. 4 shows a front perspective view of a hunting ladder guard plate 210 .
[0049] In a related embodiment, FIG. 5 shows a rear perspective view of a hunting ladder guard plate 210 . The plate hook 216 is in this embodiment configured as two separate plate hooks 216 , separated by a plate hook aperture 218 , which can provide space for an attachment on a rung, such as a ladder stabilizer 254 , as shown on FIG. 2 .
[0050] In a related embodiment, FIG. 6 shows a close-up perspective view of a bracket 204 , which is substantially u-shaped, with parallel legs extending rearwards. Here, the u-shape of the bracket 204 is rectangular with rounded corners, but the substantially u-shaped configuration of the bracket 204 can alternatively be rectangular with sharp corners or be non-rectangular and fully rounded.
[0051] In a related embodiment, FIG. 7 shows a side, partially center-cut view of a section of a hunting ladder guard 100 , showing a ladder guard plate 210 , mounted to a rung 152 , with a bracket 204 inserted through bracket apertures 212 , and locked in place with a pad lock 206 .
[0052] In a related embodiment, FIG. 8 shows a front perspective view of a hunting ladder guard 800 , wherein the bracket apertures 812 are circular to be used with an adjustable shackle padlock 806 , such that the upper end of ladder guard plate can be attached to an upper rung 152 of a ladder 150 using the plate hook 216 , and a lower end of the ladder guard 800 can be securely attached to a lower rung 152 of the ladder 150 , such that legs of an adjustable shackle padlock 806 are inserted through two consecutive bracket apertures 812 , thereby locking the adjustable shackle padlock 806 in place around the lower rung, and thereby locking the lower end of the ladder guard 100 in place, attached to the lower rung 152 .
[0053] In a related embodiment, the hunting ladder guard 800 can be used with a chain or cable inserted through bracket apertures 812 and secured in place around a rung 152 of a ladder 150 with a padlock, or the hunting ladder guard 800 can be secured with a cable lock, or similar type of locking device.
[0054] In a related embodiment, the bracket apertures 812 can be quadratic, rectangular, ellipsoid, or of other suitable shape, to facilitate use of a compatible locking device.
[0055] In various related embodiments, the hunting ladder guard 100 can be configured:
a. such that the ladder guard plate 210 is manufactured in a solid, rectangular shape, one piece design; b. to fit ladder rungs and tripod rungs in a plurality of column widths and rung height; c. such that the plate hook 216 fits snugly over and is supported by the plurality of rectangular and circular rung designs of conventional ladders; d. such that the ladder guard plate 210 , when properly installed, blocks at least three consecutive ladder rungs 152 . e. to be sturdy, lightweight, weatherproof, and portable; f. in a plurality of sizes to fit a plurality of ladder size, including non-standard ladder column widths; and/or g. with rounded corners, and no sharp edges, for safety and esthetic appeal.
[0063] In a related embodiment, the ladder guard plate 210 can further include a plate cutout 214 , which can be used as a carrying handle and for ease of positioning the device over objects protruding from the ladder 150 .
[0064] In a related embodiment, the ladder guard plate 210 and the bracket 204 can be manufactured from metal, such as a high-strength aluminum alloy or stainless steel.
[0065] In a related embodiment, the ladder guard plate 210 and the bracket 204 can be painted with a camouflage colored powder coat finish.
[0066] In a related first example embodiment, as illustrated in FIG. 4 , the ladder guard plate 210 can have a length 402 of substantially 34.5″and a width 404 of substantially 11.75″, which will fit standard 14″ wide ladders 150 .
[0067] In a related second example embodiment, the ladder guard plate 210 can have a length 402 of substantially 34.5″and a width 404 of substantially 16″.
[0068] In a related third example embodiment, illustrated in FIG. 5 , which is compatible with both the first and the second example embodiment, an upper side of the plate hook 216 is flush with a top edge of the ladder guard plate 210 , and a horizontal level distance 502 from an upper inside 504 of the plate hook 216 to an upper edge 506 of the highest positioned bracket aperture 512 is substantially 23.75″.Additionally, as illustrated in FIG. 6 , the bracket 204 can be substantially 1″ wide 602 , by substantially 1.75″ deep 604 , by substantially 2.125″ high 606 , with a thickness 608 of substantially ⅛″. Correspondingly, each bracket aperture 212 can be substantially 1.25″ wide by substantially ¼″ high, with a 1.75″ distance 508 between each of a lower edge of a first bracket aperture 212 to the higher edge of a next-following second bracket aperture, whereby a bracket 204 can fit if the rung step height is not exactly 12″ and is less than 13″. The third example embodiment can fit a ladder 150 with a 12″ rung step height, providing 0.125″ wiggle room for the bracket.
[0069] In a related embodiment, in a method of installing the hunting ladder guard 100 , a user can be facing a ladder stand and hang the cover plate on a ladder rung, at approximately shoulder height.
[0070] The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention, which fall within the true spirit and scope of the invention.
[0071] Many such alternative configurations are readily apparent, and should be considered fully included in this specification and the claims appended hereto. Accordingly, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and thus, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A ladder guard to prevent access to a hunting ladder and other types of ladders, include: a ladder guard plate, further including a plate hook, configured as an inward protruding hook that attaches to a rung of the ladder; at least two bracket apertures; and a bracket; such that the bracket with upper and lower legs, each further comprising a pad lock aperture; such ladder guard plate attaches with the plate hook to an upper rung of the ladder; and the bracket locks the guard plate to a lower rung of the ladder, with a pad lock. Also disclosed is a ladder guard, including a plate hook and two bracket apertures, such that the ladder guard is locked to a ladder using an adjustable shackle padlock. The ladder guard can further include a plate cut-out, and can be painted with camouflage colors. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to weft thread magazines for laying of weft threads in a warp knitting machine having a pair of parallel, separated, transfer chains and having a carriage reciprocatable between said chains. The carriage comprises at least one group of thread guides which can be operated to transfer the threads to holding devices on the transfer chains.
2. Discussion of the Relevant Art
In a known weft thread magazine of this type, as disclosed in U.S. Pat. No. 3,665,732, a group of thread guides which in practice comprise 12, 18 or 24 single thread guides, are attached to a carriage moving to and fro in a crosswise direction. When the thread guides are connected to the carriage, the weft threads are laid in a diagonal direction whereby the angle of the diagonal is established by the relative motion of the thread guide group. When the thread guide group is firmly attached to a sled which is movable to and fro in the longitudinal direction on the carriage, it is possible to lay the weft threads parallel to each other. It is further possible to provide two or more weft thread groups on the carriage which can lay weft threads sequentially around the same holding means of the transfer chains whereby one group of thread guides lays parallel weft threads and the other thread guides lay diagonal weft threads.
In all of these cases, the patterning possibilities are rather limited, since the pattern repeat is predetermined by the number of thread guides in a group.
A further weft thread magazine for warp knitting machines is known (DEOS No. 2401050). In this arrangement, one out of a group of different weft threads can be fed to a corresponding one of the thread guides. To this end, several sets of weft thread spools are provided for each of the thread guides and a weft thread selector and thread splicer is used to vary the weft threads. In this way, the type of material or the color of the weft thread can be altered. This expansion of patterning variety, however, brings about a lowering of the working speed. Furthermore, care must be taken that the knots are kept outside of the weft inlay segment. Furthermore, the utilization of weft threads having different properties with respect to thread volume, elasticity and the like is very difficult to implement. Additionally, substantial tension peaks occur in the threads when the knots run through the thread guide.
Accordingly, there is a need for a weft thread magazine of the known type but having an expanded possibility of new patterns and, in particular, the possibility of substantially increased pattern types.
SUMMARY OF THE INVENTION
A weft thread magazine according to the principles of the present invention is employed in a warp knitting machine having a needle bed. This magazine includes a pair of endless transfer means, each having holding means for retaining weft threads in parallel and for delivering them to said needle bed. Also included is a thread laying arrangement that can transversely reciprocate between the pair of transfer means and transport weft threads from one of the pair of transfer means to the other. The arrangement includes carriage means having a plurality of thread guides for transferring weft threads around the holding means as the thread laying arrangement reverses direction. These thread guides are reciprocatable between an operative and inoperative position. In the inoperative position, the thread guides are precluded from transferring thread to the holding means. The magazine also includes a control means for moving the thread guides between the operative and inoperative position.
By employing the foregoing apparatus, a thread guide group can be moved from an operative to an inoperative position so that, at the turning point, no transfer of the weft thread to the holding means occurs. Thus, it is possible to provide at will that the weft threads are not transferred to the holding means of the transfer chains. When the transfer chains and the carriage continue to move, this has the desired effect that a group of weft threads are either laid or not laid, that the weft threads can be laid with different diagonal angles, or that the weft threads can be laid, by choice, parallel or diagonally. This gives rise to a substantial rise in the patterning possibilities. In the preferred embodiment, this patterning is regulated by a relatively simple control means.
In a further embodiment, at least two thread guide groups are utilized which, by means of a steering arrangement, can be selectively brought into the operative or inoperative position. Thus, in addition to the previously described patterning modes, two or more thread guide groups can be layed alternatively or at the same time in a desired combination. This permits a heretofore unknown patterning repeat.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be more fully understood, it will now be described, by way of example, with reference of the accompanying drawings in which:
FIG. 1 is a schematic side view of a weft thread magazine in a warp knitting machine according to the teachings of the present invention;
FIG. 2 is a schematic plan view of the weft thread magazine and warp knitting machine of FIG. 1;
FIG. 3 is a detailed perspective representation of the two thread guide groups on the carriage of FIG. 1;
FIG. 4 is an end view of the carriage of FIG. 3;
FIG. 5 is a detailed view of an individual holding device of FIG. 1;
FIG. 6 is a schematic diagram of the operation of two thread guide groups from the apparatus of FIG. 1 in a cycle comprising six different transverse movements;
FIG. 7 is a lapping diagram generated from the diagram of FIG. 6;
FIG. 8 is another lapping diagram generated from a variation of the diagram of FIG. 6;
FIG. 9 is yet a further lapping diagram generated from a variation of the diagram of FIG. 6;
FIG. 10 is a lapping diagram for a cycle having ten transverse movements;
FIG. 11 is a schematic diagram similar to that of FIG. 6 but expanded to three thread guide groups executing transverse movements;
FIG. 12 is a lapping diagram generated from the diagram of FIG. 11;
FIG. 13 is another lapping diagram generated from a variation of the diagram of FIG. 11; and
FIG. 14 is a plan view of the arrangement of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the Figures, and in particular to FIGS. 1 and 2, they disclose a warp knitting machine 10 and weft thread magazine 11 of the instant invention. The warp knitting machine 10 includes a needle bed 12 which has a needle bar 14 having a plurality of hook needles 16 disposed thereon in a conventional manner. The needles 16 cooperate with a slider mechanism 18 and a knockover sinker 20 all of which are a conventional design. On each end of the needle bed 12 there is provided a pair of endless transfer chain means 22 and 24 which move in a longitudinal direction as shown by arrows 26 and 26'. The transfer chains are provided with a plurality of holding means 28 equally spaced and fixed to the transfer chains 22 and 24 in a conventional manner. The holding means are holders, preferably, having a pawn-like shape (an enlarged top with a narrowed neck upon a thickened base) and serve to hold the weft thread once it is wrapped therearound.
The transfer chains are endless and are led over a plurality of rollers 30, 32, 34, 36 and 38 of which at least one is connected to a source of driving power, not shown. In the transverse direction (perpendicular to both of the transfer chains) a pair of support rails 40 and 42 are disposed one above the other. A carriage 44 is driven forward and backward in a conventional manner, by means of a chain 46, belt or the like, as shown by arrow X2 in FIG. 2.
A thread laying arrangement employs carriage 44 which includes a frame 50 (FIGS. 1 and 2) and a pair of rollers or wheels 52 and 54 journaled in the upper portion of frame 50, in a conventional manner, and a pair of rollers or wheels 56 and 58 as journaled on the lower portion of the frame in the same manner. The rollers 52 and 54 are adapted to ride on the support rail 42 and the rollers 56 and 58 are adapted to ride on the support rail 40, permitting the carriage 44 to move freely thereon in a transverse direction. The carriage 44 is also provided with upper thread guide 60 (FIG. 1 only) which is provided with a plurality of apertures 61 therein through which the weft threads 62 and 63i, ii, iii, and iv are threaded. Preferably, the lower portion of the carriage frame 50 is provided with axial bearings shown herein as a bushings 64 having apertures therein which are adapted to slidably receive carrier 67 (FIGS. 1 and 2). One end of carrier 67 is provided with two sets of thread guides 70, 71 disposed thereon, for two groups of thread A and B. Carrier 67 includes an upper guide rod 68 which is also slidably mounted in bushings 64. The end of rod 68 nearest needle bed 12 is provided with a pair of rollers 72 and 74 journaled thereon. The rollers 72 and 74 are located on both sides of a flexible guide band 76 preferably made of steel. The carrier 67 and its guide rod 68 are permitted to freely move within the apertures of bushings 64 and this movement is obviously controlled by the position of rollers 72 and 74.
One end of flexible guide band 76 is preferably rigidly connected to a steering apparatus 78 which is provided with a housing 80 having an opening 82 therein adapted to receive rollers 72 and 74 therein, as well as retain band 76 by means of a nut 84 provided therefor. The steering apparatus 78 has its housing 80 coupled by means of a rod 86 and a lever 88 articulated therewith. The lever 88 is provided with a contact roller 90 journaled thereon which continually cooperates with a driven cam 92 having a curved surface 94 which cooperates with roller 90 thereby moving lever 88 and rod 86 in the direction of arrow 96 which is in the longitudinal direction. A spring 98 maintains tension on lever 88 so that contact roller 90 faithfully follows the surface 94 of cam 92.
On the opposite end of the needle bed, proximate transfer chain 22 a second steering apparatus 78' is provided. Steering apparatus 78' includes a housing 80' which is provided with an aperture 82' and is driven in the direction of arrow 96' by rod 86', lever 88' and a contact roller and cam arrangement, not shown, similar to the driving arrangement shown with regard to the steering apparatus 78. The band 76 is retained in the housing 80' by means of nut 84' and is also provided with a spring device 100 disposed between the nut and rear surface of the housing so that by tightening or loosening nut 84, the tension of the flexible guide band 76 may be adjusted. Next to the transfer chain 22, there is provided a creel 61 comprising two sets of weft thread spools, A and B, oriented on top of each other. From each of the said spool sets, weft threads 62 and 63 are each led over thread accumulators 81, 82 comprising springs 83, 84, axially supporting controlled rolls 108, 109.
From accumulators 81, 82, threads 62 and 63 are fed to upper thread guides 60, to thread guides 70, 71. In FIG. 2, upper thread guides 60 were deleted for clarity. In the drawings, only a few threads are shown for each group. It should be recognized that, in the working machine, it is contemplated to use 12, 18 or even 24 threads per group. Weft threads 62 will hereinafter be designated as threads A1 through A4 and the weft thread 63 of group B will be designated as B1 through B4.
While this specification discusses mainly the provision of two thread groups, A and B, three are contemplated (see FIG. 11), and the principles hereof should not be considered as thus numerically limited.
The specific structure of carrier 67 is most clearly illustrated in FIGS. 3, 4 and 14, a perspective, end and plan view, respectively. Carrier 67 comprises three parallel beams 68, 110 and 112, whose centers are substantially arranged as the corners of an equilateral triangle. Their lengths are equal except for guide rod 68 which is slidably mounted in upper bushings 64 of frame 50. Beams 110 and 112 are journaled between corresponding corners of triangular plates 117 and 119. Guide rod 68 is affixed to the upper corner of plate 117 and, at a mediate position, to the upper corner of plate 119, rod 68 extending beyond plate 119 and terminating with the pair of opposing rollers 74 and 72 journaled thereon.
Thread guides 70 of group A are affixed to and depend from common cross beam 110. Thread guides 71 of group B are similarly attached to cross beam 112. Cross beam 110 has affixed to it two opposing lever arms: upper arm 113 and lower arm 114 both being part of an integral structure. Journaled on arms 113, 114, are rollers 123 and 124, respectively. Cross beam 112 similarly carries two opposing lever arms 115 and 116 which also terminate in similar, terminal rollers 125 and 126, respectively. Lever arms 113 and 114 are axially displaced relative to lever arms 115 and 116 so that levers 115 and 116 are closer to plate 119 than levers 113 and 114. The rollers attached to the lever arms keeps the frictional component of the steering mechanism rather small.
In the weft thread magazine itself, wedges 140 and 142 are positioned adjacent to transfer chain 22. Similarly, wedges 144 and 146 are positioned adjacent to transfer chain 24. Wedges 140-146 are vertically reciprocatable by linkage driven from pattern wheels, not shown, to move the wedges between effectual and ineffectual positions. The ineffectual positions of all of these wedges is indicated in phantom in FIG. 3. In their effectual positions, wedge 142 can interact with lever arm 114, wedge 140 with lever arm 115, wedge 144 with lever arm 116 and wedge 146 with lever arm 113, in order to move the appropriate thread guide group A or B out of the operative position shown in full in FIG. 3 into the inoperative position as is shown fully drawn out for group B in FIG. 4 and in phantom for group A.
It is thus possible, by means of the double lever arm to steer the thread guide group on both sides in the same manner, the lever arms acting as operating elements.
Referring to FIG. 5, a more detailed view is given of the previously mentioned holding devices. The holding devices 28 are so formed that there is provided a space 130 on the outer side thereof for the holding of a thread portion 134 laid thereabout. There is also provided on holding devices 28 an inner space 132 for the passage therethrough of the inoperative thread portion 136. It is advantageous to provide holding devices 28 with holding means not only on the outside but also on the inside for the uptake of thread material since it is then possible to provide room for the passage of threads which are not displaced in the transverse direction.
The operation will first be described assuming wedges 140-146 are in their ineffectual positions shown in phantom in FIG. 3. Consequently, thread guides 70 and 71 extend vertically downward in the operative positions shown in FIG. 3. Thus the wedges act as a control means (element).
In operation, transfer chains 22 and 24 are driven in a forward or longitudinal direction as shown by arrows 26 and 26' in FIG. 1 and by arrow X1 in FIG. 2. Carriage 44 is moved in the direction of arrow X2 by means of a reciprocating drive arrangement 46 whereby it is made to come to rest for a short period of time at the end of travel of carriage 44, which occurs when rollers 72 and 74 are positioned in the housing 80 where the rearward movement is timed to take place. Carriage 44 is then moved in a longitudinal direction as shown by arrow 96 as the steel band 76 is moved by the steering apparatus coupled to cam 92, via rod 86, as explained earlier. The rearward movement is preferably adjusted to move the thread guides 70 a distance of four holding devices 28 (or a number equal to the number of threads in a group) as determined by the cam surface 94 on cam 92. As the carriage 44 starts to move towards the right, as shown in FIG. 2, a small forward movement of thread guides 70 and 71 occurs in the direction of arrow X3 because of the segment 102 of cam 92. This movement comes to a complete halt as the cam portion 104 comes into contact with contact roller 90. This occurs when the carrier 44 is located inside of the transfer chains 22 and 24.
Thus, when the carriage finds itself outside of the transfer chains 22 and 24 cam segment or portion 106 causes the linkage 86 and 88 to move the thread guide 70 sharply in a rearward direction thereby permitting the thread to move past the holding devices 28 on transfer chains 22 to 24 and the warp around is completed as the carriage then returns towards the opposite transfer chain.
The foregoing will cause the laying of parallel threads from groups A and B together in pairs between chains 22 and 24. All of the threads so laid will be perpendicular to chains 22 and 24.
However, a more complex pattern can be developed as shown in FIG. 2. Therein it will be observed that downstream thread section 69 lies inside and parallel to chain 24 (in space 132 of holder 28 as shown for thread segment 136 in FIG. 5) and was not transferred across to chain 22. This occurred since group A was brought to chain 22 but wedge 142 was in its effectual position causing thread guides 70 to move to the inoperative position illustrated in phantom in FIG. 4. Thread guide 71, being unaffected, remained in the operative position shown in phantom. Consequently, thread group B (but not A) was wrapped about holders 28 of chain 22 to form the perpendicular group B2-B4 shown in FIG. 2, as carriage 44 returned to chain 24.
As the foregoing full group B1-B4 is being laid, all of the wedges 140-146 revert to their ineffectual position so thread guides 70 and 71 are rendered operative and both thread groups A and B are wrapped around holders 28 of chain 24 as illustrated in the thread section immediately upstream from thread section 69. Once this wrap is completed, wedges 140 and 144 move to their effectual positions and wedges 142 and 146 to their ineffectual positions. Consequently, thread guides 70 and 71 will be in the positions illustrated in full in FIG. 4 when carriage 44 intercepts either chain 22 or 24. Therefore as shown for the remaining upstream sections of chains 22 and 24, threads A1-A4 are continually laid and wrapped on holders 28 for each pass between the chains. Accordingly, the threads of group A are laid in space 130 (FIG. 5) of holder 28 as illustrated for thread portion 134. However, since thread guides 71 are in the inoperative position, threads from group B are led to chain 22 and back again without wrapping. The slack that would otherwise be created by this pulling and relaxing is taken up by thread accumulators 81, 82 (FIG. 1). Thread accumulators 81, 82 ensure that the threads are always tensioned between the last holding device 28 to which they are attached and the exit opening of the thread guides 71 and 70.
The result of the foregoing selective rotation of thread guides 70 and 71 in the direction of arrows X4 and X5, respectively, is to reciprocate them between the operative and nonoperative position. It is thus possible to achieve the effect noted in FIG. 2, namely that weft threads A1 through A4 of thread guide group A are laid parallel to each other, whereas the weft threads B1 through B4 may be partially laid together with weft threads A1 through A4 and partially, however, they may be caused to run diagonal to this position.
It will now be assumed that wedges 140-146 are moved according to a predetermined pattern rendering them effectual at various time intervals. The thread guide pattern is illustrated in the diagram of FIG. 6 as producing the lapping pattern of FIG. 7.
For the embodiment of FIG. 6, there is provided on one carrier 126 two sets of thread guides 129 and 127 carrying threads of groups A and B, respectively, which may be moved from a lower operative position into an upper inoperative position, in a manner similar to that just described. There is shown a working cycle of six traverse motions W1 through W6 wherein the appropriate arrow indicates the direction of motion. Initially, it is assumed groups A and B were last wrapped on the right chain 22 and left chain 24, respectively. At the end of the traverse motions W1 and W2, both groups A and B are inoperative. At the end of traverse motions W3 and W6, group A is inoperative while group B is operative; and at the end of traverse motions W5 and W4, group B is inoperative and group A is operative. It is only in the operative position that the appropriate weft threads are laid into holding devices 28.
This leads to the lapping diagram shown in FIG. 7. While in the traverse motion of W1 and W2, no weft threads whatsoever are laid in, during traverse motion W4 and W5, only the weft threads A1 through A4, and during the traverse motions W3 and W6, only the weft threads B1 through B2 are laid in. It should be noted, however, that even during the motion of W1 and W2, the weft threads are carried across to the opposite side. However, during this motion, they are so tensioned during this return by thread accumulators 81 and 82 that they remain in the general domain of that transfer chain around whose holding means they were last laid.
FIG. 8 shows a lapping diagram of a different type which occurs when, at the end of traverse movements W1, W2, W4 and W5, only group A is operative, whereas during the traverse movements of W3 and W6, both thread groups A and B are operative. This has the consequence that the constantly operating thread guide group always lays thread groups A1 through A4 in a parallel manner, whereas the thread guide group B lays in the weft threads B1 through B4 in a wide diagonal angle.
In the lapping diagram of FIG. 9, weft threads A1 through A4 and threads B1 through B4 are displaced diagonally with relationship to each other. This occurs when, at the end of traverse movements W2 and W5, group A is operative; and, at the end of traverse movements W3 and W6, group B is operative; and at all other times all groups are inoperative.
In FIG. 10, there is provided a working cycle of ten cross movements wherein weft threads A1 through A4 and B1 through B4 are displaced diagonally with respect to each other. However, in this embodiment, thread guide group A is made operative at the end of traverse movements W3, W5, W8 and W10; and the thread guide group B is made operative at the end of traverse movements W2, W5, W7 and W10; whereas all of the remaining groups in the remaining traverse movements are inoperative.
In the embodiment of FIG. 11, there is provided in carrier 226 three groups A, B and C of thread guides 229, 228 and 227, respectively. In this arrangement, group A is only operative during traverse movements W3 and W6, group B, during traverse movements W2 and W5 and group C during traverse movements W1 and W4. This leads to the lapping diagram of FIG. 12 wherein threads A1 through A4, threads C1 through C4 and threads B1 through B4 follow each other in a repeat pattern.
In the arrangement of the lapping diagram showing in FIG. 13, during traverse movements W1 and W6, only weft threads A1 through A4 are displaced, whereas during traverse movements W2 and W3, weft threads A1 through A4 and B1 through B4 are displaced, and during traverse movements W4 and W5, the weft threads of all three groups A, B and C are displaced at the same time. This is achieved in that the thread guide group A is continually operative, thread guide group B is inoperative at the end of cross movement W6, and thread guide group C is inoperative at the end of cross movements W2 and W6.
It will thus be seen that a vast number of weft thread possibilities may be achieved. The weft threads can be laid parallel after each other (see W3 through W6 in FIG. 7 and FIG. 12), they can be laid diagonally after each other (FIG. 10), they can be laid at the same time parallel and on top of each other (FIG. 13), they can at the same time be laid over each other in a diagonal manner (FIG. 8 and FIG. 9), the weft thread laying can be suppressed (W1 through W2 in FIG. 7), the diagonals can be provided with a different angle. The different possibilities can be combined and much, much more. Through drawing in the thread inside a particular thread guide group, the pattern possibilities can again be considerably increased.
In the working example, it is shown that the thread guides 70 and 71 provide the weft threads directly to holding devices 28. The same effect may, however, be achieved with those known weft thread magazines in which the thread guides lay the weft threads into intermediate holders which then transfer the weft threads to the holders of the transfer chain.
Hereinbefore has been disclosed a simple and effective apparatus for providing a repeating pattern with inlaid weft threads. Using the foregoing teachings, it is easily possible to make certain material with a weft repeat of 120. There are many possible methods of bringing the thread guide groups from the operative into the inoperative position. It is particularly simple to do this either by lifting, or turning the guides about a longitudinal axis. It is particular advantageous to use a control arrangement wherein the thread guide groups are directly and mechanically connected to operating elements which interact with control elements that are selectively brought into the path of the operating elements and by interaction with the operating elements cause the displacement of the thread guide groups. Since the control elements are located in one position they are comparatively easy to activate, for example, by means of a pattern chain or a jacquard arrangement.
In this connection, it is advantageous (but not necessary) if the thread guide group normally is found in the operative position and the steering element is placed close to the thread transfer chains. It is sufficient merely to bring the thread guide groups into the inoperative position in the vicinity of the transfer chain in order to prevent the interaction of the weft threads with the holding devices. However, deflection of the guides can occur over a longer interval and need not, as in the preferred embodiment, deflect only at the transfer chains. While the preferred embodiment employs an operating element comprising a lever arm which is directly connected to a cross beam carrying the thread guide groups, in some embodiments, alternate operating elements including electromechanical, pneumatic or other devices are possible. Also, while the control element comprised a wedge which may be brought into the path of the lever arm, other shapes for the control element are contemplated. Furthermore, while the cross movement of the carriage itself brings about the engagement of the wedge and the lever arm, a separate motive source may be used in other embodiments.
While it is desirable to provide two lever arms in opposite directions (and that two wedges are provided therefore) in some embodiments, a single lever arm will be sufficient. Also the wedges in the vicinity of the transfer chains may be brought into the path of the lever arms in different directions. It will therefore be understood that various changes in the details, materials, arrangement of parts and operating conditions which have been herein described and illustrated in order to explain the nature of the invention may be made by those skilled in the art within the principles and scope of the instant invention. | A weft thread magazine operates in a warp knitting machine having a needle bed. This magazine includes a pair of endless transfer chains, each having a plurality of holders for retaining weft threads in parallel and for delivering them to the needle bed. Also included is a thread laying arrangement operable to transversely reciprocate between the transfer chains and to transport weft threads from one chain to the other. The arrangement also includes a carriage having a plurality of thread guides for transferring weft threads around the holders as the thread laying arrangement reverses direction. These thread guides can reciprocate between an operative and inoperative position. In the inoperative position, the thread guides are precluded from transferring thread to the holders. The magazine also includes a control device for moving the thread guides between the operative and inoperative position. | 3 |
GOVERNMENTAL INTEREST
The invention described herein may be manufactured, used and licensed by or for the Government for governmental purposes without the payment to me of any royalty thereon.
BACKGROUND OF THE INVENTION
Various means have been used in the prior art to eject a canister from a rocket fired or artillery fired projectiles in order to accurately dispense the projectile's warhead cargo accurately over the target area. The canister was generally required to be ejected from the projectile, after the projectile began to slow down in flight, in order to achieve the necessary range. Then the canister had to be opened within one to two tenths of a second, after ejection from the parent munition, in order to maintain flight direction and accuracy in hitting the intended target. The prior art device frequently used electrical, mechanical and/or electrical-mechanical devices to accomplish properly sequenced canister ejection. The problem with these prior art devices was that usually the pressure build up caused by the expulsion charge was so great that it would destroy the electrical, or electromechanical devices thus preventing properly timed activation and release. The above problems are particularly acute in 2-3 inch diameter rockets and 155 mm artillery fired projectile having smoke screening warheads which utilize white phosphorus as a smoke generating agent.
SUMMARY OF THE INVENTION
The present invention relates to short delay burster for a cannister ejecting projectile having a shielded multi-screened delay column disposed in a choke configured delay housing. The delay burster is designed to withstand the high pressure forces of an expulsion charge while assuring initiation of the delay and proper opening of the canister.
An object of the present invention is to provide a short delay burster for canister ejecting projectile which will reliably permit the projectile payload to be dispersed over an intended target area.
Another object of the present invention is to provide a short delay burster for a canister ejecting projectile which will insure against a delay column, used to initiate opening of a canister, from being blown away by the explusion charge.
Another object of the present invention is to provide a short delay burster for a canister ejecting projectile which can open a dispensing canister within 1 to two tenths of a second after ejection.
A further object of the present invention is to provide a short delay burster for a canister ejecting projectile which will reliably maintain the projectile's flight direction and effectiveness over the target area.
For a better understanding of the present invention, together with other and further objects thereof, reference is made to the following descriptions taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial longitudinal cross-sectional view of the delay burster assembly positioned in an artillery fired projectile.
FIG. 2 is an end view taken along line 2--2 of FIG. 1.
Throughout the following description like reference numerals are used to denote like parts of the drawings.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIGS. 1 and 2, a tubularly shaped projectile housing 10 has a forward ogive end 12 and a transverse bulkhead 14 having an internally threaded axially aligned bore 16 positioned therein. Bulkhead 14 transversely separates the forward ogive end 12 from a main cylindrically shaped cargo cavity 18 which contains an ejectable cylindrically shaped container 20 containing smoke generating chemicals such as white phosphorus 21. Expulsion-initiating charge 22, fixedly axially positioned in forward ogive end 12, has an explosive material 23 therein whose high pressure gas output is directed toward an axially positioned delay burster assembly 24 and cannister 20. Delay burster assembly 24 main elements comprise a choke housing member 26, a retainer member 28, a multi-mesh filter screen stack 30, an ignition composition 32, a detonator 34, and a length primacord of 36 crimped to the necked down rear end 38 of choke housing 26. The choke housing 26 has an externally threaded front end 40 fixedly screwed into bulkhead core 16. An internally threaded axial counterbore 42 communicates with an axial choke cavity 44, which in turn communicates with a second axial cavity which has a restricting orifice 46 created by the circular inwardly protruding interior wall section 47. The ignition composition 32 may be a gasless ignition powder such as type TYP A-1A, MIL-P-22264 with an additive of 1% varnish. The detonator 34 disposed intermediate ignition composition 32 and primacord 36 may be a type M35, as defined in MIL-D-46207. Primacord satisfactory for this application may be primacord 100 grain PETN/FT such as manufactured by Ensign-Bricford Co., Simsbury, Conn. The circular externally threaded retainer member 28 has an axial ignition bore 48 therein and a slotted front end 50 to permit clamping of filter screen stack 30 intermediate retainer member 28 and shoulder 52 of housing member 26. The filter screens are made of 304 stainless steel wire mesh. The stack is composed of four different size meshes arranged in the following sequential order. A first mesh having 24×24 holes to the square inch made of 0.016 inch diameter wire, a second mesh having 100×100 holes to the square inch made of 0.0035 inch diameter wire, a third mesh having 50×250 holes to the square inch size made of 0.0045 to 0.0055 inch diameter wire, and a fourth mesh size having 50×50 holes to the square inch made of 0.009 inch diameter wire. The first 24×24 filter screen mesh is positioned in abutment with retainer member 28 and the 50×50 mesh size filter screen is operatively positioned in abutment with the shoulder 52 and ignition composition 32.
The delay burster assembly 24 is assembled by loading the ignition composition 32 into the choke cavity 44 and axial cavity 45 in two increments at 1800 lb dead load pressure. The first increment is press loaded into the choke housing 26 through threaded end 54 of choke cavity 44. The second increment is press loaded into axial cavity 45 through the bottom end 56 of necked down rear end section 38. The front surface of ignition composition 32 is coated with a nitrocellulose cement 58, MIL-A-32484, Type I to form a moisture proof seal thereon. Prior to crimping the necked down rear end housing 38 on primacord 36 the front peripheral surface 60 and the rear end 62 are coated with the aforementioned nitrocellous cement. Dentonator 34 is then loaded into rear end 56 and pushed forward until it is in abutment with ignition composition 32. The front end 64 of primacord 36 after being coated with nitrocellulous cement is pushed into the bottom open end 56 until it is in abutment with detonator 34 and given a 360° crimp. The next step of the delay burster subassembly operation is to load the filter screen stack 30 with the 24×24 mesh facing the retainer member 28. The final step of subassembly for the delay burster is to threadedly screw retainer member 28 into threaded axial counterbore 42 so that it is in firm contact with the 24×24 mesh element. The delay burster assembly 24 is then operatively threaded into the bulkhead internally threaded bore 16 so that its longitudinal axis is in axial alignment with the longitudinal axis of cylindrical canister 20.
In operation after the projectile 10 is launched and has traveled sufficiently toward the target area a fuzing system not shown initiates the canister expulsion charge 22 which simultaneously initiates ignition composition 32 through axial ignition bore 48. The restriction 46 prevents the delay column 32 from being blown through the tubular delay housing midsection 66. The multi-filter screen stack prevents the top of the ignition composition charge 32 from being eroded away and enables the delay burster assembly 24 to operate so that the canister 20 is opened within one to two tenth seconds after ejection, thus permitting the projectile to maintain proper flight direction until the warhead has reached the intended target area.
While there has been described and illustrated specific embodiments of the invention, it will be obvious that various changes, modification and additions can be made herein without departing from the field of the invention which should be limited only by the scope of the appended claims. | A short delay burster for a canister ejecting projectile utilizes a multish screen operatively disposed in a choke configuration housing and held therein by an orificed retainer to permit the delay to be initiated by an expulsion charge while withstanding the high pressure shock wave of the expulsion charge explosion. | 5 |
RELATED APPLICATION DATA
[0001] This application claims the benefit pursuant 35 U.S.C. §119 of the filing date of U.S. provisional patent application No. 60/611,388, filed Sep. 21, 2004, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to sumps and, more particularly, to a liquefied natural gas (LNG) sump for containment of LNG spills on an offshore gravity based structure or other offshore installation.
[0004] 2. Description of the Related Art
[0005] Gravity based structures (GBS) have been used in the design of offshore oil and gas storage facilities for more than 30 years in many parts of the world, predominantly in areas of severe storms for years to design. Due to their strength and reliability, gravity-based structures have been such as the North Sea offshore Norway and Scotland, and in an area offshore Newfoundland where energy operators must contend with floating icebergs. Recently, GBS's are being proposed for the storage of LNG.
[0006] LNG is natural gas cooled to cryogenic temperatures (−161 C (−256 F)) through liquefaction, and is transported and stored in its liquid state. Since LNG has never before been stored in a GBS, dealing with LNG spills in a GBS environment is a new issue.
[0007] U.S. Pat. No. 3,657,895 discloses a platform for offshore wells for which a curbing around the periphery of the platform contains oil spills onto the deck platform, and the deck of the platform slopes downwardly from the curbing to an opening in the platform surrounding the well.
[0008] U.S. Pat. No. 3,675,431 discloses an off-shore storage tank for liquefied gas. The tank has an outer shell of which at least the lower part, which is immersed in the water, is made of solid concrete, and does not include a sump.
[0009] U.S. Pat. No. 3,727,418 discloses a sub-aqueous storage of liquefied natural gas. The patent discloses a submerged, jacketed container having an interior which is coupled to a balancing fluid in another container. The balancing fluid is coupled to the water surrounding both containers.
[0010] U.S. Pat. No. 3,984,059 discloses a marine loading system for liquefied natural gas handling. Various plants sites in the system are connected by coaxial ducting. There is no disclosure of a sump.
[0011] U.S. Pat. No. 4,188,157 discloses an offshore structure handling cryogenic fluids such as liquefied natural gas. The structure includes a cell-matrix. The patent does not disclose an LNG sump.
[0012] U.S. Pat. No. 4,202,648 discloses a floating plant for offshore liquefaction, temporary storage, and loading of liquefied natural gas. The plant includes a semi-submersible platform with storage tanks for LNG arranged in the submerged section of the platform. The patent does not disclose an LNG sump.
[0013] U.S. Pat. No. 4,209,267 discloses an improvement in storage systems for liquefied natural gas, to provide increased security in cases of tank rupture. The safety system includes a dike, impounding wall or drainage channel constructed of compacted earth, concrete, metal and/or other suitable substance, surrounding an aboveground steel insulated tank used to store the liquefied gas. A drop shaft is used to communicate the diked area with an underground tunnel for temporary accumulation and subsequent safe disposal of liquid which has escaped from the storage tank. Inert gas is used to neutralize the hazards of a spill, and stored liquid is pumped to a storage tank.
[0014] U.S. Pat. No. 4,217,848 discloses a floating gas liquefaction installation having a liquefaction unit and a sealed, thermally insulated tank space. The patent does not disclose of an LNG sump.
[0015] U.S. Pat. No. 4,302,130 discloses an offshore platform with storage facilities for natural gas. This patent also does not disclose of an LNG sump.
[0016] U.S. Pat. No. 4,365,576 discloses improvements in an offshore platform and submarine storage facility for highly chilled liquefied gas. This patent also does not disclose of an LNG sump.
[0017] U.S. Pat. No. 4,404,988 discloses an apparatus for draining a liquid which has been inadvertently freed from a primary storage container and captured in a containment space. A pump delivers spilled liquid to a remote location.
[0018] Thus, there is a need for systems and methods for handling LNG spills when LNG is stored in a GBS.
SUMMARY OF THE INVENTION
[0019] The present invention is directed to an LNG sump that provides containment for an LNG spill on an offshore GBS or other offshore installation.
[0020] According to an embodiment of the present invention, a sump includes a preferably long, relatively narrow cylindrical structure that provides sufficient LNG spill containment while minimizing the rate of evolution of gaseous methane at the surface due to the relatively small surface area. The cylinder can be insulated and is preferably arranged to fit neatly into a GBS compartment. Spills from a loading platform can enter the sump area through a trough through the GBS wall.
[0021] The LNG sump may require insulation and/or heat tracing to protect the GBS walls from low temperature during a spill event. The LNG sump may be supported by GBS floor sitting on insulation blocks. A cryogenic sump pump maybe installed in the sump to remove rainwater or the like. Spilled LNG will be allowed to boil-off within the sump.
[0022] According to an embodiment of the present invention, an LNG sump is provided for a GBS. The LNG sump includes a sump containment structure having a predetermined volume and floor surface area. The volume and floor surface area are selected in order to allow spilled LNG contained within the sump containment structure to vaporize at a predetermined, safe rate. A trough is provided for collecting spilled LNG on the GBS, such as at the processing area and on a jetty, and delivering the spilled LNG to the sump containment structure.
[0023] According to an embodiment of the present invention, an LNG sump for a gravity based structure (GBS) includes containment means for collecting spilled LNG and for allowing the spilled LNG contained to vaporize at a predetermined rate. Collecting means is also provided for collecting spilled LNG on the GBS and delivering the spilled LNG to said containment means.
[0024] According to an embodiment of the present invention, a method for handling LNG spills on a GBS includes a step of collecting spilled LNG and delivering the spilled LNG to a containment means, and a step of allowing the spilled LNG contained to vaporize at a predetermined rate.
[0025] Further applications and advantages of various embodiments of the present invention are discussed below with reference to the drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a diagram of an LNG sump according to an embodiment of the present invention.
[0027] FIG. 2 is a perspective view showing installation of a LNG sump in an offshore GBS in accordance with an embodiment of the invention.
[0028] FIG. 3 is second perspective view showing installation of the LNG sump according to an embodiment of the invention.
[0029] FIG. 4 is a top plan view showing installation of the LNG sump according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0030] As shown in FIG. 1 , an LNG sump 102 has a long relatively narrow cylindrical shape, which has the effect of providing sufficient LNG spill containment while minimizing the rate of evolution of gaseous methane at the surface due to the relatively small surface area. The cylinder may be insulated ( 106 , not shown as completely covering sump) and should fit neatly into a GBS compartment 104 . Electrical heat tracing, such provided by a heat blanket 108 , can be provided on the outside of the LNG sump 102 and used to protect the surrounding concrete from cryogenic temperatures while allowing some control over the rate of vapor evolution. The electrical tracing or heat blanket fitted outside of the insulation.
[0031] A trough 110 a collects spilled LNG from the process area and delivers it to the LNG sump 102 . A second trough 110 b can be used to collect spilled LNG from a jetty or the like, and delivers the spilled LNG to the LNG sump 102 via separate inlet 112 through a slot 120 in the GBS wall. Consideration may be given to the expansion and contraction of the pipes due to chilling and warming.
[0032] A sump pump 114 may be provided in the bottom of the sump 102 for removing water and other liquid. Guides 116 can be provided for supporting the sump 102 inside compartment 104 . Guides 116 can be insulated with insulation blocks 117 where it contacts sump 102 . An insulation block 118 can be provided at the bottom of the LNG sump 102 .
[0033] In the event of a spill, LNG is collected by gravity in the LNG sump 102 via the troughs 110 a, b provided about the GBS where spills may occur. Since the surface area in the bottom of the LNG sump 102 is small, LNG can be allowed to vaporize at a calculated rate that is safe and acceptable to operators. As shown, the exemplary LNG sump 102 is a cylinder more than 30 meters in height with only a 3 meter diameter.
[0034] Further, the LNG vaporization rate can be adjusted by adjustment means—it may be reduced by use of foam insulation or increased by use of the electrical/heat tracing on the LNG sump 102 outer walls. Insulation and heat tracing may be used together. The concrete GBS compartment 104 is prevented from reaching cryogenic temperatures by the use of the insulation and/or heat tracing.
[0035] Since LNG has never before been stored in a GBS, dealing with spills in this environment has never before been an issue. The inventive geometry of the present invention avoids the large footprint required by deck mounted sumps. Further, the fact that it is mounted within the GBS avoids wave action on the LNG sump 102 . The present invention may include other LNG spill containers such as deck-mounted sumps, outboard mounted sumps, etc.
[0036] The LNG sump preferable includes, but is not limited to, a long thin cylindrical containment structure extending into the GBS compartment. A single LNG spill sump is preferred for the GBS. One skilled in the art will understand that volume (due to spill size) and location (due to elevation) can be controlled by the loading platform (jetty) area spill. Preferably, volume of the sump 102 should be in range of 200 to 220 cubic meters, and the area of the open top should be minimized.
[0037] One skilled in the art will understand that the sump may not need to be insulated for process reasons. For example, during a spill event the exterior of the sump 102 can ice up and be self insulating to an extent.
[0038] The LNG sump 102 may be constructed of suitable materials for handling cryogenic temperatures, such as, but not limited to, concrete and aluminum. Aluminum may be preferred due to its low weight and compatibility with the cryogenic temperatures.
[0039] The LNG sump 102 may be located exterior to the GBS. An exterior location requires a portion of the sump to be below sea level. Support, wave loading, and fatigue will need to be considered. The sump is preferably located as close as possible to the GBS to minimize support requirements. In the unlikely event that the LNG sump 102 ruptures, rapid phase transition (RPT) loads may occur. One skilled in the art should consider a rupture when locating the sump.
[0040] The location within the GBS (in an exterior compartment) is preferred. This location makes the LNG sump 102 easier to support. Spills from the loading platform will enter the LNG sump 102 area via a trough 110 a through the GBS wall. The LNG sump 102 may require insulation and heat tracing to protect the GBS walls 104 from low temperatures during a spill event. The LNG sump 102 may be supported by GBS floor sitting on insulation blocks 118 .
[0041] The diameter (surface area) of the LNG sump is based on the volume requirement, the fixed elevation of the GBS floor and fixed elevation of the loading platform. A cryogenic sump pump 114 may be installed in the LNG sump 102 to remove rainwater or the like. As described above, spilled LNG will be allowed to boil off.
[0042] FIG. 2 is a perspective view showing installation of a LNG sump 102 in an offshore GBS 100 , in accordance with an embodiment of the invention. As shown, a trough 110 a feeds the sump 102 .
[0043] FIG. 3 is second perspective view showing installation of the sump according to an embodiment of the invention. From this view, both troughs 110 a, b can be seen.
[0044] FIG. 4 is a top plan view showing installation of the sump according to an embodiment of the invention.
[0045] Thus, a number of preferred embodiments have been fully described above with reference to the drawing figures. Although the invention has been described based upon these preferred embodiments, it would be apparent to those of skilled in the art that certain modifications, variations, and alternative constructions would be apparent, while remaining within the spirit and scope of the invention. | A liquefied natural gas (LNG) sump is provided for a gravity based structure (GBS). The sump includes a sump containment structure having a predetermined volume and floor surface area. The volume and floor surface area are selected in order to allow spilled LNG contained within the sump containment structure to vaporize at a predetermined, safe rate. A trough is provided for collecting spilled LNG on the GBS, such as at the processing area and on a jetty, and delivering the spilled LNG to the sump containment structure. | 8 |
BACKGROUND OF THE INVENTION
[0001] Transcriptional regulation is a major event in cell differentiation, proliferation, and apoptosis. Transcriptional activation of a set of genes determines cell destination and for this reason transcription is tightly regulated by a variety of factors. One of its regulatory mechanisms involved in the process is an alteration in the tertiary structure of DNA, which affects transcription by modulating the accessibility of transcription factors to their target DNA segments. Nucleosomal integrity is regulated by the acetylation status of the core histones. In a hypoacetylated state, nucleosomes are tightly compacted and thus are nonpermissive for transcription. They are relaxed by acetylation of the core histones, with the result being permissiveness to transcription. The acetylation status of the histones is governed by the balance of the activities of histone acetyl transferase (HAT) and histone deacetylase (HDAC). Recently, HDAC inhibitors have been found to arrest growth and apoptosis in several types of cancer cells, including colon cancer, T-cell lymphoma, and erythroleukemic cells. Given that apoptosis is a crucial factor in detecting cancer progression, HDAC inhibitors are promising reagents for cancer therapy as effective inducers of apoptosis (Koyama, Y., et al., Blood 96 (2000) 1490-1495).
[0002] Several structural classes of HDAC inhibitors have been identified and are reviewed in Marks, P. M., et al., Journal of the National Cancer Institute 92 (2000) 1210-1216. More specifically, WO 98/55449 (by The University of Queensland et al, “Hydroxamic Acid Compounds Having Anticancer And Anti-Parasitic Properties”), and U.S. Pat. No. 5,369,108 (by Breslow, R., et al., “Potent Inducers Of Terminal Differentiation And Methods Of Use Thereof”) report alkanoyl hydroxamates with HDAC inhibitory activity.
[0003] We have now found that certain tricyclic alkylhydroxamate derivatives possess anti-cell-proliferation properties which are more potent than those in the aforementioned references. These properties are due to HDAC inhibition.
DESCRIPTION OF THE INVENTION
[0004] According to the invention there is provided a tricyclic alkylhydroxamate derivative of the formula I
[0005] wherein
[0006] A denotes a bond, the groups —CH 2 —O—, —CH 2 —S—, —CH 2 —CH 2 —, or —NH—CO—;
[0007] X denotes the group —NR 3 —, ═CO, or —CH(OH,)—;
[0008] Y denotes an oxygen atom, a sulfur atom, or the group —NR 4 —;
[0009] Z denotes a straight chain alkylene group comprising 4, 5, 6, 7, or 8 carbon atoms, wherein one CH 2 group may be replaced by an oxygen or a sulfur atom, or wherein 2 carbon atoms form a C═C double bond, and which is either unsubstituted or substituted by one or two substituents selected from (1-4C)alkyl and halogen atoms;
[0010] R 1 and R 2 denote substituents independently selected from a hydrogen atom, halogen atoms, (1-4C)alkyl, trifluoromethyl, hydroxy, (1-4C)alkoxy, benzyloxy, (1-3C)alkylenedioxy, nitro, amino, (1-4C)alkylamino, di[(1-4C)alkyl]-amino, or (1-4C)alkanoylamino groups;
[0011] R 3 and R 4 independently denote hydrogen atoms or (1-4C)alkyl groups;
[0012] their enantiomers, diastereoisomers, racemates, salts and mixtures thereof.
[0013] A suitable value for a substituent when it is a halogen atom is, for example, fluoro, chloro, bromo and iodo; when it is (1-4C)alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl; when it is (1-4C)alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy or butoxy; when it is (1-4C)alkylamino is, for example, methylamino, ethylamino or propylamino; when it is di-[(1-4C)alkyl]amino is, for example, dimethylamino, N-ethyl-N-methylamino, diethylamino, N-methyl-N-propylamino or dipropylamino; when it is (1-4C)alkanoylamino is, for example, formylamido, acetamido, propionamido or butyramido; and when it is (1-3C)alkylenedioxy is, for example, methylenedioxy, ethylenedioxy or propylenedioxy.
[0014] Preferred tricycles of formula I are dibenzoxepine, dibenzazepine, fluorene or carbazol.
[0015] Y is preferred an oxygen atom. Z is a straight chain alkylene group with 4 to 8 carbon atoms, preferably 4 to 7. The chain can be substituted by one or two halogen atoms, preferably chlorine, or a C 1 -C 4 -alkyl group, preferably methyl. One —CH 2 -group of the chain can be replaced by an oxygen or sulfur atom, however, this group should not be the first or last member of the chain. A CH 2 —CH 2 -group of the chain can also form a —CH═CH-group.
[0016] Preferred compounds of the invention include tricyclic alkylhydroxamate derivatives of the formula I
[0017] wherein
[0018] A denotes a bond, the groups —CH 2 —O—, or —NH—CO—;
[0019] X denotes the group —NR 3 —, ═CO, or —CH(OH)—;
[0020] Y denotes an oxygen atom, a sulfur atom, or the group —NR 4 —;
[0021] Z denotes a straight chain alkylene group comprising 4, 5, 6, 7, or 8 carbon atoms, wherein one CH 2 group may be replaced by an oxygen or a sulfur atom, or wherein 2 carbon atoms form a C═C double bond, and which is either unsubstituted or substituted by one or two substituents selected from (1-4C)alkyl and halogen atoms;
[0022] R 1 and R 2 denote substituents independently selected from halogen atoms, (1-4C)alkyl, trifluoromethyl, hydroxy, (1-4C)alkoxy, benzyloxy, (1-3C)alkylenedioxy, nitro, amino, (1-4C)alkylamino, di[(1-4C)alkyl]-amino, or (1-4C)alkanoylamino groups;
[0023] R 3 and R 4 independently denote hydrogen atoms or (1-4C)alkyl groups;
[0024] their enantiomers, diastereoisomers, racemates, salts and mixtures thereof.
PREPARATION OF THE COMPOUNDS OF THE INVENTION
[0025] A tricyclic alkylhydroxamate derivative of the formula I, or a pharmaceutically-acceptable salt thereof, may be prepared by any process known to be applicable to the preparation of chemically-related compounds. Such processes, when used to prepare a tricyclic alkylhydroxamate derivative of the formula I, or a pharmaceutically-acceptable salt thereof, are provided as a further feature of the invention and are illustrated by the following representative examples in which, unless otherwise stated, A, X, Y, Z, R 1 , R 2 , R 3 , and R 4 have any of the meanings defined hereinbefore. The starting materials may be obtained by standard procedures of organic chemistry. The preparation of such starting materials is described within the accompanying non-limiting examples. Alternatively starting materials are obtainable by analogous procedures to those illustrated which are within the ordinary skills of an organic chemist.
[0026] a) One preferred method for the preparation of compounds of the formula I is the deprotection of compounds of the formula II
[0027] wherein R 5 is a suitable protecting group. Compounds of the formula II are new and included in the present invention.
[0028] Suitable protecting groups are the benzyl-, p-methoxybenzyl-, tert.butyloxy-carbonyl-, trityl-, or silyl groups such as the trimethylsilyl- or dimethyl-tert.butylsilyl-group. The reactions carried out depend on the type of the protecting group. When the protecting group is a benzyl- or p-methoxybenzyl group, the reaction carried out is a hydrogenolysis in an inert solvent such as an alcohol like methanol or ethanol, in the presence of a noble metal catalyst such as palladium on a suitable carrier such as carbon, barium sulfate, or barium carbonate, at ambient temperature and pressure. When the protecting group is the tert.butyloxycarbonyl-, trityl-, or a silyl group such as the trimethylsilyl- or dimethyl-tert.butylsilyl-group, the reaction is carried out in the presence of acids at a temperature between −20° C. and 60° C., preferably between 0° C. and ambient temperature. The acid may be a solution of hydrochloric acid in an inert solvent such as diethyl ether or dioxane, or trifluoro acetic acid in dichloromethane. Alternatively, when the protecting group is a silyl group such as the trimethylsilyl or dimethyl-tert.butylsilyl group, the reaction is carried out in the presence of a fluoride source such as sodium fluoride or tetrabutyl ammonium fluoride in an inert solvent such as dichloromethane.
[0029] Compounds of the formula II are obtained by the reaction of a tricyclic alkylhydroxamate of the formula III
[0030] with a compound formula IV
W-Z-CONH—O—R 5 (IV)
[0031] wherein W is a displaceable group and Z and R 5 have the meaning defined hereinbefore, in the absence or presence of a suitable base.
[0032] A suitable displaceable group W is, for example, a halogeno, or sulphonyloxy group, for example a chloro, bromo, methanesulphonyloxy or toluene-p-sulphonyloxy group. A suitable base is, for example, an organic amine base such as, for example, pyridine, 2,6-lutidine, collidine, 4-dimethylaminopyridine, triethylamine, morpholine, N-methylmorpholine or diazabicyclo[5.4.0]undec-7-ene, or for example, an alkali or alkaline earth metal carbonate or hydroxide, for example sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide.
[0033] The reaction is conveniently carried out in the presence of a suitable inert solvent or diluent, for example an alkanol or ester such as methanol, ethanol, isopropanol or ethyl acetate, a halogenated solvent such as methylene chloride, chloroform or carbon tetrachloride, an ether such as tetrahydrofuran or 1,4-dioxane, an aromatic solvent such as toluene, or a dipolar aprotic solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidin-2-one or dimethylsulfoxide. The reaction is conveniently carried out at a temperature in the range, for example, 10 to 250° C., preferably in the range 40-200° C.
[0034] The compounds of the general formula III are either commercially available or can be prepared according to the following literature references or in analogous manners. Compounds of the formula III wherein A denotes a bond and X denotes the group NR 3 —, can be prepared according to the German Patent Application DE 2928483 (Lauer, K., and Kiegel, E.; Boehringer Mannheim GmbH). Compounds of the formula III wherein A denotes a bond, the group —CH 2 CH 2 —, or —CH 2 —O— and X denotes the group ═CO, can be prepared according to German Patent Application DE 2208893 (Winter, W., et al.; Boehringer Mannheim Gmbh).
[0035] Compounds of the formula IV are prepared by reacting compounds of formula W-Z-COOH (commercially available) with the compounds of the formula H 2 N—O—R 5 (commercially available) wherein W, Z, and R 5 have the meaning defined hereinbefore. This is a two step reaction. In the first step, the carboxylate becomes activated. This reaction is carried out in an inert solvent or diluent, for example, in dichloromethane, dioxane, or tetrahydrofuran, in the presence of an activating agent. A suitable reactive derivative of an acid is, for example, an acyl halide, for example an acyl chloride formed by the reaction of the acid with an inorganic acid chloride, for example thionyl chloride; a mixed anhydride, for example an anhydride formed by the reaction of the acid and a chloroformate such as isobutyl chloroformate; an active ester, for example an ester formed by the reaction of the acid and a phenol such as pentafluorophenol, an ester such as pentafluorophenyl trifluoroacetate or an alcohol such as methanol, ethanol, isopropanol, butanol or N-hydroxybenzotriazole; an acyl azide, for example an azide formed by the reaction of the acid and an azide such as diphenylphosphoryl azide; an acyl cyanide, for example a cyanide formed by the reaction of the acid and a cyanide such as diethylphosphoryl cyanide; or the product of the reaction of the acid and a carbodiimide such as dicyclohexylcarbodiimide. The reaction is carried out between −30° C. and 60° C., conveniently at or below 0° C. In the second step, hydroxylamine is added to the solution at the temperature used for the activation, and the temperature is slowly adjusted to ambient temperature.
[0036] b) Another preferred method for the preparation of compounds of the formula I involves the reaction of compounds of the formula V
[0037] with hydroxylamine. This reaction typically involves a two-step one-pot procedure. In the first step, the carboxylate of the formula V becomes activated. This reaction is carried out in an inert solvent or diluent, for example, in dichloromethane, dioxane, or tetrahydrofuran, in the presence of an activating agent. A suitable reactive derivative of an acid is, for example, an acyl halide, for example an acyl chloride formed by the reaction of the acid with an inorganic acid chloride, for example thionyl chloride; a mixed anhydride, for example an anhydride formed by the reaction of the acid and a chloroformate such as isobutyl chloroformate; an active ester, for example an ester formed by the reaction of the acid and a phenol such as pentafluorophenol, an ester such as pentafluorophenyl trifluoroacetate or an alcohol such as methanol, ethanol, isopropanol, butanol or N-hydroxybenzotriazole; an acyl azide, for example an azide formed by the reaction of the acid and an azide such as diphenylphosphoryl azide; an acyl cyanide, for example a cyanide formed by the reaction of the acid and a cyanide such as diethylphosphoryl cyanide; or the product of the reaction of the acid and a carbodiimide such as dicyclohexylcarbodiimide. The reaction is carried out between −30° C. and 60° C., conveniently at or below 0° C. In the second step, hydroxylamine is added to the solution, at the temperature used for the activation, and the temperature is slowly adjusted to ambient temperature.
[0038] Compounds of the formula V are prepared from compounds of the formula VI
[0039] wherein R 6 is an alkyl group, for example, a methyl, ethyl, or tert.butyl group or benzyl group, by hydrolysis. The conditions under which the hydrolysis is carried out depend on the nature of the group R 6 . When R 6 is a methyl or ethyl group, the reaction is carried out in the presence of a base, for example, lithium hydroxide, sodium hydroxide, or potassium hydroxide in an inert solvent or diluent, for example, in methanol or ethanol. When R 6 is the tert.butyl group, the reaction is carried out in the presence of an acid, for example, a solution of hydrochloric acid in an inert solvent such as diethyl ether or dioxane, or trifluoro acetic acid in dichloromethane. When R 6 is the benzyl group, the reaction is carried out by hydrogenolysis in the presence of a noble metal catalyst such as palladium on a suitable carrier, such as carbon.
[0040] Compounds of the formula VI are prepared from compounds of the formula III
[0041] by reaction with compounds of the formula VII
W-Z-COO—R 6 (VII)
[0042] in the presence of a suitable base.
[0043] A suitable base is, for example, an organic amine base such as, for example, pyridine, 2,6-lutidine, collidine, 4-dimethylaminopyridine, triethylamine, morpholine, N-methylmorpholine or diazabicyclo[5.4.0]undec-7-ene, or, for example, an alkali or alkaline earth metal carbonate or hydroxide, for example sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide.
[0044] The reaction is conveniently carried out in the presence of a suitable inert solvent or diluent, for example an alkanol or ester such as methanol, ethanol, isopropanol or ethyl acetate, a halogenated solvent such as methylene chloride, chloroform or carbon tetrachloride, an ether such as tetrahydrofuran or 1,4-dioxane, an aromatic solvent such as toluene, or a dipolar aprotic solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidin-2-one or dimethylsulfoxide. The reaction is conveniently carried out at a temperature in the range, for example, 10 to 250° C., preferably in the range 40-200° C.
[0045] Compounds of formula VII are commercially available.
[0046] c) A third preferred method for the production of compounds of the formula I involves the reaction of compounds of the formula VIII
[0047] wherein R 7 is an (1-4C)alkyl group, for example, a methyl or ethyl group, with hydroxylamine in the presence of a suitable base.
[0048] The reaction is carried out in an inert solvent or diluent such as methanol or ethanol at temperatures between 0° C. and 100° C., conveniently at or near ambient temperature, and at a pH between 9 and 11. A suitable base is, for example, an alcoholate, for example, sodium methylate.
[0049] d) Those compounds of the formula I wherein one of the substituents is an amino group may be prepared by the reduction of a derivative of the formula I wherein the substituent is a nitro group. The reduction may conveniently be carried out by any of the many procedures known for such a transformation. The reduction may be carried out, for example, by the hydrogenation of a solution of the nitro compound in an inert solvent or diluent as defined hereinbefore in the presence of a suitable metal catalyst such as palladium or platinum. A further suitable reducing agent is, for example, an activated metal such as activated iron (produced by washing iron powder with a dilute solution of an acid such as hydrochloric acid). Thus, for example, the reduction maybe carried out by heating a mixture of the nitro compound and the activated metal in a suitable solvent or diluent such as a mixture of water and an alcohol, for example, methanol or ethanol, to a temperature in the range, for example, 50 to 150° C., conveniently at or near 70° C.
[0050] e) Those compounds of the formula I wherein X denotes the —CH(OH)— group may be prepared by the reduction of a derivative of the formula I wherein X denotes the ═CO group. The reduction may conveniently be carried out by any of the many procedures known for such a transformation. The reduction may be carried out, for example, by hydrogenation in an inert solvent or diluent as defined hereinbefore in the presence of a suitable metal catalyst such as palladium or platinum, for example, in methanol or ethanol, at a temperature in the range, for example, 0 to 100° C., conveniently at or near ambient temperature.
[0051] f) Those compounds of the formula I wherein one of the substituents is an (1-4C)alkanoylamino group, are prepared by acylation of a derivative of the formula I wherein the substituent is an amino group. A suitable acylating agent is, for example, any agent known in the art for the acylation of amino to acylamino, for example an acyl halide, for example an alkanoyl chloride or bromide, conveniently in the presence of a suitable base, as defined hereinbefore, an alkanoic acid anhydride or mixed anhydride, for example acetic anhydride or the mixed anhydride formed by the reaction of an alkanoic acid and an alkoxycarbonyl halide, for example an alkoxycarbonyl chloride, in the presence of a suitable base as defined hereinbefore. In general the acylation is carried out in a suitable inert solvent or diluent as defined hereinbefore and at a temperature, in the range, for example, −30 to 120° C., conveniently at or near ambient temperature.
[0052] Compounds of the formula VIII are prepared from a compound of the general formula III reacted with a compound of formula W-Z-COOR 7 , in like manner to the reaction of a compound of formula III with one of formula VII.
[0053] The enantiomers or diastereoisomers of the compounds of formula I can be obtained by usual methods as column chromatography or crystallization or optical resolution of enantiomers by treatment with optically active acids or bases or by using optically active starting materials.
[0054] “Pharmaceutically acceptable salts” refer to conventional acid-addition salts or base-addition salts that retain the biological effectiveness and properties of the compounds of formula I and are formed from suitable non-toxic organic or inorganic acids or organic or inorganic bases. Sample acid-addition salts include those derived from inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfamic acid, phosphoric acid and nitric acid, and those derived from organic acids such as p-toluenesulfonic acid, salicylic acid, methanesulfonic acid, oxalic acid, succinic acid, citric acid, malic acid, lactic acid, fumaric acid, and the like. Sample base-addition salts include those derived from ammonium, potassium, sodium and, quaternary ammonium hydroxides, such as for example, tetramethylammonium hydroxide. The chemical modification of a pharmaceutical compound (i.e., a drug) into a salt is a technique well known to pharmaceutical chemists to obtain improved physical and chemical stability, hygroscopicity, flowability and solubility of compounds. See, e.g., H. Ansel et. al., Pharmaceutical Dosage Forms and Drug Delivery Systems (6th Ed. 1995) at pp. 196 and 1456-1457.
[0055] According to a further aspect of the invention there is provided a pharmaceutical composition which comprises a tricyclic alkylhydroxamate derivative of the formula I, or enantiomer, diastereoisomer, racemate, pharmaceutically-acceptable salt or mixture thereof, in association with a pharmaceutically-acceptable diluent or carrier. The composition may be in a form suitable for oral administration, for example as a tablet or capsule, for parenteral injection (including intravenous, subcutaneous, intramuscular, intravascular or infusion) as a sterile solution, suspension or emulsion, for topical administration as an ointment or cream or for rectal administration as a suppository. In general the above compositions may be prepared in a manner using conventional excipients. The tricyclic alkylhydroxamate will normally be administered to a warm-blooded animal at a unit dose within the range 5-5000 mg per square meter body area of the animal, i.e. approximately 0.1-100 mg/kg, and this normally provides a therapeutically-effective dose. A unit dose form such as a tablet or capsule will usually contain, for example 1-250 mg of active ingredient. Preferably a daily dose in the range of 1-50 mg/kg is employed. However the daily dose will necessarily be varied depending upon the host treated, the particular route of administration, and the severity of the illness being treated. Accordingly the optimum dosage may be determined by the practitioner who is treating any particular patient.
[0056] According to a further aspect of the present invention there is provided a tricyclic alkylhydroxamate derivative of the formula I as defined hereinbefore for use in a method of treatment of the human or animal body by therapy. We have now found that the compounds of the present invention possess anti-cell-proliferation properties which are believed to arise from their histone deacetylase inhibitory activity. Accordingly the compounds of the present invention provide a method for treating the proliferation of malignant cells. Accordingly the compounds of the present invention are expected to be useful in the treatment of cancer by providing an anti-proliferative effect, particularly in the treatment of cancers of the breast, lung, colon, rectum, stomach, prostate, bladder, pancreas and ovary. It is in addition expected that a derivative of the present invention will possess activity against a range of leukemias, lymphoid malignancies and solid tumors such as carcinomas and sarcomas in tissues such as the liver, kidney, prostate and pancreas.
[0057] Thus according to this aspect of the invention there is provided the use of a tricyclic alkylhydroxamate derivative of the formula I, or a pharmaceutically-acceptable salt thereof, as defined hereinbefore in the manufacture of a medicament for use in the production of an anti-cell-proliferation effect in a warm-blooded animal such as man.
[0058] According to a further feature of this aspect of the invention there is provided a method for producing an anti-cell-proliferation effect in a warm-blooded animal, such as man, in need of such treatment which comprises administering to said animal an effective amount of a tricyclic alkylhydroxamate derivative as defined hereinbefore.
[0059] The anti-cell-proliferation treatment defined hereinbefore may be applied as a sole therapy or may involve, in addition to the compounds of the invention, one or more other anti-tumor substances, for example those selected from, for example, mitotic inhibitors, for example vinblastine; alkylating agents, for example cis-platin, carboplatin and cyclophosphamide; inhibitors of microtubule assembly, like paclitaxel or other taxanes; antimetabolites, for example 5-fluorouracil, capecitabine, cytosine arabinoside and hydroxyurea, or, for example, intercalating antibiotics, for example adriamycin and bleomycin; immunostimulants, for example trastuzumab; DNA synthesis inhibitors, e.g. gemcitabine; enzymes, for example asparaginase; topoisomerase inhibitors, for example etoposide; biological response modifiers, for example interferon; and anti-hormones, for example antioestrogens such as tamoxifen or, for example antiandrogens such as (4′-cyano-3-(4-fluorophenylsulphonyl)-2-hydroxy-2-methyl-3′-(trifluormethyl) propionanilide, or other therapeutic agents and principles as described in, for example Cancer: Principles & Practice of Oncology, Vincent T. DeVita, Jr., Samuel Hellmann, Steven A. Rosenberg; 5th Ed., Lippincott-Raven Publishers, 1997. Such conjoint treatment maybe achieved by way of the simultaneous, sequential or separate dosing of individual components of the treatment. According to this aspect of the invention there is provided a pharmaceutical product comprising a tricyclic alkylhydroxamate derivative of the formula I as defined hereinbefore and an additional anti-tumor substance as defined hereinbefore for the conjoint treatment of cancer.
[0060] The invention will now be illustrated in the following non-limiting examples in which, unless otherwise stated:
[0061] (i) evaporations were carried out by rotary evaporation in vacuo and work-up procedures were carried out after removal of residual solids such as drying agents by filtration;
[0062] (ii) operations were carried out at ambient temperature, that is in the range 18-25° C. and under an atmosphere of an inert gas such as argon or nitrogen;
[0063] (iii) column chromatography (by the flash procedure) and high pressure liquid chromatography (HPLC) were performed on Merck Kieselgel silica or Merck Lichroprep RP-18 reversed-phase silica obtained from E. Merck, Darmstadt, Germany;
[0064] (iv) yields are given for illustration only and are not necessarily the maximum attainable;
[0065] (v) melting points were determined using a Mettler SP62 automatic melting point apparatus, an oil-bath apparatus or a Kofler hot plate apparatus.
[0066] (vi) the structures of the end-products of the formula I were confirmed by nuclear (generally proton) magnetic resonance (NMR) and mass spectral techniques (Micromass Platform II machine using APCI or Micromass Platform ZMD using electrospray);
[0067] (vii) intermediates were not generally fully characterized and purity was assessed by thin layer chromatography.
EXAMPLE 1
[0068] [0068]
8-(11-Oxo-6,11-dihydro-dibenzo[b,e]oxepin-2-yloxy)-octanoic Acid Hydroxyamide
[0069] (a) In an ice bath, 14 ml triethylamine was added to a suspension of 3.2 g (20 mmol) O-benzylhydroxylamine hydrochloride in 150 ml dichloromethane. Stirring was continued until the solution became clear. Then, 4.5 g (20 mmol) omega-bromo octanoic acid was added, followed by 5.6 g (22 mmol) bis-(2-oxo-3-oxazolidinyl)-phosphorylchloride. Stirring was continued at ambient temperature for 18 h. The solution was extracted twice with 150 ml each of 1M aqueous hydrochloric acid and twice with 150 ml each of 1M aqueous sodium bicarbonate. The organic solvent was removed i.vac. to give 5.1 g (78%) of 8-bromo-octanoic acid benzyloxy-amide as a colorless oil. MS: 330 (M+H + ).
[0070] (b) 488 mg (3.5 mmol) Potassium carbonate was added to a solution of 400 mg (1.8 mmol) 2-hydroxy-6H-dibenzo[b,e]oxepin-11-one and 580 mg (1.8 mmol) 8-bromo-octanoic acid benzyloxy-amide in dimethyl formamide. The slurry was heated to 100° C. for 14 h. After cooling to ambient temperature, water was added and extracted with ethyl acetate. The organic phase was washed with water, dried over sodium sulfate, filtered, and the solvent was evaporated. The residue was purified by column chromatography using ethyl acetate/heptane 1:1 as eluent. There was thus obtained 420 mg (50%)) 8-(11-Oxo-6,11-dihydro-dibenzo[b,e]oxepin-2-yloxy)-octanoic acid benzyloxyamide as a colorless oil. MS: 474 (M+H + ); 472 (M−H + ).
[0071] (c) 400 mg (0.845 mmol) 8-(11-Oxo-6,11-dihydro-dibenzo[b,e]oxepin-2-yloxy)-octanoic acid benzyloxyamide in 50 ml methanol was hydrogenated in the presence of palladium on calcium carbonate at ambient temperature and pressure. The catalyst was removed by filtration and the solvent was evaporated. The residue was purified by column chromatography (methanol/water 75:25). There was thus obtained 90 mg (28%) of the title compound as an amorphous solid. MS: 382 (M−H + ); 384 (M+H + ).
EXAMPLE 2
[0072] [0072]
rac-8-(9-Hydroxy-9H-fluoren-2-yloxy)-octanoic Acid Hydroxyamide
[0073] (a) In a manner analogous to that of example 1(b), 8-bromo-octanoic acid benzyloxy-amide (example 1(a); 0.3 g, 1.3 mmol) was reacted with 2-hydroxy-fluoren-9-one (0.30 g, 1.5 mmol) in the presence of potassium carbonate (0.21 g, 1.5 mmol) and dimethyl formamide (10 ml) to give 8-(9-oxo-9H-fluoren-2-yloxy)-octanoic acid benzyloxyamide as an almost colorless wax (yield 0.43 g, 63%; purified by column chromatography using silica gel and ethyl acetate:heptane=1:1 as eluent). MS (M−H 30 )=442.
[0074] (b) In a manner anologous to that of example 1(c), 8-(9-oxo-9H-fluoren-2-yloxy)-octanoic acid benzyloxyamide (430 mg, 1 mmol) was hydrogenated to give the title compound (160 mg) in 46% yield as an amorphous solid. MS (M−H + )=354.
EXAMPLE 3
[0075] [0075]
8-(9H-Carbazol-2-yloxy)-octanoic Acid Hydroxyamide
[0076] (a) In a manner analogous to that of example 1(b), 8-bromo-octanoic acid benzyloxy-amide (example 1(a); 0.3 g, 1.1 mmol) was reacted with 2-hydroxy-9H-carbazol (0.3 g, 1.1 mmol) in the presence of potassium carbonate (0.15 g, 1.1 mmol) and DMF as solvent to give 8-(9H-carbazol-2-yloxy)-octanoic acid benzyloxyamide as an almost colorless wax (yield 0.1 g, 20%; purified by column chromatography using silica gel and ethyl acetate as eluent). MS (M+H + )=483.
[0077] (b) In a manner anologous to that of example 1(c), 8-(9H-carbazol-2-yloxy)-octanoic acid benzyloxyamide (90 mg, 430 mmol) in tetrahydrofuran was hydrogenated in the presence of palladium on barium sulfate to give the title compound as a crystalline solid (16 mg). MS (M−H + )=339.
EXAMPLE 4
[0078] [0078]
8-(9H-Carbazol-4-yloxy)-octanoic Acid Hydroxyamide
[0079] (a) In a manner analogous to that of example 1(b), 8-bromo-octanoic acid benzyloxy-amide (example 1(a); 0.54 g, 1.6 mmol) was reacted with 4-hydroxycarbazol (0.3 g, 1.6 mmol) in the presence of potassium carbonate (0.23 g, 1.6 mmol) in dimethyl formamide to give 8-(9H-carbazol-4-yloxy)-octanoic acid benzyloxyamide as an almost colorless oil (yield 0.3 g, 42%; purified by column chromatography using silica gel and ethyl acetate:heptane=4:6 as eluent). MS (M−H + )=429.
[0080] (b) In a manner anologous to that of example 1(c), 8-(9H-Carbazol-4-yloxy)-octanoic acid benzyloxyamide (300 mg, 0.7 mmol) was hydrogenated in the presence of palladium on barium sulfate to give the title compound (110 mg) in 46% yield as an amorphous solid. MS (M−H + )=339.
EXAMPLE 5
[0081] [0081]
7-(9H-Carbazol-2-yloxy)-heptanoic Acid Hydroxyamide
[0082] (a) In an ice bath, 2.4 ml triethylamine was added to a suspension of 2.7 g (17 mmol) O-benzylhydroxylamine hydrochloride in 100 ml dichloromethane. 3.6 g (17 mmol) 7-bromo heptanoic acid was added, followed by 5.3 g (21 mmol) bis-(2-oxo-3-oxazolidinyl)-phosphorylchloride. Stirring was continued at ambient temperature for 18 h. The solution was extracted twice with 150 ml each of 1M aqueous hydrochloric acid and twice with 150 ml each of 1M aqueous sodium bicarbonate. The organic solvent was removed i.vac. and the residue was purified by column chromatography (silica gel; ethyl acetate:heptane 1:1) to give 1.55 g (30%) of 7-bromo-heptanoic acid benzyloxy-amide as a colorless oil. MS: 314 (M+H + ).
[0083] (b) In a manner analogous to that of example 1(b), 7-bromo-heptanoic acid benzyloxy-amide (1.8 g, 5.7 mmol) was reacted with 2-hydroxycarbazole (1.05 g, 5.7 mmol) in the presence of potassium carbonate (1.2 g, 8.6 mmol) in dimethyl formamide to give 7-(9H-carbazol-2-yloxy)-heptanoic acid benzyloxyamide as an almost colorless wax (yield 0.53 g, 22%; purified by column chromatography using silica gel and ethyl acetate:heptane=4:6 to 6:4 as an eluent). MS (M−H + )=415.
[0084] (c) In a manner analogous to that of example 1(c), 7-(9H-carbazol-2-yloxy)-heptanoic acid benzyloxyamide (530 mg, 1.3 mmol) was hydrogenated to give the title compound in 62% yield (260 mg) as a crystalline solid. mp 198° C. MS (M−H + )=325.
EXAMPLE 6
[0085] [0085]
6-(9H-Carbazol-2-yloxy)-hexanoic Acid Hydroxyamide
[0086] (a) 2-Hydroxycarbazole (0.5 g, 2.7 mmol), ethyl 6-bromohexanoate (0.6 g, 2.7 mmol), and potassium carbonate (0.4 g, 3.0 mmol) in dimethyl formamide (10 ml) were heated to 120° C. for 24 h. Water was added and extraction with ethyl acetate was performed. The combined organic phases were washed with water and dried (sodium sulfate). The solvent was removed i.vac. and the residue was purified by column chromatography (silica gel, ethyl acetate:heptane=1:1) to give ethyl 6-(9H-carbazol-2-yloxy)-hexanoate (290 mg, 33%) as a colorless solid. MS (M−H + ) 324.
[0087] (b) Ethyl 6-(9H-carbazol-2-yloxy)-hexanoate (270 mg, 0.8 mmol) and 1 N aqueous lithium hydroxide (2 ml, 2 mmol) in 15 ml methanol was heated to reflux for 1 h. The solvent was removed, the residue was acidified by 1 ml 2N aqueous hydrochloric acid. The precipitate was collected to give 6-(9H-carbazol-2-yloxy)-hexanoic acid (230 mg, 93%) as a colorless solid. MS (M−H + ) 296.
[0088] (c) 6-(9H-carbazol-2-yloxy)-hexanoic acid (220 mg, 0.74 mmol) in tetrahydrofuran (10 ml) was cooled to 0° C. Isobutyl chloroformiate (101 mg, 0.74 mmol) and N-methyl morpholine (112 mg, 1.1 mmol) was added and stirred at 0° C. for 15 min.
[0089] (d) Hydroxylamine hydrochloride (77 mg, 1.1 mmol) was added to a cold (0° C.) solution of potassium hydroxide (62 mg, 1.1 mmol) in methanol (2 ml). The precipitate was removed and the solution was added to a solution of the activated carboxylic acid (c). Stirring was continued for 1 h at ambient temperature and the solvent was removed i.vac. The residue was purified by column chromatography (silica gel, ethal acetate:heptane 1:1) to give the title compound (53 mg, 23%) as a colorless solid. mp 192° C. MS (M−H + ) 311.
EXAMPLE 7
[0090] [0090]
5-(9H-Carbazol-2-yloxy)-pentanoic Acid Hydroxyamide
[0091] (a) In a manner analogous to that of example 6(a), ethyl 5-bromo-pentanoate (685 mg, 3.28 mmol) was reacted with 2-hydroxycarbazole (600 mg, 3.28 mmol) to give ethyl 5-(9H-carbazol-2-yloxy)-pentanoate (350 mg, 34%) as a colorless solid. MS (M−H + ) 310.
[0092] (b) In a manner analogous to that of example 6(b), ethyl 5-(9H-carbazol-2-yloxy)-pentanoate (400 mg, 1.3 mmol) was saponified to give 5-(9H-carbazol-2-yloxy)-pentanoic acid (350 mg, 96%) as a colorless solid. MS (M−H + ) 282.
[0093] (c) In a manner analogous to that of example 6(c), 5-(9H-carbazol-2-yloxy)-pentanoic acid (350 mg, 1.2 mmol) was converted to the title compound to give 130 mg (30%) as colorless solid (MS (M−H + ) 297.
EXAMPLE 8
[0094] In an analogous manner to that described in the examples 1-7 the following compounds are prepared:
[0095] (a) 7-(9H-Carbazol-4-yloxy)-heptanoic acid hydroxyamide
[0096] (b) 7-(9H-Carbazol-3-yloxy)-heptanoic acid hydroxyamide
[0097] (c) 7-(9H-Carbazol-1-yloxy)-heptanoic acid hydroxyamide
[0098] (d) 7-(9-Methyl-carbazol-2-yloxy)-heptanoic acid hydroxyamide
[0099] (e) 7-(9H-carbazol-2-yloxy)-5-methyl-heptanoic acid hydroxyamide
[0100] (f) 7-(9H-carbazol-2-yloxy)-4-methyl-heptanoic acid hydroxyamide
[0101] (g) 7-(9H-carbazol-2-yloxy)-3-methyl-heptanoic acid hydroxyamide
[0102] (h) 7-(9H-carbazol-2-yloxy)-2-methyl-heptanoic acid hydroxyamide
[0103] (i) 8-(9H-carbazol-2-yloxy)-2-methyl-octanoic acid hydroxyamide
[0104] (j) 7-(9H-carbazol-2-yloxy)-4-oxa-heptanoic acid hydroxyamide
[0105] (k) 7-(9H-carbazol-2-yloxy)-3-methyl-4-oxa-heptanoic acid hydroxyamide
[0106] (l) 7-(9H-carbazol-2-yloxy)-3-oxa-heptanoic acid hydroxyamide
[0107] (m) 7-(9H-carbazol-2-yloxy)-3-oxa-5cis-heptenoic acid hydroxyamide
[0108] (n) 7-(9H-carbazol-2-yloxy)-3-oxa-5trans-heptenoic acid hydroxyamide
[0109] (o) 7-(9H-carbazol-2-yloxy)-2-methyl-3-oxa-heptanoic acid hydroxyamide
EXAMPLE 9
Evaluation of Inhibitory Properties of the Compounds of the Invention
[0110] To measure the inhibitory properties of the compounds of the invention, a screening assay was performed using an aminocoumarin derivative of an omega-acetylated lysine as substrate for the enzyme. This assay has been described in detail in the literature Hoffman, K., et al., Nucleic Acids Res. 27 (1999) 2057-2058). Using the protocol described therein, there was measured the inhibitory effect of the compounds at a concentration of 10 nM. The observed inhibition rates for selected compounds are the following table:
Title compound of example No. Inhibitory effect at 10 nM in % 1 62 2 79 3 86 4 97 5 100 6 80 7 69
[0111] In the same assay, suberanilohydroxamic acid (SAHA), which was included as a reference, showed an inhibitory effect of 42% at 10 nM. | Compounds of formula I
wherein R1, R2, A, X, Y and Z have the meanings provided in the specification, and their enantiomers, diastereoisomers, racemates, pharmaceutically acceptable salts and mixtures thereof. These compounds have HDAC inhibitory activity for inhibiting cell proliferation. Also provided is a process of manufacturing these compounds. | 2 |
FIELD OF THE INVENTION
This invention relates to an automobile roof having a lid associated with a roof opening.
BACKGROUND OF THE INVENTION
More particularly, the invention relates to a roof having a rigid lid which, in its closed position, closes a roof opening, out of which it is at least partially displaceable, and comprising a sliding liner which is displaceable beneath a rear, fixed portion of the roof. The sliding liner in its closed position closes an opening formed in a fixed vehicle roof liner beneath the roof opening, and a front edge of which liner, at its maximum opening displacement, lies behind the rear edge of the roof opening.
This type of automobile roof is intended to include sliding roofs, sliding-lifting roofs, lifting flaps and ridge sliding roofs (known as spoiler roofs). The rigid lid is, for the purposes of the present invention, preferably a translucent or transparent glass lid, but it may also be constructed as a sheet metal lid.
DESCRIPTION OF THE PRIOR ART
For roof constructions of this type, sliding liners have long been known. Especially in the case of automobile roofs having a glass lid, it is desirable when the glass lid is closed, to shield against solar radiation by the sliding liner. But even when the rigid lid is entirely or partly open, the sliding liner may be used either for completely exposing the roof opening or for covering this opening partly to completely. Where the roof opening is completely exposed by the sliding liner, it is desirable for the forward edge of the latter to be located completely behind the rear edge of the opening in the fixed automobile roof liner, so that the sliding liner shall not penetrate into the opening, which usually has smaller dimensions than the roof opening, and thereby reduce its maximum open area. This is not, however, achieved in all roof constructions.
In one known sliding roof with a lining lid (DE-GM No. 17 64 195) the lining lid cover i.e. the sliding liner, is movable independently of the sliding lid, but is coupled with the latter for the opening movement. This is advantageous, because the sliding liner, when the roof is opened, is automatically entrained into its rearward position, but otherwise remains open for entry of light independently of the opened or closed position of the sliding lid. If the sliding liner is to be opened when the sliding lid is closed, it must be displaced by hand into its open position. A gripping recess at the forward edge of the sliding liner is used here as a hand-operating device. In order, however, to enable this gripping recess again to be gripped when the sliding liner is completely slid back when the sliding lid is closed, the forward edge of the sliding liner must project with its gripping recess before the front edge of the opening in the fixed vehicle roof liner. Thus a maximum opening area cannot be achieved. A disadvantage of this construction is also that, when the sliding lid is open, the sliding liner cannot be slid forwards in order to cover the opened roof opening, because the coupling means acting between sliding lid and sliding liner in the opening displacement do not permit this.
In another known sliding roof (DE-PS No. 29 23 904), a sliding liner is coupled with a sliding lid in such a manner that, in the completely opened position of the sliding lid, the front edge of the sliding liner lies behind the rear edge of the opening in a fixed vehicle roof liner. For the closure movement of the sliding liner starting from this position, a restoring assembly is provided, by means of which the sliding liner, as the sliding lid closes, can be automatically entrained into an intermediate position, in which the sliding liner projects with its gripping recess, located in the forward region of the sliding liner, into the opening. By this construction, the result is indeed achieved that the sliding liner, when the sliding lid is fully opened, disappears beneath the fixed vehicle roof liner, but when the sliding lid is fully opened, on account of the engagement of an entraining assembly which causes the common opening displacement of sliding lid and sliding liner, the sliding liner cannot be displaced forwards for partly or completely covering the roof opening or liner opening. Thus, in the maximum ventilating position of the sliding lid, i.e. in its fully opened displacement, the possibility does not exist of shielding against solar radiation by means of the sliding liner. If, in this known sliding roof, starting from a fully opened position of the sliding lid and thus also of the sliding liner, the sliding lid and sliding liner are to be brought into an intermediate position, in which the roof opening and the opening in the fixed liner are only partly opened, then the disadvantage exists that the sliding lid must first be fully closed in order that the sliding liner shall be accessible for hand engagement. Thereafter, the sliding lid must then be slid back into the desired open position. In no case, however, can the sliding liner be displaced in the direction of closure beyond the front edge of the sliding lid.
In a further known sliding roof (DE-OS No. 33 38 372), a second entraining assembly, capable of being uncoupled, is provided between sliding lid and sliding liner, which in the coupled condition, during closure of the sliding lid, automatically entrains the sliding liner into its closed position. A closing displacement of the sliding liner by hand is thereby indeed rendered unnecessary, if the second entraining assembly is coupled, but with this sliding roof construction also the possibility does not exist, with the lid fully opened, of displacing the sliding liner forwards for partly or completely covering the roof opening or the opening in the fixed roof liner.
OBJECT OF THE INVENTION
It is therefore an object of the present invention to provide an automobile roof in which the sliding liner, even when the sliding lid is open, can be displaced into its closure direction for completely or partly covering the roof opening or the liner opening.
SUMMARY OF THE INVENTION
According to the present invention, there is provided an automobile roof having a rigid lid which, in its closed position, closes a roof opening, out of which it can be at least partly displaced, and comprising a sliding liner which is displaceable beneath a rear, fixed portion of the roof, closes, when in its closed position, an opening formed in a fixed vehicle roof liner beneath the roof opening, and the front edge of which, in the maximum opened displacement, lies beneath a rear edge of the opening of the fixed vehicle roof liner, and the sliding liner being displaceable by actuating elements connected only with it, independently of the rigid lid.
Thus, the entraining coupling between rigid lid and sliding liner, present in all the known, above-described sliding roofs, is avoided. In every position of the sliding lid, therefore, the sliding liner can be displaced into any desired position, without the sliding lid needing to be moved for this purpose. This includes, of course, also a complete or partial closure displacement of the sliding liner when the rigid lid is fully or partly open.
Preferably, the sliding liner is connected with movement transmission elements of a stationarily mounted drive apparatus. By these means the driver can actuate the sliding liner without having to handle it directly. The operation of the drive apparatus can be carried out from a position of the vehicle in the immediate vicinity of the driver, so that the latter is not distracted from the traffic on the road in order to displace the sliding liner, as was the case hitherto in some known sliding roofs, in which the driver had to search with one hand for the handle on the sliding liner and then to displace the sliding liner with outstretched arm by overcoming a possible difficult resistance to movement.
Preferably, the drive apparatus comprises an electric motor which can be operated in both directions of rotation, a pinion of which engages force-transmittingly into the movement transmission elements. The use of an electric motor facilitates a stepless adjustment of the sliding liner by means of a switch, which can be mounted within the immediate reach of the driver on the dashboard or on a bracket situated in front of the two front seats. The sliding liner is advantageously guided on lateral guide rails and connected, in the region of the guide rails, with the movement transmission elements. The movement transmission elements are not visible either from the interior or from the exterior of the vehicle.
With advantage, the guide rails each comprise a laterally open guide channel, into which the sliding liner engages by at least two sliding pieces, of which a rear piece is firmly connected with a drive cable guided in compression-stiff manner in the guide channel, which cable is in engagement with the pinion of the electric motor. The drive of the sliding liner is thus provided by drive cables used as movement transmission elements, which have proved highly satisfactory for actuating movement functions in automobile body construction for many years.
The sliding pieces are with advantage connected with the sliding liner adjustably in the direction of sliding of the sliding liner. This arrangement permits, in a simple manner, the setting of the sliding liner relative to the opening in the fixed roof liner and relative to the position of the sliding pieces in the guide channels.
One especially favourable arrangement of the guide rails for the sliding liner is obtained if the guide rails are constructed in one piece with lateral guide rails provided for the rigid lid.
The electric motor constituting the drive apparatus is preferably mounted behind the completely slid-open sliding liner, where sufficient space is available to accommodate it, especially since modern geared motors used in automobile construction are extremely flat.
A drive apparatus equipped with an electric motor does indeed constitute the preferred embodiment but the invention can also be realised without the use of a motor. For this purpose it is advantageous if the sliding liner is guided on lateral guide rails and is connected, at its front edge, with a preferably flexible, hand-operated device which, even at the maximum opened displacement, extends into the opening of the fixed roof liner. This flexible hand-operating device, for example a pulling band or the like, can be inconspicuously fitted and does not reduce the full opening size of the opening provided in the fixed vehicle roof liner.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention, and to show how the same may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, in which:
FIG. 1 is a plan view of a partly cut away automobile roof,
FIG. 2 is a plan of a sliding roof guide frame showing the components fitted or guided thereon, but without the rigid lid,
FIG. 3 is a section taken along the line III--III in FIG. 2, but showing part of the rigid lid and part of the automobile roof,
FIG. 4 is a section taken along the line IV--IV in FIG. 2 similar to the section according to FIG. 3,
FIG. 5 is a view, partly cut away, of the components shown in FIG. 4 along the line V--V, and
FIG. 6 is a longitudinal section through part of the rear region of an automobile roof in accordance with an alternative embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
From FIG. 1, the fixed roof portion 1 of a passenger automobile can be seen, in the forward region of which a rectangular roof opening, rounded at the corners, is situated which is bounded by an opening edge 2. In FIG. 1, the roof opening is closed by a rigid lid 3 of glass, which is sealed with respect to the fixed roof part 1 by an edge gap seal 4 of elastomeric material, extending around and fixed to it and bridging the gap between the outer periphery of the lid 3 and the opening edge 2. The example shown of an automobile roof relates to a sliding-lifting roof, i.e. the rigid lid 3 is slidably guided by front sliding elements 5 and rear sliding elements 6, disposed in pairs, on guide rails 7 of a guide frame 8 mounted on either side of the roof opening, so that the lid can either by displaced beneath the rear fixed roof part 1, after its rear edge has been lowered, or, also starting from the closed position shown in FIG. 1, can be opened by raising its rear edge and pivoting about a pivot axis orientated transversely to the direction of travel near its front edge, in the manner of a ventilating flap. The pivot axis is defined by pivot pins 9 (FIG. 3), mounted on the front sliding elements 5.
As FIG. 2 shows, the single-piece guide frame 8 has a generally U-shaped plan. The two lateral arms of the guide frame 8 are connected together at their rear ends by a transverse member 10. The guide frame 8 is so shaped in cross-section (FIGS. 3, 4) that it possesses, at front and sides, a continuous, outwardly projecting flange 11, by means of which it is fixed to the fixed roof portion 1. Adjoining the flange 11 on the inside, the guide frame 8 constitutes an upwardly open water channel drainage 12, which is bounded on the inside by the guide rail 7, formed in one piece with it.
The front and rear sliding elements 5, 6 respectively are slidably guided on the guide rail 7 in the manner shown in FIGS. 3 and 4. For this purpose, the cross-section of the guide rail 7 is generally of U-shape and possesses, in the upper regions of its two arms, inwardly open guide channels opposite to each other for guiding the threaded cable 13, used for actuating the lid 3. In the guide channel not used in each case by a threaded cable 13, the sliding elements 5 and 6 are guided by guide projections 14, adapted to the channel cross-section.
The flexible threaded cables 13 are displaced in their guide channels by a drive pinion 15, engaging into their thread turns, of a gear apparatus 17, mounted on the front transverse portion of the guide frame 8 and actuated by a hand crank 16, for causing the adjustment movements of the lid 3. The rear sliding elements 6 are in engagement, by guide pins 18 fixed to them, with guide blocks 19 mounted laterally on the lid 3, as can be seen from FIGS. 4 and 6. This guide block engagement controls both the sliding movement and also the raising-out and pivoting-in movement of the lid 3. Since this invention does not concern this aspect of the automobile roof, the movement drive for the lid 3 is not further described.
On the side of the guide rail 7 remote from the water drainage channel 12, there is a further, laterally open, back-cut guide channel 20, which serves for guiding a sliding liner 21. In FIG. 2, this sliding liner 21, which may be equipped with ventilation openings or slits or the like, is illustrated in its closed position by full lines.
The sliding liner 21 is a stiff plate, rounded at its corners. At the two sides of the sliding liner 21, a total of four lugs 22, spaced apart, is releasably fixed to the upper face of the liner, which lugs engage with their outwardly pointing ends into the guide channel 20 adjacent to each and are firmly connected there to roller-shaped sliding pieces 23, which are slidably introduced in the guide channel 20. The lugs 22 are equipped, in the edge region of the sliding liner 21, with elongate holes 24, through which fixing screws 25 adjustably engage, by which the sliding pieces 23 are attached, adjustable in the direction of sliding, to the sliding liner 21.
On the two rear sliding pieces and coaxial with them, the active cable ends of a drive cable 26 for each are fixed, by injection moulding, tamping or cold forming. The drive cables 26 are guided displaceably in the guide channels 20 and in two guide tubes 27 and 28 (FIGS. 1, 2). The guide tubes 27 and 28 are each connected to one guide channel 20 and are bent towards each other through transition radii in such a manner that they run parallel to each other behind the guide frame 8. Their parallel position is secured by connecting lugs 29 (FIG. 2). On the free ends of the guide tubes 27 and 28, lengths of tubing 30, 31 respectively are fitted on, into which the passive ends of the drive cables 26 run during the opening displacement of the sliding liner 21.
The drive cables 26 are constructed as flexible threaded cables guided in a compression-stiff manner and constitute the actuating elements or movement transmission elements for the sliding liner 21. A pinion 32 engages into the turns of their threads, which pinion forms the gear output side of an electric motor 33, connected to a reduction gear and capable of being operated in either rotational direction. The electric motor 33 and its gear connected to it are fixed to the transverse member 10 and thus behind the sliding liner 21 when the latter is slid completely open. The guide tubes 27 and 28 of course possess, in their mutually parallel zone, appropriate cut-outs for engagement with the pinion 32 and are at a distance apart which facilitates engagement of the pinion 32 with the thread turns of the drive cable 26 through the openings in the tubes.
To actuate the electric motor 33, an actuating switch (not shown) is advantageously disposed within the immediate reach of the driver. After the switch has been actuated in the desired direction of displacement, the sliding liner 21 moves in either the opening direction or the closure direction, completely independently of the position of the rigid lid 3, it being possible for the sliding liner 21 to be moved steplessly into any intermediate position.
The present automobile roof may be constructed also without a drive apparatus, in accordance with the embodiment shown in FIG. 6. For this purpose, a flexible hand-operating device is provided, mounted at the centre of the front edge of the sliding liner 21, which device, in the example shown, consists of a simple band or of a cord 34, carrying at its outer end an actuating ring 35. The cord 34 and actuating ring 35 extend, even when the sliding liner 21 is slid fully open, into the opening in the fixed vehicle roof liner 36, so that the flexible hand-operating device can be gripped for the closure movement. The sliding liner 21 can, therefore, lie in its maximum open displacement, with its front edge behind the rear edge of the opening of the fixed roof liner 36.
The opening in the fixed roof liner 36 is bounded by a peripheral closure profile 37, which is pushed both onto the edge of the fixed roof liner 36 and also, at front and sides, onto a fixing flange 38 of the guide frame 8. At the rear edge, the closure profile 37 is pushed onto a transverse plate 39, which is disposed between the two lateral arms of the guide frame 8. Beneath the rear edge gap between the rigid lid 3 and the fixed roof portion 1, there is a water conducting plate 40, displaceable together with the rigid lid 3 beneath the rear roof portion, this guide plate serving for conducting away into the lateral water channels 12 water that has penetrated through the rear edge gap. | In an automobile roof constructed, for example, as a sliding-lifting roof, and having a rigid lid, a sliding liner displaceable on lateral guide rails is provided, which is displaceable by motor operation or by hand by actuating elements connected only with it, independently of the setting of the rigid lid, and which possesses no entraining coupling with the lid. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority to Great Britain patent application number 0330251.0, filed Dec. 31, 2003 and PCT/SE2004/001652, filed Nov. 15, 2004.
1. FIELD OF THE INVENTION
The present invention relates to a steering wheel for a motor vehicle and a method of manufacturing a steering wheel for a motor vehicle.
BACKGROUND AND SUMMARY OF THE INVENTION
A typical automotive steering wheel has an inner frame formed of metal, the frame having a central portion or boss to be connected to a steering column and a plurality of spokes which extend radially outwardly from the boss to a peripheral rim. Typically the rim makes a full circle.
The frame is provided with a covering, which, in a prior proposed steering wheel, may comprise an inner core formed of polyurethane foam and an outer covering or skin formed of a plastics material such as a thermoplastic material. The polyurethane foam is light, but is a toxic material and, with present day technology, cannot be recycled.
A steering wheel must have specific dimensions, and the rim part of a steering wheel must have a dimension suitable for it to be readily grasped by hand.
The present invention seeks to provide an improved steering wheel in which polyurethane foam is not utilised but in which the weight of the steering wheel is maintained within an acceptable range.
According to a first aspect of the present invention, there is provided a steering wheel for a motor vehicle, the steering wheel having a metal frame, the metal frame defining a boss portion to be connected to a steering column, at least one spoke and a peripheral rim, at least the peripheral rim being provided with a surrounding integral plastics moulding, there being at least one cavity within the integral plastics moulding.
According to another aspect of this invention there is provided a steering wheel for a motor vehicle, the steering wheel having a metal frame, the metal frame defining a boss portion to be connected to a steering column, at least one spoke and a peripheral rim, at least the peripheral rim being provided with a surrounding integral plastics moulding, wherein there is a single closed cavity within the integral plastics moulding, the walls of the cavity being defined by the plastic moulding.
Advantageously, the rim of the frame is located at a position within the surrounding moulding which, when viewed in section, is such that the metal rim of the frame is off-set from the centre of the moulding.
Conveniently, the rim of the frame is provided with two orthogonal arms, the centre of gravity of the rim of the frame at any point being adjacent the centre of the moulding provided on the rim of the frame.
According to a further aspect of this invention there is provided a steering wheel for a motor vehicle, the steering wheel having a metal frame, the metal frame defining a boss portion to be connected to a steering column, at least one spoke and a peripheral rim, at least the peripheral rim being provided with a surrounding integral plastics moulding, wherein there is at least one cavity within the integral plastics moulding, and the peripheral rim includes a pair of orthogonal arms and is located at a position within the surrounding moulding which, when viewed in section, is off-set from the centre of the moulding.
Preferably, at least part of the moulding surrounding the rim is provided with a flexible over-moulding. Alternatively at least part of the rim is provided with a wood or leather outer sleeve.
According to another aspect of the present invention there is provided a method of making a steering wheel, the method comprising the steps of: preparing a mould defining a cavity to receive a frame for a steering wheel, the frame having a portion defining a boss to be secured to a steering column, at least one spoke and a rim connected to the spoke; the mould defining a mould cavity surrounding at least the rim, the mould cavity being provided with an injector arrangement to inject a molten plastics material and a propellant into part of the mould chamber to receive the rim of the steering wheel, the method further comprising the steps of: locating the mould in a force field, injecting plastics material into the mould at such a position, relative to the force field, that a predetermined part of the mould becomes filled with the plastics material; allowing the plastics material in contact with the surface of the mould to at least partially solidify; injecting a propellant into the mould cavity so that still molten plastics material spaced from the walls of the mould is driven into parts of the mould further from the injector arrangement; and permitting the thus driven plastics material to solidify on the walls of the mould, thus producing a steering wheel having an integral moulding surrounding the rim of the frame, with that integral moulding incorporating a chamber or cavity.
Preferably, the propellant is air. Alternatively, the propellant is another gas. In another alternative embodiment, the propellant is water.
Preferably, the injector arrangement is withdrawn from the cavity within the integral moulding and the cavity is sealed.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be more readily understood, and so that further features thereof may be appreciated, embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings in which:
FIG. 1 is a perspective view of a steering wheel,
FIG. 2 is a sectional view taken on the line II-II of the steering wheel of FIG. 1 ,
FIG. 3 is a view corresponding to FIG. 2 but illustrating a modified embodiment of the invention,
FIG. 4 is a sectional view taken through a mould utilised to form a steering wheel of the type shown in FIG. 1 ,
FIG. 5 is an elevational view of one part of the mould of FIG. 4 , and
FIG. 6 is a sectional view taken on the line VI-VI of FIG. 5 .
DETAILED DESCRIPTION OF THE INVENTION
Referring initially to FIG. 1 , a steering wheel 1 is provided with a frame 2 formed of metal, the frame 2 defining a central region or boss 3 which has an aperture 4 to secure the boss 3 to a steering column of a motor vehicle (not shown). A plurality of spokes 5 are provided which extend generally radially outwardly from the boss 3 of the steering wheel. The spokes 5 extend to a rim 6 (shown in more detail in FIG. 2 ). The rim 6 is of generally circular form and is mounted on each of the spokes 5 . The rim 6 is formed of angle section having two arms 7 , 8 extending at right angles to each other.
The frame 2 has formed thereon an integrally plastics material moulding 9 which, in this embodiment, coats the rim 6 of the steering wheel and also the parts of the spokes 5 which are closest to the rim. The moulding 9 is of circular section when considered in a direction tangential to the rim, as can be seen in FIG. 2 . The moulding 9 has a substantially circular exterior 10 . Formed within the moulding 9 is a cavity 11 , the cavity 11 being filled with air.
As can be understood from considering FIG. 2 , the form of the rim 6 of the frame is such that the rim 6 is off-set from the centre of the moulding 9 . The rim therefore does not obstruct a region which is located substantially centrally within the circular exterior 10 of the integral moulding 9 . The cavity 11 occupies this space. The form of the rim 6 , with the two orthogonally extending arms 7 , 8 means that the effective centre of gravity of the rim is, however, at a point which is relatively close to the centre of the moulding 9 , as considered in section, as shown in FIG. 2 . The cavity 11 is positioned partially within a channel defined by the free ends of arms 7 , 8 .
The presence of the cavity 11 serves to minimise the overall weight of the steering wheel 1 , but the steering wheel still has the desired external dimensions.
The integral moulding 9 may optionally be provided with an outer layer 12 , as shown in FIG. 3 , formed of a material that is relatively soft or pliable to provide the steering wheel with the appropriate “feel”. Alternatively, the outer layer 12 covering the moulding 9 may be by an outer sleeve of leather or of wood (leather or wood outer sleeve is schematically shown as outer layer 12 in FIG. 3 for illustrative purposes only).
The cavity 11 may conveniently be created using a blow moulding technique.
FIGS. 4 to 6 illustrate a mould 20 which may be utilised to form a steering wheel such as the steering wheel 1 of FIG. 1 . The mould 20 comprises two co-operating mould parts 21 , 22 , although it is to be appreciated that in a modified embodiment of the invention a more complicated mould could be utilised. The two parts of the mould define a mould cavity 23 . The mould cavity 23 defines a mould portion 24 in which the rim 6 of the steering wheel is to be moulded, a portion 25 in which the parts of the moulding which surround the spokes are to be moulded, and a portion 26 dimensioned to accommodate solely the frame 2 of the steering wheel. The mould 20 is designed to touch the frame 2 of the steering wheel relatively tightly so that a plastics material may be injected into the mould and will form the integral moulding 9 , as desired, without providing any coating on the boss 3 of the frame 2 and without providing any coating on the parts of the spokes 5 which are closest to the boss 3 .
At the lower-most part of the mould (i.e. at the “6-o′clock” position of the rim) a retractable injector 27 is preferably provided. A single injector may be provided to inject both a molten plastics material and a propellant of compressed gas, compressed air or even a liquid such as water under pressure, although in a modified embodiment of the invention a plurality of injectors may be provided.
In alternative embodiments the injector may be fixed in position, not being retractable, and may be on a terminal part of an appropriately positioned spoke.
The mould 20 , in the preferred embodiment, is located at an appropriate orientation with regard to a surrounding force field which, in the described embodiment, is the force field of gravity. The mould is thus located in an upright position so that the injector 27 is located at the lower-most part of the portion 24 of the mould cavity 23 which is to form the rim of the steering wheel.
The frame 2 is located within the mould. The frame 2 may be spaced from certain parts of the mould by spacer elements. The spacer elements may be formed on the mould 20 or may be formed on the frame, or may be spacer elements which are inserted into the mould simultaneously with the frame.
Molten plastics material is injected into the lower part of the mould cavity 23 through the injector 27 . The plastics material is injected into the cavity at a high temperature which may be in excess of 200° C. The plastics material may be injected such that the plastics material substantially half-fills the mould cavity 23 . The plastics material closest to the walls of the mould will, because the walls of the mould are cold, begin to cool and will solidify to form a solidified “tube” of plastic adjacent the wall of the mould, whilst the plastics material spaced further from the wall will remain in a fluid condition. Thus, when a portion of the rim 6 of the steering wheel 1 is considered in cross-section, as in FIG. 2 , the plastics material of the integral moulding 9 adjacent the periphery of the circular exterior 10 will be solidified whilst the plastics material in the central region, corresponding to the position of the cavity 11 , will still be liquid or fluid.
A propellant in the form of a compressed air, compressed gas or even a fluid such as water may then be injected through the injector 27 . The propellant will not displace the already partially solidified plastics material adjacent the walls of the mould, but will displace the still-molten plastics material which is not in contact with the walls of the mould. This material will thus be forced, as a slug of fluid material, through the mould cavity until the material emerges into the upper part of the mould cavity 23 . The molten material will then come into contact with the walls of the mould forming the upper part of the mould cavity and will solidify when in contact with those walls, leaving the cavity 11 defined through the moulding 9 .
When the moulding process is complete, the injector 27 is withdrawn from the cavity and the complete steering wheel 1 is removed from the cavity 23 . If water was injected into the mould cavity as the propellant, the water will drain out of the steering wheel as it is removed from the mould, and the cavity 11 within the rim may then be sealed. If gas or air was used as the propellant, the cavity 11 may simply be sealed.
The resultant steering wheel 1 has a weight equivalent to the weight of a steering wheel fabricated using polyurethane foam. The steering wheel may be manufactured relatively cheaply and may be manufactured in many different designs. The steering wheel may be manufactured using only recyclable materials, and it may be possible to utilise the process of the invention with an overall cost reduction and an overall man power reduction.
In the preferred embodiment the force field of natural gravity is utilised. In a modified embodiment the mould could be placed on a centrifuge and the force field of centrifugal force could be utilised.
While the above description constitutes the preferred embodiment of the present invention, it will be appreciated that the invention is susceptible to modification, variation, and change without departing from the proper scope and fair meaning of the accompanying claims. | A steering wheel ( 1 ) has spokes ( 5 ) extending outwardly from a boss ( 3 ) to a rim ( 6 ). The rim has an inner frame ( 6 ) with an integrally moulded plastics coating ( 9 ) which has an internal cavity ( 11 ). The presence of the cavity minimises the overall weight of the steering wheel. The cavity is formed by initially injecting hot plastics material into a substantially vertical mould and subsequently blowing air into the lower part of the mould after some of the plastic adjacent the mould of walls has cooled. | 8 |
This is a Division of application Ser. No. 08/550,285 filed Oct. 31, 1995 now U.S. Pat. No. 5,709,335, which is a File Wrapper Continuation of application Ser. No. 08/261,167, filed Jun. 17, 1994, now abandoned.
FIELD OF THE INVENTION
The invention relates generally to surgical stapling appliances and more particularly to an improved apparatus and method for the anastomotic surgical stapling of luminal organs, such as vascular lumens.
BACKGROUND OF THE INVENTION
Various instruments are known in the prior art for end-to-end and end-to-side anastomotic surgical stapling together of parts of the alimentary canal (i.e., esophagus, stomach, colon, etc.). These instruments employ staple cartridges, generally in the shape of a hollow cylinder, of different sizes to accommodate tubular organs of varying diameters. End-to-end and end-to-side anastomoses are achieved by means of at least one ring of surgical staples.
The traditional technique for surgical stapling anastomosis is to position the stapling cartridge within the tubular organ to be stapled. The cut end of the tubular organ is inverted (i.e., folded inwardly) over the annular end of the staple cartridge creating an inverting anastomosis upon stapling. An essential requirement of the inverting anastomotic technique is the incorporation of knives within the staple cartridge housing to trim excess tissue from the anastomotic connection.
The prior art anastomotic stapling instruments form generally circular anastomotic connections, and have been largely limited to alimentary organs. With respect to end-to-side vascular anastomosis, circular connections, rather than an elliptical connections, are sometimes disadvantageous as they are less physiologic or natural. This unnatural connection may create turbulence in the blood flow as it courses through the anastomosis, damaging the intima (i.e., inner wall) of the blood vessel and predisposing it to forming blood clots.
In the present state of the art, end-to-end and end-to-side anastomosis between blood vessels have typically been accomplished by hand-sewn suturing techniques. These techniques are time consuming, not as reliable as stapling, and subject to greater human error than stapling. Current stapling instruments used for alimentary canal are not suitable, however, for vascular anastomosis due to their large sizes and inability to provide non-circular and low turbulence anastomoses. A typical prior art instrument has a circumference of approximately 8 cm (3 in), far too thick to accommodate coronary arteries and veins, which have circumferences ranging from 0.50 to 1.0 cm and from 1.5 to 2.5 cm, respectively.
An additional drawback of prior stapling instruments is the inability to provide an everted (i.e., folded outwardly) anastomosis. An inverted vascular anastomosis would expose the cut ends of the blood vessels to the vessel lumen and could lead to the formation of blood clots. For this reason, hand-sewn everted anastomoses for vascular connections are preferable, despite time and reliability drawbacks.
Accordingly, it is a general object of the present invention to provide an improved instrument and method for vascular anastomosis.
It is also an object of the present invention to provide a surgical stapling instrument small enough to accommodate vascular lumens.
Another object of the present invention is to provide a surgical stapling instrument for everted anastomosis.
Another object of the present invention is to provide a method for surgical stapling that does not require the removal of excess tissue from the anastomotical connection.
Still another object of the present invention is to provide an instrument and method for vascular anastomosis that is less time-consuming and more reliable than the prior art.
SUMMARY OF THE INVENTION
The present invention provides a novel instrument and method for vascular anastomoses which overcomes the drawbacks of prior art designs and achieves the aforesaid advantages.
Very generally, the surgical stapling instrument of the present invention is for stapling a tubular tissue structure having at least one distal end to a luminal structure, such as a vascular lumen or another tubular tissue structure. The instrument comprises a rod having a circumference sufficient to pass within the tubular tissue structure, an anvil mounted on the rod, and a generally tubular staple cartridge for containing a plurality of staples. The anvil has an array of staple deforming means theron and is of a size sufficient to pass through a surgically formed opening in and to be accommodated within the luminal structure. The inner passage of the staple cartridge is sufficient to axially accommodate the tubular tissue structure between the rod and the inner surface of the staple cartridge, and sufficient to allow the staple cartridge to be moved axially along the rod. The staple delivery end of the staple cartridge is positioned toward the staple deforming means of the anvil and has an outer dimension small enough so that the tubular tissue structure can be everted thereover. A clamping mechanism secures the everted portion of the tubular tissue structure and the luminal structure adjacent to the sugically formed opening between the staple cartridge and the anvil. A plurality of staples may then be ejected to pass through the everted portion of the tubular tissue structure and the luminal structure to engage the staple deforming means to deform the staples and create a bond between the tubular tissue structure and the luminal structure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary side elevation view, in cross section, of one embodiment of the anastomosis device constructed in accordance with the present invention and illustrating an end of the tubular tissue structure everted over the device end.
FIG. 2 is a front elevation view, in cross-section, of the anastomosis device taken substantially along the plane of the line 3--3 in FIG. 1.
FIG. 3 is a rear elevation view, in cross-section, of the anastomosis device taken substantially along the plane of the line 2--2 in FIG. 1
FIG. 4 is a side elevation view, in cross-section, of the anvil of the anastomosis device taken substantially along the plane of the line 4--4 in FIG. 3
FIG. 5 is a front elevation view, in cross-section, of an alternative embodiment of FIG. 3 illustrating a teardrop-shaped configuration.
FIG. 6 is a rear elevation view, in cross-section, of the anvil of the alternative embodiment of FIG. 5 taken substantially along the plane of the line 2--2 in FIG. 1
FIG. 7 is an exploded top perspective view, partially cut-away, of the anastomosis device of FIG. 1.
FIG. 8 is an enlarged, exploded, top perspective view, partially cut-away, of a staple cartridge assembly of the anastomosis device of FIG. 1.
FIG. 9 is an enlarged, side elevation view, in cross-section, of the anvil and staple cartridge assembly of the anastomosis device of FIG. 1 illustrating the deformation of a staple.
FIGS. 10-12 is a sequence of top perspective views illustrating the loading of a tubular tissue structure in the anastomosis device of FIG. 1
FIG. 13 is an enlarged, side elevation view, in partial cross-section, showing the positioning of the anvil of the anastomosis device through a luminal structure.
FIG. 14 is a reduced top perspective view of the anastomosis device of FIG. 1 mounted to the luminal structure.
FIG. 15 is a reduced top perspective view of the tubular tissue structure anastomotized to the luminal structure using the anastomosis device of FIG. 1.
FIG. 16 is a front elevation view of a grafted tubular tissue structure anastomotized to a coronary artery of the heart through the anastomosis device of FIG. 1.
FIG. 17 is an exploded top perspective view of an alternative embodiment of the anastomosis device of the present invention.
FIG. 18 is a fragmentary, enlarged top perspective view of a staple cartridge assembly of the alternative embodiment anastomosis device of FIG. 17.
FIG. 19 is an end view of the staple cartridge assembly of FIG. 18.
FIGS. 20-22, 24, 25, 27 and 28 is sequence of top perspective views illustrating the application of the alternative embodiment anastomosis device of FIG. 17 for proximal anastomosis of the grafted tubular tissue structure to the ascending aorta.
FIGS. 23 and 26 is a sequence of fragmentary, top perspective views illustrating the loading of a tubular tissue structure in the alternative embodiment anastomosis device of FIG. 17.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIGS. 1-7, there is shown a structural embodiment of the present invention which is best suited for anastomotic stapling of a tubular vessel having two distal or untethered ends. As will be evidenced by the detailed description below, this embodiment, i.e., distal stapler, is ideal for use during cardiopulmonary bypass surgery for making the primary anastomotic connection of a bypass vein to a coronary artery or to the aorta.
Referring now to FIG. 1, a portion 10 of the wholly configured distal stapler of the present invention, as shown in FIG. 7, comprises an elongated central rod 12 with anvil 14 mounted at its distal end 16. Anvil 14 is in the form of a circular, elliptical or tear drop-shaped disk and is mounted, by suitable means such as welding, to the end of central rod 12 transversely thereof and at the center of the anvil. The edges of anvil 14 are beveled or otherwise generally rounded to enable anvil 14 to slip easily through incisions in vascular walls--much like a button through a button hole.
The central rod 12 has a circumference sufficient to permit the rod to axially extend through a tubular vessel, indicated in phantom at 20, to be stapled. Central rod 12 also axially extends within tubular housing 22, driver pins 24 and staple cartridge 26, together forming a contiguous shaft 28 having an inner circumference sufficient to accommodate tubular vessel 20 sandwiched between them and central rod 12. Staple cartridge 26 has an outer circumference sufficient to accommodate everted end 34 of tubular vessel 20. Lip 36 of cartridge 26 is tapered to facilitate eversion of tubular vessel 20. Anvil 14 has circumference of a size equivalent to the outer circumference of staple cartridge 16.
Circumferences of vascular vessels range from 0.50 to 1.0 cm for coronary arteries and from 1.5 to 2.5 cm for veins. Accordingly, all circumferences, discussed above, of stapler 10 are of a size to optimally coaxially accommodate the vein to be stapled.
The end of central rod 12 opposite anvil 14 is centrally mounted, preferably welded, on a cylindrical base 40 which extends coaxially within tubular housing 22 (as shown in FIG. 7 by reference number 106) and has a circumference sufficient to be slidable within tubular housing 22. The accommodated tubular vessel 20 extends along central rod 12 to cylindrical base 40. Provided on the surface of central rod 12 proximal to base 40 is circumferential groove 44 for facilitating the securing of tubular vessel 20 to rod 12 by means of string 46. Similarly, circumferential groove 48 and string 50 are provided to secure everted end 34 of vessel 20 to staple cartridge 26. An alternative embodiment of staple cartridge 26 for securing an everted vein comprises tiny hooks around the circumference at end 36 of the cartridge. Other suitable means for accomplishing the securing function may be used as well.
Referring now to FIG. 2, there is shown a cross-sectional view of stapler 10 of the present invention in the direction of arrows 2--2 of FIG. 1. Here, the staple delivery end 60 of a circular staple cartridge is illustrated encasing a circular array of staple delivery means or staple shafts 62. The present invention is not limited to a single staple shaft array, however. It is commonly known in the art to employ a plurality of concentric arrays or rows of staple shafts for anastomotic procedures. Extending from staple shaft array 62, is an array of narrow channels 68, each narrow channel corresponding to each staple shaft. Channel array 68 is used solely for manufacturing purposes and is not a necessary element of the invention. Central rod 64 and its base 66 are axially and centrally located within the cylindrical staple cartridge 60.
FIG. 3 shows the underside view of anvil 70 in the direction of arrows 3--3 of FIG. 1. The anvil 70 has an array 74 of means for deforming staples. Central rod attachment 72 is centrally located on anvil 70 which provides an array of staple deforming means 74, comprised here of an array of recess pairs, for bending staples projected from corresponding array of staple shafts 62 of the staple cartridge of FIG. 2.
Depicted in FIG. 4 is a cross-sectional view of anvil 70 in the direction of arrows 4--4 of FIG. 3. Each recess pair 76 is curved to bend staple legs radially inward. The projected staples can be made to bend radially inward or radially outward depending on the spacing 78 between the recess of each paired recess 76. Alternatively, each recess can be positioned orthogonal to its present position to bend the staple legs at right angles to their axis of projection.
Although the present invention is primarily described and depicted as forming staple bonds that are circular and as having component circumferences that are circular, other embodiments are realized for forming staple bonds having elliptical, tear drop or other generally oval circumferences. Accordingly, the anvil and associated staple recess array, and the cartridge housing and associated staple shaft array of these alternative stapler embodiments have circumferences in the shape of the desired staple bond. For example, FIGS. 5 and 6 illustrate an anvil and staple cartridge, respectively, having tear-drop shaped circumferences.
FIG. 5 shows a cross-sectional view of a tear-drop shaped staple cartridge. The staple delivery end 80 of the staple cartridge is llustrated encasing a tear drop array of staple delivery means or staple shafts 82. Extending from staple shaft array 82, is an array of narrow channels 84, each narrow channel corresponding to each staple shaft. Channel array 84 is used solely for manufacturing purposes and is not a necessary element of the invention. Central rod 86 and its base 88 are coaxially and centrally located within the cylindrical portion of dear drop staple cartridge 80.
FIG. 6 shows the underside view of a tear drop shaped anvil 90. Central rod attachment 92 is centrally located on the circular portion of anvil 90 which provides an array of staple deforming means comprised of recess pairs 94 for bending staples projected from corresponding array of staple shafts 82 of the staple cartridge of FIG. 5.
Referring now to FIG. 7, there is shown stapler 100 of the same embodiment depicted in FIGS. 1-4. A tubular housing 102 coaxially contains central rod 104 and rod base 106, the end of central rod 104 opposite that of anvil 114 being suitably mounted, such as by welding, to rod base 106 (connection not shown). Threadedly mounted to and extending perpendicular from rod base 106 is a short stem 108, positioned at approximately half the length of base 106. The top of stem 108 has cylindrical knob 110 transversely mounted. Stem 108 is moveable within narrow channel 112, cut within housing 102 and running parallel to the axis travelled by central rod 104 and rod base 106. Channel 112 limits the rotational movement of stem 108 and thereby maintains a proper radial orientation between anvil 114 and staple cartridge 116 during reciprocation.
Weldedly mounted to and protruding perpendicularly from cylindrical face 118 of housing 102 and paralleling rod 104 is cylindrical array of staple driver pins 120, all drivers pins being identical and each having the form of a solid parallelogram. Staple cartridge 116 encases, from end to end, cylindrical array of hollow staple shafts 122 which holds a plurality of preloaded staples (not pictured). All shafts 122 are identical and each has height and width dimensions such that a corresponding staple driver pin 120 is slidable therein.
In order to have an optimally functioning stapler, it is necessary to maintain a clean and clear passageway for central rod 104, base 106 and staple shafts 122. Accordingly, one embodiment of the present invention comprises a disposable cartridge which is disposed of and replaced after one anastomotic stapling. Another embodiment provides a slidable sleeve around the driver pin array to prevent blood and tissue from getting caught therein.
For anastomosis to be successful, it is imperative not to injure the living tissue being stapled by overcompressing it between anvil 114 and staple cartridge 116 or by a staple bond that is exceedingly tight. Accordingly, overcompression of the tissue is prevented in the present invention by limiting the length of driver pins 120. Other embodiments are known in the prior art for accomplishing this objective. For example, U.S. Pat. No. 4,573,468 employs mutually coacting stops located on the inner surface of a tubular housing and on the surface of a coaxial rod to provide variable degrees of engagement between tissues to be stapled so as to ensure against overcompression of the tissue. A spring-loaded engagement between the rod and tubular housing is also applicable for the present invention. Other means suitable for this purpose will be aparent to those having ordinary skill in the art.
Finally, FIG. 7 illustrates threaded end 124 of rod base 106 which extends beyond the length of housing 102 to threadedly engage with cylindrical nut 126 which has internally threaded throughbore 128 extending the full length of cylindrical nut 126 to allow end 124 to exit therethrough.
FIGS. 8 and 9 illustrate the mechanical interaction between the staple driver, staple cartridge and anvil upon engagement. FIG. 8 illustrates staple driver array 200 mounted on face 202 of tubular housing 204 slidably engaged within staple shaft array 206 of staple cartridge 208. Staple array 210 is projected from staple cartridge 208 and through the tissues to be stapled (not shown). FIG. 9 shows a close-up of a staple being driven by driver pin 252 and projecting through cartridge 254 through tissues 256 and 258. The legs 260 and 262 of staple 250 then engage with and bend along the curved recesses 264 and 266, respectively, of anvil 268 to form a bond between tissues 256 and 258.
Referring now to FIGS. 10-16, with like numbers referring to like elements, there is illustrated the steps of the anastomotic procedure using the structural embodiment described above. Now referring to FIG. 10 specifically, the anvil-headed end of rod base 302 is inserted into transected vein 304 having a length in the range of 10-18 cm (4-7 inches). End 308 (the end to be stapled) of vein 304 is positioned proximate to anvil 306. Opposing end 310 of vein 304 is tied with string 312 to central rod 314 at a circumferential depression (not shown) proximate to base 302.
FIG. 11 shows the step of inserting central rod 314 with attached vein 304 into staple cartridge 318 and tubular housing 316 such that staple cartridge 318 is proximate to anvil 306. FIG. 12 illustrates the next several steps of the method of the present invention which can be performed in any order. The end of vein 304 is everted over staple cartridge 318 and tied with string 320 securing it to staple cartridge 318 (covered by vein 304). Threaded stem 322 of cylindrical knob 324 is threadedly engaged with a threaded bore (not shown) base 302, the bore being aligned with narrow channel 326. Cylindrical nut 328 is threadedly engaged with the threaded end 300. As indicated in FIG. 13, anvil 306 is positioned within lumen 330 of vascular artery 332 via incision 334. A cross-section of a portion of vein 304 is shown everted over the staple delivery end of staple cartridge 318.
In FIG. 14, central rod 314 (not visible) and rod base 302 (not visible) are optimally coaxially positioned within tubular housing 316 by means of sliding knob 324 along channel 326 toward vascular artery 332. Nut 328 is rotated in a clockwise direction to engage it with tubular housing 316 causing rod base 302 to become rigidly interconnected with nut 328. As the clockwise turning continues, rod base 302 is drawn through the bore in nut 328, bringing the staple cartridge 336 and anvil 306 within artery 332 together. An embodiment employing mutually coacting stops (not shown) would, at this point, be at the first coacting position or the "loaded" position. The clockwise motion is continued so that everted vein 304 engages with the wall of artery 332 and until the staple drivers (not visible) are actuated, driving the staples (not visible) through the tissues to create a bond 338 (FIG. 15). If mutually coacting stops are employed, the configuration would be in the "firing" position.
Finally, FIG. 16 illustrates heart 350 having aorta 352, pulmonary artery 354, right atrium 356, right ventricle 358, left ventricle 360, left atrial appendage 362, right coronary artery 364, left anterior descending artery 368, and diagonal artery 370. Here, vein 304 has been anastomotically stapled to left anterior descending artery 368.
To complete the anastomotic procedure of the bypass vein 304, the unstapled end of the anastomotized vein 304 must now be connected to aorta 352. However, another structural embodiment of the present invention, referred to as the "proximal" stapler, is needed since the embodiment described above, i.e., the "distal" stapler, requires the vein to have two distal or untethered ends. Accordingly, FIGS. 17-28 describe a structure and method thereof for a second embodiment of the present invention which is suited for the anastomotic stapling of a tubular vessel having only one distal end, the other end having already been anastomotically stapled.
Referring now to FIGS. 17-19, with like numbers referencing like elements, there is shown anastomotic stapler 400 having handle 402 with elongated vessel rod 404 and elongated driver rod 406 mounted perpendicularly to handle face 408 and parallel to each other, both being of approximately the same length. Vessel rod 404 has a centrally mounted generally circular anvil 410. Vessel rod 404 has a circumference sufficient to coaxially accommodate a tubular vessel (not shown) to be stapled to the aorta. Driver rod 406, having threaded end 412 and handle 414, extends through bore 416 of handle 402.
Stapler 400 also comprises staple cartridge 418, enlarged in FIG. 18 for purposes of describing its detail. Referring then to FIG. 18, there is shown the staple cartridge of FIG. 17 in its open position having top and bottom units 420 and 422, respectively. Units 420 and 422 are engaged at one side by hinge 424 which allows cartridge 418 to be opened and closed. Staple cartridge 418 has two parallel bores 426 and 428 with inner circumferences sufficient to coaxially accommodate vessel rod 404 with a coaxially accommodated vein (not shown) and driver rod 406, respectively. Staple delivery end 430 extends from staple cartridge 418 along the axis of bore 426 to accommodate the everted end of a vein to be stapled. Bore 428 is internally threaded to be threadedly engagable with driver rod end 412.
For a proper fit between units 420 and 422, a detent-recess pair is provided having detent 432 extending from inner surface 434 of top unit 420 which mates with recess 436 within inner surface 438 of bottom unit 422. To secure closing, a curved clip 440 is provided to fit around cylindrical casing 442 of bore 428.
When in a closed position, staple cartridge 418 has cylindrical staple delivery means or staple shaft array (not shown) encased in staple delivery end 430 which mates with cylindrical driver pin array 444 mounted on driver 446. Both the hollow shafts and the solid driver pins have height and width measurements that allow them to be slidably engageable with each other. Driver 446 is slidable along surface 448 of top unit 420 and surface 450 of bottom unit 422 to the point of engagement with shoulder 452 of top unit 420 upon which driver pin array 444 becomes engaged within the staple shaft array, projecting preloaded staples from the end of staple delivery end 430. Shoulder 452 limits the engagement of driver pin array 444 so that the tissue being stapled is not overcompressed. Modifications of the this embodiment can employ mutually coacting stops or spring-loaded type configurations between the driver and staple cartridge to prevent against overcompression of the tissue.
FIG. 19 shows a front view of staple cartridge 418 in its closed position with top unit 420 engaged with bottom unit 422. Clip 440 securely fits around cylindrical casing 442. Staple deforming end or staple shaft array 454 is shown on the face of staple delivery end 430.
FIGS. 20-28, with like numbers referencing like elements, depict the various steps of the anastomotic procedure using the structural embodiment in FIGS. 17-19 described above. Referring now to FIG. 20, vessel rod 500 is inserted through aorta 502 of heart 504 via incisions 506 and 508 on opposing walls of aorta 502 such that anvil 510 is centrally positioned within aorta 502.
In FIG. 21, the end of vessel rod 500 is then inserted into the distal end of vein 512 with anvil 510 still centrally positioned within aorta 502. Next, as shown in FIG. 22, vessel rod 500 with accommodated vein 512 is positioned within the corresponding bore 514 in open staple cartridge 516. Rod 500 and vein 512 should be positioned such that a sufficient length of distal end 518 of vein 512 extends beyond the end of cartridge 516 such that distal end 518 can be everted over cylindrical sleeve 520 of cartridge 516 (See FIG. 23). Once vein 512 has been optimally positioned, staple cartridge 516 is clamped around it and secured with clip 522, illustrated in FIG. 24. Now, distal end 518 of vein 512 is everted over sleeve 520 and is securely tied with string 524.
Referring now to FIG. 25, driver rod 526 is slid into bore 528 of handle 530 and then threadedly engaged with bore 532 of staple cartridge 516. FIG. 26 shows a close-up of staple cartridge 516 as it appears in its closed position.
Moving now to FIG. 27, there is shown driver handle 534 rotated in a clockwise direction, bringing together anvil 510 and cylindrical sleeve 520. The clockwise rotation is continued until the aorta wall 502 is engaged with the distal end 518 of vein 512 upon which the staple driver pins (not visible) are fully engaged within each of the corresponding staple shafts (not visible), driving the staples (not visible) through the engaged tissue to create anastomotic bond 536 between aorta 502 and vein 512 (See FIG. 28).
It will be understood that the foregoing is only illustrative of the principles of the present invention, and that various modifications can be made by those skilled in the art without departing from the scope and spirit of the invention. For example, the particular stapler structural configurations shown are not critical and other configurations can be used if desired. One possible alternative for the configuration illustrated in FIG. 17 is to have a vessel rod that is retractable (e.g., by means of a telescoping rod). In addition, the vessel rod of this alternative embodiment can be curved to facilitate the anastomotic procedure if necessary. Also, the structure and method of the present invention can be employed thoracoscopically.
Accordingly, it is intended that the appended claims will cover any such modifications or embodiments that fall within the scope of the invention. | A surgical stapling instrument for stapling a tubular tissue structure having at least one distal end to a luminal structure, such as a vascular lumen or another tubular tissue structure. The instrument comprises a rod having a circumference sufficient to pass within the tubular tissue structure, an anvil mounted on the rod, and a generally tubular staple cartridge for containing a plurality of staples. The anvil has an array of staple deforming theron and is of a size sufficient to pass through a sugically formed opening in and to be accommodated within the luminal structure. The inner passage of the staple cartridge is sufficient to axially accommodate the tubular tissue structure between the rod and the inner surface of the staple cartridge, and sufficient to allow the staple cartridge to be moved axially along the rod. The staple delivery end of the staple cartridge is positioned toward the staple deforming of the anvil and has an outer dimension small enough so that the tubular tissue structure can be everted thereover. A clamping mechanism secures the everted portion of the tubular tissue structure and the luminal structure adjacent to the sugically formed opening between the staple cartridge and the anvil. A plurality of staples may then be ejected to pass through the everted portion of the tubular tissue structure and the luminal structure to engage the staple deforming to deform the staples and create a bond between the tubular tissue structure and the luminal structure. The staple cartridge and/or anvil may be configured to provide a non-circular anastomotic connection having more natural, less turbulent blood flow therethrough. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Application No. 62/209,814 filed Aug. 25, 2015, the entire contents of which is incorporated herein by reference.
BACKGROUND
[0002] The present disclosure relates to electromagnetic propulsion systems, and more particularly to propulsion systems having wireless power transfer systems.
[0003] Electromagnetic propulsion systems operate to move a first structure relative to a stationary second structure generally through magnetic levitation. Without tethers, it is difficult to provide on-board power to the moving first structure.
[0004] Self-propelled elevator systems, as one non-limiting example, may utilize such magnetic propulsion systems. Such ropeless elevator systems are useful in certain applications (e.g., high rise buildings) where the mass of the ropes for a roped system is prohibitive and/or there is a need for multiple elevator cars in a single hoistway. Elevator cars typically need power for ventilation, lighting systems, operation of doors and brakes, control units, communication units and to recharge batteries installed, for example, on an elevator car controller. Moreover, elevator cars may require back-up systems in case of a power failure. Existing systems use moving cables or current collectors/sliders to connect a moving elevator car with power lines distributed along the elevator hoistway.
SUMMARY
[0005] An electromagnetic propulsion system according to one, non-limiting, embodiment of the present disclosure includes a plurality of primary windings; a permanent magnet arranged to move with respect to the plurality of primary windings; a secondary winding disposed in a non-moving relationship with the permanent magnet; and an excitation energy applied to the plurality of primary windings for creating a magnetic field including a base component and low frequency harmonic components, and wherein the base component substantially contributes toward motion between the plurality of primary windings and the permanent magnet and the low frequency harmonic components contributes toward generating an electro-motive force in the secondary winding based on displacement between the plurality of primary windings and the permanent magnet.
[0006] Additionally to the foregoing embodiment, the magnetic field includes a high frequency component that contributes toward generating the electro-motive force in the secondary winding and based on variation with respect to time.
[0007] In the alternative or additionally thereto, in the foregoing embodiment, the permanent magnet and the secondary winding are carried by an elevator car which is propelled in response to the excitation energy.
[0008] In the alternative or additionally thereto, in the foregoing embodiment, the low frequency harmonics component and the high frequency component are used to transfer electrical power from the plurality of primary windings to the elevator car through the secondary winding.
[0009] In the alternative or additionally thereto, in the foregoing embodiment, the electromagnetic propulsion system is a linear electromagnetic motor.
[0010] In the alternative or additionally thereto, in the foregoing embodiment, the electromagnetic propulsion system is a compound motion electromagnetic motor.
[0011] An elevator system according to another, non-limiting, embodiment includes an elevator car arranged to move along a hoistway defined by a structure; an electrically powered subsystem carried by the elevator car; a plurality of primary windings engaged to the structure and positioned along the hoistway; a permanent magnet coupled to the elevator car, the plurality of primary windings and the permanent magnet configured to impart motion to the elevator car; an excitation energy applied to the plurality of primary windings for creating a magnetic field including a base component and a low frequency harmonics component, and wherein the base component substantially contributes toward the motion of the elevator car; and a secondary winding coupled to the elevator car and disposed adjacent to the permanent magnet, and wherein the low frequency harmonics component generates an electro-motive force in the secondary winding based on displacement between the plurality of windings and the elevator car for providing electrical power to the electrically powered subsystems.
[0012] Additionally to the foregoing embodiment, the magnetic field includes a high frequency component that contributes toward generating the electro-motive force in the secondary winding and based on variation with respect to time.
[0013] In the alternative or additionally thereto, in the foregoing embodiment, the electrically powered subsystem includes at least one of a battery, a ventilation unit, a lighting system, door operation unit, brake unit, display unit, a control unit, and a communication unit.
[0014] In the alternative or additionally thereto, in the foregoing embodiment, the elevator system includes a controller configured to sequentially control the energization of the plurality of primary windings.
[0015] In the alternative or additionally thereto, in the foregoing embodiment, the elevator system is ropeless.
[0016] In the alternative or additionally thereto, in the foregoing embodiment, the elevator system includes a power converter disposed in the elevator car and configured to convert an induced voltage and current from the secondary winding to suitable AC or DC voltage and current.
[0017] The foregoing features and elements may be combined in various combinations without exclusivity, unless expressly indicated otherwise. These features and elements as well as the operation thereof will become more apparent in light of the following description and the accompanying drawings. However, it should be understood that the following description and drawings are intended to be exemplary in nature and non-limiting.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Various features will become apparent to those skilled in the art from the following detailed description of the disclosed non-limiting embodiments. The drawings that accompany the detailed description can be briefly described as follows:
[0019] FIG. 1 depicts a multicar elevator system in an exemplary embodiment;
[0020] FIG. 2 is a top down view of a car and portions of a linear propulsion system in an exemplary embodiment;
[0021] FIG. 3 is a schematic of the linear propulsion system;
[0022] FIG. 4 is a schematic of the elevator system with a wireless power transfer system;
[0023] FIG. 5 is a graph of total excitation currents;
[0024] FIG. 6 is a graph of base frequency and high frequency components of the total excitation currents in FIG. 5 ;
[0025] FIG. 7 is a graph of a field produced by the high frequency components;
[0026] FIG. 8 is a block diagram illustrating magnetic field components produced by energized primary windings of the propulsion system; and
[0027] FIG. 9 is a schematic of a second embodiment of a propulsion system with a wireless power transfer system.
DETAILED DESCRIPTION
[0028] The following patent applications assigned to the same assignee and filed on the same day as the present disclosure are herein incorporated by reference in their entirety (identified via docket numbers: 79766US01 (U320411US); 78887US01 (U320410US); 78800US01 (U320415US); and 77964US01 (U320409US).
[0029] FIG. 1 depicts a self-propelled or ropeless elevator system 20 in an exemplary embodiment that may be used in a structure or building 22 having multiple levels or floors 24 . Elevator system 20 includes a hoistway 26 having boundaries defined by the structure 22 and at least one car 28 adapted to travel in the hoistway 26 . The hoistway 26 may include, for example, three lanes 30 , 32 , 34 each extending along a respective central axis 35 with any number of cars 28 traveling in any one lane and in any number of travel directions (e.g., up and down). For example and as illustrated, the cars 28 in lanes 30 , 34 , may travel in an up direction and the cars 28 in lane 32 may travel in a down direction.
[0030] Above the top floor 24 may be an upper transfer station 36 that facilitates horizontal motion to elevator cars 28 for moving the cars between lanes 30 , 32 , 34 . Below the first floor 24 may be a lower transfer station 38 that facilitates horizontal motion to elevator cars 28 for moving the cars between lanes 30 , 32 , 34 . It is understood that the upper and lower transfer stations 36 , 38 may be respectively located at the top and first floors 24 rather than above and below the top and first floors, or may be located at any intermediate floor. Yet further, the elevator system 20 may include one or more intermediate transfer stations (not illustrated) located vertically between and similar to the upper and lower transfer stations 36 , 38 .
[0031] Referring to FIGS. 1 through 3 , cars 28 are propelled using a linear propulsion system 40 having at least one, fixed, primary portion 42 (e.g., two illustrated in FIG. 2 mounted on opposite sides of the car 28 ), moving secondary portions 44 (e.g., two illustrated in FIG. 2 mounted on opposite sides of the car 28 ), and a control system 46 (see FIG. 4 ). The primary portion 42 (i.e. stator) includes a plurality of windings 48 mounted at one or both sides of the lanes 30 , 32 , 34 in the hoistway 26 . Each secondary portion 44 may include two rows of opposing permanent magnets 50 A, 50 B mounted to the car 28 . Primary portion 42 is supplied with drive excitations from the control system 46 to generate a magnetic flux that imparts a force on the secondary portions 44 to control movement of the cars 28 in their respective lanes 30 , 32 , 34 (e.g., moving up, down, or holding still). The plurality of windings 48 of the primary portion 42 are generally located between and spaced from the opposing rows of permanent magnets 50 A, 50 B. It is contemplated and understood that any number of secondary portions 44 may be mounted to the car 28 , and any number of primary portions 42 may be associated with the secondary portions 44 in any number of configurations.
[0032] Referring to FIG. 3 , the control system 46 may include power sources 52 , power converters 54 (e.g. motor or propulsion drives), buses 56 and a controller 58 . The power sources 52 are electrically coupled to the power converters 54 via the buses 56 . In one non-limiting example, the power sources 52 may be direct current (DC) or alternating current (AC) power sources. DC power sources 52 may be implemented using storage devices (e.g., batteries, capacitors), and may be active devices that condition power from another source (e.g., rectifiers connected to power grid, generators, etc.). The power converters 54 may receive DC or AC power from the buses 56 and may provide drive excitations to the primary portions 42 of the linear propulsion system 40 . Each power converter 54 may be a converter that converts DC or AC power from bus 56 to a multiphase (e.g., three phases illustrated in FIG. 3 , and two phases illustrated in FIG. 4 ) drive excitation provided to a respective section of the primary portions 42 . The primary portion 42 may be divided into a plurality of modules or sections, with each section associated with a respective power converter 54 .
[0033] The controller 58 provides control signals to each of the power converters 54 to control generation of the drive excitation. Controller 58 may use pulse width modulation (PWM) control signals to control generation of the drive excitations by the power converters 54 . Controller 58 may be implemented using a signal processor-based device programmed to generate the control signals. The controller 58 may be distributed as a part of each drive 54 to generate control signal for corresponding drive. The controller 58 may also be part of an elevator control system or elevator management system. Elements of the control system 46 may be implemented in a single, integrated module, and/or be distributed along the hoistway 26 .
[0034] Referring to FIG. 4 , a wireless power transfer system 60 of the elevator system 20 may be used to power loads or elevator car subsystems 62 in or on the elevator car 28 . The power transfer system 60 may be an integral part of the control system 46 thereby sharing various components such as the controller 58 (see FIG. 3 ), buses 56 , power source 52 , power converters 54 , primary portion(s) 42 and other components. The subsystems 62 may include batteries or energy storage devices, a ventilation unit, a lighting system, a door operation unit, brake unit, display unit, a control unit, a communication unit, and others. The subsystems 62 may be alternating current (AC) loads, such as fans of the ventilation unit and others, utilizing a traditional power frequency such as, for example, about 60 Hz. Alternatively, or in addition thereto, the subsystems 62 may include direct current (DC) loads, such as the display unit. The international patent application WO 2014/189492 published under the Patent Cooperation Treaty on Nov. 27, 2014, filed on May 21, 2013, and assigned to Otis Elevator Company of Farmington, Conn., is herein incorporated by reference in its entirety.
[0035] Referring to FIGS. 4 and 5 , the primary assembly 42 may include a plurality of primary windings 64 at a first phase and a plurality of primary windings 66 at a second phase offset from the first phase. The power converter 54 (e.g. switching power converter controlled with PWM) receives power from the power supply 52 and may convert the power to a predetermined base frequency, voltage, number of phases (two illustrated in FIG. 4 ) and controlled excitation current of the primary windings 64 , 66 . The energy from the converter 54 is outputted to the primary windings 64 , 66 . The total excitation current received by each primary winding 64 , 66 is illustrated in FIG. 5 . The mechanical propulsion is produced by the low frequency (i.e., base frequency) component of the excitation, which is generally at a low frequency that may be in a range of about 0 Hz to 100 Hz (i.e., wherein 0 Hz may be when the car is held at a stationary position by the excitation of the primary windings).
[0036] Generally inherent in the switching power converter 54 is the modulation of switches that may produce switching frequency ripple. The switching frequency ripple components are utilized by the wireless power transfer system 60 . More specifically and as best shown in FIG. 6 , the total excitation current (i x ) of the winding 64 may be broken down into a base frequency component (i xb ) at the low base frequency and a ripple or switching frequency component (i xs ) at a much higher excitation switching frequency (i.e. switching frequency ripple) that may be in a range of about 1 kHz to 100 kHz. Similarly, the total excitation current (i y ) of the winding 66 may be broken down into a base frequency component (i yb ) at the low frequency and a switching frequency component (i ys ) at the much higher excitation switching frequency. The base frequency components (i yb ) of the respective total excitation currents (i x ), (i y ) may generally be used by the propulsion system 40 to levitate and/or propel the elevator car 28 . The switching frequency components (i xs ), (i ys ) may be used by the wireless power transfer system 60 to power the elevator car loads 62 . Referring to FIG. 7 , a graph illustrates the probable resultant field produced by the switching frequency components (i xs ), (i ys ). Alternatively, or in addition to this excitation the primary winding can be supplied with a high frequency excitation, which is much greater than the base frequency but lower than the switching frequency, to transfer wireless power to the secondary.
[0037] The wireless power transfer system 60 may further include components generally in or carried by the elevator car 28 . Such components may include a secondary winding 68 configured to be induced with a voltage or current when the energized primary windings 64 , 66 are proximate thereto, a resonant component 70 that may be active and/or passive, and a power converter 72 . The secondary winding 68 may induce a current when the winding is proximate to the energized primary windings 64 , 66 , and may be induction based, or resonance based constructed to resonate generally at the frequency of the excitation switching ripple or at the harmonic components of the switching frequency ripple. Although not illustrated, the secondary windings 68 may have a pole pitch that is not equal to a pole pitch of the primary windings 64 , 66 . The secondary windings 68 of the power transfer system 60 may generally wrap about one or both of the permanent magnets 50 A, 50 B of the secondary portion 44 of the propulsion system 40 .
[0038] The resonant component 70 receives energy from the secondary winding 68 and may be passive or active. As a passive resonant component 70 , the component is generally a capacitor and capable of storing or operating on AC power. As an active resonant component 70 , the component 70 is configured to mitigate the effects of a weak or variable coupling factor (i.e., varies when the secondary winding 68 passes the primary windings 64 , 66 ). That is, the resonant component 70 may function to level-out the induced output current and voltage from the secondary winding 68 .
[0039] The power converter 72 in the elevator car 28 is configured to receive high frequency power from the resonant component 70 . The converter 72 may reduce the high frequency power to a suitable low frequency power (e.g., low power frequency of 60 Hz or other) that is compatible with AC loads 62 in the elevator car 28 . The converter 72 may further function to convert the high frequency power to DC power, which is then stored in an energy storage device (not illustrated). An example of an energy storage device may be a type of battery.
[0040] The ability to induce current in the secondary winding 68 at the high switching frequency (i.e., as oppose to low frequency) may optimize the efficiency of induced power transfer from the primary windings 64 , 66 to the secondary winding 68 . Moreover, the high switching frequency generally facilitates the reduction in size of many system components such as the secondary winding 68 , the resonant component 70 and the converter 72 amongst others. Reducing the size of components improves packaging of the system and may reduce elevator car 28 weight.
[0041] The secondary winding 68 may be designed and deployed such that the base frequency components (i xb ), (i yb ) do not create any variable field upon the secondary winding, and only the high switching frequency field (i.e. produced by converter switching) produces a varying field across the secondary winding to enable wireless power transfer. The elevator system 20 is highly reliable, safe, and is not limited by the mechanical and electrical limitations of a contact based power transfer system. The elevator system 20 may utilize existing excitation arrangements on the stationary side for the wireless power transfer function. Moreover, the system 20 may utilize the ripple components produced by the switching of the power converter 54 which may already exist in typical systems. The system 20 is relatively simple and robust, and may not require additional switching or modulation of the primary excitation, and additional power converter and winding on the stationary side of the system. The present disclosure may also be utilized for any information exchange between the stationary and moving sides.
[0042] Referring to FIG. 8 , a method of utilizing the wireless power transfer system 60 applies the theory of induction of electro-motive force due to the change of magnetic flux with respect to space and time. As previously described electrical power may be transferred wirelessly from the primary windings 44 , 46 to the secondary windings 68 by suitable excitation on the primary windings 44 , 46 . The total magnetic field (B TF ) 80 created by the energized primary windings may consist of three components: (1) a base component (B BF ) 82, (2) low frequency harmonic components (B LF ) 84, and (3) high frequency components (B HF ) 86 . The components 82 , 84 , 86 are expressed in the following equation:
[0000] B TF =B BF +B LF +B HF (1)
[0043] The base frequency harmonics component 82 interacts with the magnetic field of the permanent magnets 50 A, 50 B to create a force for propulsion. The low frequency harmonics component 84 creates an electro-motive mainly due to a change in position and may be expressed by the following equation:
[0000] e LF =dB LF /dx (2)
[0044] The high frequency component 86 creates an electro-motive force mainly due to its variation with respect to time, and can be expressed by the following equation:
[0000] e HF =dB HF /dt (3)
[0045] Therefore, the low frequency harmonics component 84 and the high frequency component 86 , created by the primary windings 44 , 46 may be utilized to transfer electrical power wireless to the elevator car 28 . In addition to the dynamic condition, under static conditions when the elevator car 28 is stationary, wireless power transfer may be achieved by modifying the base flux (eq. 1) and by utilizing the high frequency component 86 (eq. 3). The low frequency harmonic components 84 may be produced by using the combination of winding structure and excitation currents. Power transfer using low frequency harmonic components 84 may produce pulsating forces for set of primary and secondary windings. Such pulsating forces can be effectively cancelled on the car by proper phase displacement between the low frequency components in various sets of primary secondary winding. It is further contemplated and understood that the wireless transfer methods may be applicable to any type of electromagnetic dynamic system with linear, rotary and/or compound motions.
[0046] Low frequency harmonic components 84 for wireless power transfer can be created by using the combination of winding structure and excitation currents. Power transfer using low frequency harmonic components 84 may produce pulsating forces for set of primary and secondary windings. Such pulsating forces can be effectively cancelled on the car 28 by proper phase displacement between the low frequency harmonic components 84 in various sets of primary secondary winding.
[0047] Referring to FIG. 9 , a second embodiment of a propulsion system is illustrated wherein like components to the first embodiment have like element numbers except with the addition of a prime symbol suffix. A propulsion system 40 ′ may not be linear and instead may be a compound motion electromechanical motor that may include rotation (i.e. rotating motor), or a combination of rotary and linear motion. A wireless power transfer system 60 ′ may be integral to the propulsion system 40 ′. It is further contemplated and understood that the systems 40 ′, 60 ′ may not be limited to elevators and may be applied to any variety of applications that may require wireless power transfer to a moving structure 28 ′ from a stationary structure 22 ′.
[0048] While the present disclosure is described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the present disclosure. In addition, various modifications may be applied to adapt the teachings of the present disclosure to particular situations, applications, and/or materials, without departing from the essential scope thereof. The present disclosure is thus not limited to the particular examples disclosed herein, but includes all embodiments falling within the scope of the appended claims. | An electromagnetic propulsion system includes a plurality of primary windings and a permanent magnet arranged to move with respect to the plurality of primary windings. A secondary winding of the system is disposed in a non-moving relationship with the permanent magnet. An excitation energy is applied to the plurality of primary windings for creating a magnetic field that includes a base component and low frequency harmonic components. The base component substantially contributes toward motion between the plurality of primary windings and the permanent magnet and the low frequency harmonic components substantially contributes toward generating an electro-motive force in the secondary winding based on displacement between the plurality of primary windings and the permanent magnet. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to image forming apparatuses, such as copy machines, printers, facsimile machines, plotters, and multifunction peripherals (MFP) incorporating multiple image forming functions, such as copying and printing functions. More particularly, the present invention relates to an image forming apparatus having multiple image formation speed modes.
[0003] 2. Description of the Related Art
[0004] An image forming apparatus is known in which a low-speed mode or a high-speed mode can be selected by a user. In the low-speed mode, image quality may be given priority, while in the high-speed mode, speed (productivity) may be given priority. In this type of an image forming apparatus, a drive source, such as a motor, may be connected to an image carrier, such as a photosensitive drum, via a series of drive gears. When the gear ratio of the series of drive gears is fixed, the high-speed mode and the low-speed mode may be switched by varying the number of rotations of the drive source.
[0005] In this type of an image forming apparatus, noise may increase in the high-speed mode. The noise during an image formation operation is known to be largely due to the noise level of the gear meshing frequency of drive source gears. The gear meshing frequency is the number of times two gears mesh with each other per second. For example, the gear meshing frequency of a drive source is the number of times a motor gear and a transmission gear mesh with each other per second. Thus, the gear meshing frequency, and hence the noise level, can be reduced by decreasing the number of rotations of the motor in the drive source. Desirably, the gear meshing frequency should be lowered below 100 Hz because the sound of such frequencies is difficult for humans to hear.
[0006] The drive source in this type of image forming apparatus may include a so-called FG (frequency-generating) output motor equipped with a frequency generator. Typically, the FG output motor has a pattern of frequency-generating pulse shapes (“FG pattern”) disposed opposite a magnet of a rotating part of the motor. As the motor rotates, electromagnetic induction is caused between the magnet and the FG pattern, thereby producing a pulse current. Based on the pulse current, a feedback control is performed so that the rotating speed of the motor can be controlled (see Japanese Laid-Open Patent Application No. 09-46995, for example). The FG output motors are frequently used as a drive source for image forming apparatuses because of their inexpensive rotation control mechanism.
[0007] As mentioned above, the high-speed mode and the low-speed mode may be switched by changing the number of rotations of the drive source when the gear ratio the series of drive gears is fixed. In this case, when the rotation speed of the drive source in the high-speed mode is lowered in order to reduce the noise level of the gear meshing frequency of the drive source gears, the number of rotations for the low-speed mode also decreases because of the fixed gear ratio. As a result, the frequency generator may not be able to produce a sufficient level of pulse signal for the feedback control of the rotation speed of the motor.
[0008] Japanese Laid-Open Patent Application No. 2002-089638 discusses a drive apparatus including various motors, a simple planetary gear mechanism as an intermediate speed-reduction mechanism, and various speed-reduction units. In this drive apparatus, the motors and the speed-reduction units can be selectively engaged with the simple planetary gear mechanism on an input and an output end, respectively, in order to reduce vibration and noise.
[0009] Japanese Laid-Open Patent Application No. 2007-212806 discusses a rotating drive apparatus including a drive source, a series of gears, and a driven member. The gears are coupled via planetary gears for increasing accuracy of rotation of an output shaft and reducing the size in the shaft axial direction, while allowing the detachment of the driven member from the rotating drive apparatus.
SUMMARY OF THE INVENTION
[0010] In one aspect of the present invention, a swing gear mechanism includes a frame having a first and a second arch-shaped guide opening having a first end and a second end; a first swing gear supported by the frame with a shaft of the first swing gear being guided in the first arch-shaped guide-opening; a second swing gear supported by the frame with a shaft of the second swing gear being guided in the second arch-shaped guide opening; and a drive gear meshed with the first and the second swing gears and configured to rotate in a first or a second direction. The first swing gear and the second swing gear are displaced to the first end of the corresponding arch-shaped guide openings upon rotation of the drive gear in the first direction, or to the second end of the corresponding arch-shaped guide openings upon rotation of the drive gear in the second direction.
[0011] In another aspect of the present invention, an image forming apparatus includes the swing gear mechanism.
[0012] In yet another aspect of the present invention, an image forming apparatus has a high-speed mode and a low-speed mode and includes a drive source configured to be rotated in a first direction or a second direction; an image carrier configured to be rotated by the drive source; an optical scanning unit configured to scan the image carrier with a beam of light in order to form an electrostatic latent image on the image carrier; a developing unit configured to develop the electrostatic latent image on the image carrier into a visible image; a transfer unit configured to transfer the visible image onto a recording medium directly or indirectly; and a speed switch unit configured to select the high-speed mode or the low-speed mode by switching a rotation direction of the drive source. The speed switch unit includes a drive gear attached to a rotating shaft of the drive source; a first drive gear series configured to transmit a rotating power of the drive source upon rotation in the first direction to the image carrier; and a second drive gear series configured to transmit a rotating power of the drive source upon rotation in the second direction to the image carrier, the second drive gear series having a larger reduction ratio than the first drive gear series. The speed switch unit is configured to cause the drive gear to be selectively connected to the first drive gear series or the second drive gear series depending on the rotating direction of the drive source.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 illustrates a laser color printer as an image forming apparatus according to an embodiment of the present invention;
[0014] FIG. 2 illustrates a drive mechanism of the laser color printer in a high-speed mode;
[0015] FIG. 3A illustrates a swing-gear mechanism in the drive mechanism of the laser color printer;
[0016] FIG. 3B illustrates an assembly of a motor (drive source) and the swing-gear mechanism;
[0017] FIG. 4 illustrates the drive mechanism of the laser color printer according to the present embodiment in a low-speed mode;
[0018] FIG. 5 is a graph indicating torque sound pressure level with respect to the number of rotations of the drive source; and
[0019] FIG. 6 illustrates a drive mechanism according to a conventional technology.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] FIG. 1 illustrates a laser color printer 100 as an image forming apparatus according to an embodiment of the present invention. In the laser color printer 100 , photosensitive drums (image carriers) 20 Y (yellow), 20 M (magenta), 20 C (cyan), and 20 K (black) are disposed side by side along an extended surface of an intermediate transfer belt 21 which is supported by support rollers 102 a , 102 b , and 102 c . The laser color printer 100 further includes an optical scan unit 105 (exposure unit); charging units (not shown), developing units 106 Y, 106 M, 106 C and 106 K; a primary transfer roller (not shown) disposed inside the intermediate transfer belt 21 ; a cleaning unit (not shown); and a neutralizing unit (not shown).
[0021] The optical scan unit 105 is configured to emit laser beams L 1 , L 2 , L 3 , and L 4 in accordance with image information signals for the various colors. The laser beams L 1 , L 2 , L 3 , and L 4 hit the photosensitive drums 20 Y, 20 M, 20 C, and 20 K, thereby forming electrostatic latent images of the various color components on the photosensitive drums 20 Y, 20 M, 20 C, and 20 K. The latent images are thereafter rendered into visible toner images by the developing units 106 Y, 106 M, 106 C, and 106 K, as well known in the art.
[0022] The toner images of the various colors are successively transferred onto the intermediate transfer belt 21 , forming an overlaid color image. The overlaid image is then transferred onto a transfer sheet 120 (recording medium) by the secondary transfer roller 102 d . The transfer sheet 120 is fed from the sheet-feeding cassette 111 at a predetermined timing. Thereafter, the intermediate transfer belt 21 is cleaned by the cleaning unit. The transfer sheet 120 with the color image transferred thereon is transported to the fusing unit 114 where the color image is fused onto the transfer sheet 120 using heat and pressure. The fused transfer sheet is then ejected onto an ejected sheet tray 110 .
[0023] FIG. 2 illustrates a drive mechanism 1 for the image forming apparatus 100 . In FIG. 2 , the intermediate transfer belt 50 (indicated by broken lines) is supported across belt gears 36 and 15 , which are integrally formed with the support rollers 102 a and 102 b , respectively. The drive mechanism 1 includes a drive gear 3 for driving the photosensitive drum 20 K and a drive gear 5 for driving the color photosensitive drums 20 Y, 20 M, and 20 C. The drive gears 3 and 5 are fixed to rotating shafts 6 a of FG-output-type motors 6 (drive source), as will be described below.
[0024] The drive gear 3 is meshed with a speed-reduction gear 7 . The speed-reduction gear 7 is meshed with a drum gear 9 that is integral with the photosensitive drum 20 K. The speed-reduction gear 7 is also meshed with a speed-reduction gear 11 . The speed-reduction gear 11 is coupled with a belt gear 15 via an idler gear 13 . The belt gear 15 is integral with the support roller 102 b . Rotation of the motor 6 for the drive gear 3 in counter-clockwise direction (“second direction”) causes the drum gear 9 to rotate in a direction indicated by the corresponding arrow (counter-clockwise direction) via the speed-reduction gear 7 . At the same time, the belt gear 15 is caused to rotate in a direction indicated by the corresponding arrow (clockwise direction).
[0025] The drive gear 5 for driving the color photosensitive drums 20 Y, 20 M, and 20 C is meshed with swing gears 17 and 19 . The swing gear 17 is engageable with a speed-reduction gear 21 . The other swing gear 19 is engageable with a speed-reduction gear 22 meshed with the speed-reduction gear 21 . The speed-reduction gear 21 is also meshed with a drum gear 23 that is integral with the photosensitive drum 20 M. Idler gears 25 and 27 are meshed with the speed-reduction gear 21 on an input end. The idler gear 25 is further engaged with a drum gear 31 via a speed-reduction gear 29 . The drum gear 31 is integral with the photosensitive drum 20 Y. The idler gear 27 is also engaged with a drum gear 35 via a speed-reduction gear 33 . The drum gear 35 is integral with the photosensitive drum 20 C.
[0026] The belt gear 36 is integral with the support roller 102 a ( FIG. 1 ). Toner supply units 38 Y, 38 M, 38 C, and 38 K are configured to supply the various colors of toner to the developing unit 106 Y, 106 M, 106 C, and 106 K. The speed-reduction gear 22 is disposed above a center line of the photosensitive drum 20 M (magenta); namely, the drum gear 23 . In this way, the space between the photosensitive drums 20 M and 20 C and additionally defined by the toner supply unit 38 C, for example, can be effectively utilized for a structure (including the swing gears 17 and 19 and guide openings 43 and 45 ) for enabling the switching between the high-speed mode and the low-speed mode, as will be described later.
[0027] FIG. 3A illustrates a swing-gear mechanism, and FIG. 3B illustrates an assembly of the FG-output-type motor 6 , the drive gear 5 , and the swing gears 17 and 19 . The FG-output-type motor 6 to which the drive gear 5 is fixed may include a frequency generator for detecting a rotation speed by an electromagnetic pattern generating method. The electromagnetic pattern generating method may involve generating a pulse signal using an electromagnetic pattern (rotation speed detecting unit) disposed between a rotating part and a fixed part (which are not illustrated) of the motor 6 when the motor 6 rotates by a predetermined angle. The time interval of generation of such pulse signals may be detected as a speed and supplied for a feedback control.
[0028] Referring to FIG. 3B , the motor 6 is supported on a motor circuit board 37 (drive source fixing unit) and a frame 39 . On the motor circuit board 37 , there may be formed the FG pattern as a part of the aforementioned electromagnetic pattern. The swing gears 17 and 19 are supported between the frame 39 and another frame 41 having the guide openings 43 and 45 in them. The swing gears 17 and 19 are movable in the guide openings 43 and 45 . The swing gears 17 and 19 are pressurized in a thrust direction by thrust springs 47 and 49 . The gears 17 and 19 are integral with shafts that are movable in the guide openings 43 and 45 . The guide openings 43 and 45 have a smooth arc shape so that the shafts of the gears 17 and 19 can smoothly move therein. The ends of the guide openings 43 and 45 have a shape conforming to the circumferential surface of the shafts of the swing gears 17 and 19 .
[0029] When the motor 6 rotates in one direction or the other, the swing gears 17 and 19 are displaced in the guide openings 43 and 45 by a pressing force provided by the rotation of the motor 6 , so that the swing gears 17 and 19 rotate with their shafts abutted against one or the other end of the guide openings 43 and 45 . FIG. 3A illustrates the case where the swing gear 17 is displaced to the right while the swing gear 19 is displaced to the left with reference to the drawing in a swinging motion when the motor 6 rotates in counter-clockwise direction (“second direction”) in the low-speed mode.
[0030] On the other hand, in the high-speed mode, the motor 6 rotates in clockwise direction (“first direction”) with reference to FIGS. 2 and 3 , for example. In this case, the swing gear 17 is displaced to the left and meshed with the speed-reduction gear 21 as illustrated in FIG. 2 , so that the color photosensitive drums 20 M, 20 Y, and 20 C are rotated at high speed. In this case, the swing gear 17 , the speed-reduction gear 21 , and the drum gear 23 constitute a first drive gear series for the high-speed mode, the swing gear 17 being the most upstream gear. The swing gear 19 , the speed-reduction gear 22 , the speed-reduction gear 21 and the drum gear 23 constitute a second drive gear series (for the low-speed mode), with the swing gear 19 being the most upstream gear.
[0031] When the motor 6 rotates in the first (clockwise) direction with reference to FIG. 2 , for example, the swing gear 19 is disengaged from the speed-reduction gear 22 , so that the second drive gear series is rendered incapable of transmitting drive power. Referring to FIG. 4 , when the motor 6 rotates in the second (counter-clockwise) direction for the low-speed mode, the swing gear 19 is meshed with the speed-reduction gear 22 , so that the color photosensitive drums 20 M, 20 Y, 20 C are rotated at a low speed. In the low-speed mode, the swing gear 17 is disengaged from the speed-reduction gear 21 , thus rendering the first drive gear series incapable of transmitting drive power. The structure including the drive gear 5 , the first drive gear series, the second drive gear series, and the swing-gear mechanism may be hereafter referred to as a “speed switch unit”.
[0032] Table 1 below illustrates a specification of the drive mechanism 1 according to an embodiment of the present invention.
[0000]
TABLE 1
Torque of photosensitive drum and roller
0.5 N · m
102b
Number of photosensitive drums driven by
3
drive gear 5
Gear transmission efficiency
0.95
Rotation speed (rpm) of photosensitive
94.03
drum (high-speed mode)
Rotation speed (rpm) of photosensitive
47.02
drum (low-speed mode)
Rotation speed (rpm) of support roller
117.00
102b (high-speed mode)
Rotation speed (rpm) of support roller
58.50
102b (low-speed mode)
Number of teeth of drive gear 5
8
*The number of teeth of drive gear 5 may be selected depending on the cost of bar material prior to formation of teeth in it.
[0033] In accordance with the present embodiment, the number of rotations of the motor 6 in the high-speed mode may be set at 700 rpm, as illustrated in Table 2. 700 rpm is a relatively low speed that can be controlled by a FG-output-type motor and that satisfies the condition that the gear meshing frequency be below 100 Hz, which corresponds to the low-frequency sound that is hard for humans to hear. In this case, the gear meshing frequency is 93.3 Hz, indicating a sufficient decrease in noise.
[0034] In accordance with the present embodiment, in order to switch to the low-speed mode, the motor 6 is rotated in the second direction so that the motor 6 is engaged with the speed-reduction gear 21 via the swing gear 19 and the speed-reduction gear 22 . Thus, a lower rotation speed is achieved by increasing the reduction ratio compared to the case where the motor 6 is rotated in the first direction.
[0035] Thus, the difference in the number of rotations of the photosensitive drums between the high-speed mode and the low-speed mode is provided by varying the reduction ratio of the drive gear series while the number of rotations of the motor 6 is set at a constant value of 700 rpm, for example. In this way, two or more speed modes can be realized without changing the rotation speed of the motor 6 , so that the rotation speed of the motor 6 can be set to a low speed at all times that contributes to a decrease in noise. Thus, the gear meshing frequency of the drive gear 5 can be made lower than the low-frequency sound of 100 Hz in any of the multiple speed modes.
[0000]
TABLE 2
Drive gear
5 (for color drums)
3 (for (K) drum)
3 (for belt 50)
Gear
5→17→
5→19→22→
3→7→9
3→7→9
3→11→
3→11→
sequence
21→23
21→23
13→15
13→15
Speed mode
High
Low
High
Low
High
Low
Rpm of
700.0
700.0
1400.0
700.0
1400.0
700.0
drive
source
Gear ratio
7.4
14.9
14.9
14.9
12.0
12.0
Output (W)
18
9
13
6
13
6
Shaft
0.126
0.252
0.089
0.089
0.089
0.089
torque
(N · m)
Sound
50.0
49.0
53.0
49.0
53.0
49.0
pressure
level
(dBA)
Meshing
93.3
93.3
186.7
93.3
186.7
93.3
frequency
(Hz)
*Reduction ratio is the ratio of the numbers of rotation of the drive source to the photosensitive drum or the support roller.
[0036] Table 2 corresponds to a case where the aforementioned speed switch unit (including the drive gear, the first and the second drive gear series, and the swing-gear mechanism) is not applied to the drive gear 3 for the photosensitive drum 20 K (for black). However, in another embodiment of the present invention, the speed switch unit may be applied to the drive gear 3 for the photosensitive drum 20 K in the same way as for the color photosensitive drums 20 Y, 20 M, and 20 C for enhanced noise reduction purposes.
[0037] FIG. 5 is a graph indicating torque and sound pressure level with respect to the number of rotations (rpm). The initial rpm of “700” is the number of rotations in the high-speed mode. The second rpm of “700” is the number of rotations in the low-speed mode. In the low-speed mode, torque increases due to the increased reduction ratio. The corresponding values are shown in Table 3.
[0000]
Sound pressure level
rpm
Torque (N · m)
(dBA)
700.0 (High-
0.126
49.0
speed mode)
700.0 (Low-
0.252
50.0
speed mode)
1400.0
0.126
53.0
[0038] FIG. 6 illustrates a conventional drive mechanism in which the speed switch unit according to the foregoing embodiment of the present invention is not used. As illustrated, the drive gear 5 is directly meshed with the speed-reduction gear 21 . Thus, drive power from the drive source is transmitted by a series of drive gears including the drive gear 5 , the speed-reduction gear 21 , and the drum gear 23 in a fixed manner, so that the rotation direction of the motor 6 is fixed to the second direction (counter-clockwise direction).
[0039] In this conventional example, the number of rotations of the motor 6 in the low-speed mode may be fixed at 700 rpm while the high-speed mode may be provided by doubling the rotation speed of the motor 6 to 1400 rpm. In this case, in the high-speed mode, the gear meshing frequency of the drive gear 5 is 186.7 Hz as illustrated in Table 4 below, which is far above the low-frequency sound threshold of 100 Hz, resulting in a large noise level. If the rotation speed in the high-speed mode is lowered in order to reduce the noise, the decrease in rotation speed is directly reflected in the low-speed mode because of the fixed reduction ratio of the drive gear series. As a result, the rotation speed in the low-speed mode greatly decreases, making it impossible to control the FG-output-type motor 6 .
[0000]
TABLE 4
Drive gear
5 (for color drums)
3 (for (K) drum)
3 (for belt 50)
Gear
5→21→23
5→21→23
3→7→9
3→7→9
3→11→
3→11→
sequence
13→15
13→15
Speed mode
High
Low
High
Low
High
Low
Rpm of
1400.0
700.0
1400.0
700.0
1400.0
700.0
drive
source
Gear ratio
14.9
14.9
14.9
14.9
12.0
12.0
Output (W)
18
9
13
6
13
6
Shaft
0.126
0.126
0.089
0.089
0.089
0.089
torque
(N · m)
Sound
53.0
49.0
53.0
49.0
53.0
49.0
pressure
level
(dBA)
Meshing
186.7
93.3
186.7
93.3
186.7
93.3
frequency
(Hz)
*Reduction ration values may be in integers so that an image position error due to motor vibration can be cancelled.
[0040] Although this invention has been described in detail with reference to certain embodiments, variations and modifications exist within the scope and spirit of the invention as described and defined in the following claims.
[0041] The present application is based on Japanese Priority Application No. 2009-198660 filed Aug. 28, 2009, the entire contents of which are hereby incorporated by reference. | An image forming apparatus has a high-speed mode and a low-speed mode and includes a speed switch unit configured to select the high-speed mode or the low-speed mode by switching a rotation direction of a drive source. The speed switch unit includes a drive gear attached to a rotating shaft of the drive source; a first drive gear series transmitting a rotating power of the drive source upon rotation in a first direction to an image carrier; and a second drive gear series transmitting a rotating power of the drive source upon rotation in a second direction to the image carrier, the second drive gear series having a larger reduction ratio than the first drive gear series. The speed switch unit causes the drive gear to be selectively connected to the first drive gear series or the second drive gear series depending on the rotating direction of the drive source. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/022,926 filed Jan. 23, 2008, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates in general to hybrid drive systems for vehicles and other mechanisms. In particular, this invention relates to an electro-hydraulic machine for use with such a hybrid drive system.
Drive train systems are widely used for generating power from a source and for transferring such power from the source to a driven mechanism. Frequently, the source generates rotational power, and such rotational power is transferred from the source of rotational power to a rotatably driven mechanism. For example, in most land vehicles in use today, an engine generates rotational power, and such rotational power is transferred from an output shaft of the engine through a driveshaft to an input shaft of an axle so as to rotatably drive the wheels of the vehicle.
In some vehicles and other mechanisms, a hybrid drive system is provided in conjunction with the drive train system for accumulating energy during braking of the rotatably driven mechanism and for using such accumulated energy to assist in subsequently rotatably driving the rotatably driven mechanism. To accomplish this, a typical hybrid drive system includes an energy storage device and a reversible energy transfer machine. The reversible energy transfer machine communicates with the energy storage device and is mechanically coupled to a portion of the drive train system. Typically, the hybrid drive system can be operated in either a retarding mode, a neutral mode, or a driving mode. In the retarding mode, the reversible energy transfer machine of the hybrid drive system accumulates energy by braking or otherwise retarding the rotatably driven mechanism of the drive train system and stores such energy in the energy storage device. In the neutral mode, the hydraulic drive system is disconnected from the drive train system and, therefore, is substantially inoperative to exert any significant driving or retarding influence on the rotatably driven mechanism. In the driving mode, the reversible energy transfer machine of the hybrid drive system supplies the accumulated energy previously stored in the energy storage device to assist in subsequently rotatably driving the rotatably driven mechanism.
One commonly known hybrid drive system uses pressurized fluid as the actuating mechanism. In such a hydraulic hybrid drive system, a fluid energy storage device (such as an accumulator) and a reversible hydraulic machine are provided. Another commonly known hybrid drive system uses electricity as the actuating mechanism. In such an electric hybrid drive system, an electrical energy storage device (such as a battery) and a reversible electric machine are provided. Other hybrid drive systems are known in the art that use other actuating mechanisms.
Regardless of the specific actuating mechanism that is used, the hybrid drive system can improve the performance of the drive train system (such as fuel economy, for example) by recovering and storing energy during deceleration and by retrieving and supplying the stored energy for use during a subsequent acceleration. However, the hybrid drive system does not improve the performance of the drive train system during idle situations, such as when a vehicle in which the drive train system is provided is not moving. During such idle situations, the performance of the drive train system can be improved by turning off the engine. However, the drive train system may include one or more accessories that may be necessary or desirable to be operated while the engine is not operated. Such accessories can be electrically operated (such as lighting systems, navigation systems, audio systems, and the like), hydraulically operated (such as steering systems, braking systems, air conditioning systems, and the like), or a combination thereof. Thus, it would be desirable to provide an improved structure for a hybrid drive system that is capable of operating such accessories while the engine is not operated.
SUMMARY OF THE INVENTION
This invention relates to a combined hybrid drive system and electro-hydraulic machine. The hybrid drive system is adapted to decelerate a rotatably driven mechanism, accumulate the energy resulting from such deceleration, and use the accumulated energy to subsequently accelerate the rotatably driven mechanism. The electro-hydraulic machine is operatively connected to the hybrid drive system and is adapted to be operated in one or more of a plurality of modes to improve the performance of the hybrid drive system.
Various aspects of this invention will become apparent to those skilled in the art from the following detailed description of the preferred embodiment, when read in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The sole FIGURE is a schematic diagram of a drive train system including a hybrid drive system and an electro-hydraulic machine in accordance with this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, there is illustrated in FIG. 1 a drive train system, indicated generally at 10 , for generating power from a source and for transferring such power from the source to a driven mechanism. The illustrated drive train system 10 is a vehicular drive train system that includes an engine 11 that generates rotational power to an axle assembly 12 by means of a hybrid drive system, indicated generally at 20 . However, the illustrated vehicle drive train system 10 is intended merely to illustrate one environment in which this invention may be used. Thus, the scope of this invention is not intended to be limited for use with the specific structure for the vehicular drive train system 10 illustrated in FIG. 1 or with vehicle drive train systems in general. On the contrary, as will become apparent below, this invention may be used in any desired environment for the purposes described below.
The illustrated hybrid drive system 20 includes a power drive unit 21 that is connected between the engine 11 and the axle assembly 12 . The illustrated power drive unit 21 is, in large measure, conventional in the art and is intended merely to illustrate one environment in which this invention may be used. Thus, the scope of this invention is not intended to be limited for use with the specific structure for the power drive unit 21 illustrated in FIG. 1 . The illustrated power drive unit 21 includes an input shaft 22 that is rotatably driven by the engine 11 . An input gear 23 is supported on the input shaft 22 for rotation therewith. The input gear 23 is connected for rotation with a primary pump drive gear 24 that, in turn, is connected for rotation with an input shaft of a primary pump 25 . Thus, the primary pump 25 is rotatably driven whenever the engine 11 is operated. The purpose of the primary pump 25 will be explained below.
The illustrated power drive unit 21 also includes a main drive clutch 26 that selectively connects the input shaft 22 to an output shaft 27 . When the main drive clutch 26 is engaged, the input shaft 22 is connected for rotation with the output shaft 27 . When the main drive clutch 26 is disengaged, the input shaft 22 is not connected for rotation with the output shaft 27 . The output shaft 27 is connected for rotation with an input shaft of the axle assembly 12 . Thus, the axle assembly 12 is rotatably driven by the engine 11 whenever the main drive clutch 26 is engaged.
The illustrated power drive unit 21 further includes a low drive clutch 30 that selectively connects the output shaft 27 to a low drive clutch gear 31 . The low drive clutch output gear 31 is connected for rotation with both a first low drive output gear 32 and a second low drive output gear 33 . The first low drive output gear 32 is connected for rotation with a first shaft 32 a that, in turn, is connected for rotation with an input shaft of a first pump/motor 34 . Similarly, the second low drive output gear 33 is connected for rotation with a second shaft 33 a that, in turn, is connected for rotation with an input shaft of a second pump/motor 35 . Thus, when both the main drive clutch 26 and the low drive clutch 30 are engaged, the output shaft 27 rotatably drives both the first pump/motor 34 and the second pump motor 35 . The purpose for both the first pump/motor 34 and the second pump motor 35 will be explained below.
Similarly, the illustrated power drive unit 21 further includes a high drive clutch 36 that selectively connects the output shaft 27 to a high drive clutch gear 37 . The high drive clutch output gear 37 is connected for rotation with both a first high drive output gear 38 and a second high drive output gear 39 . The first high drive output gear 38 is connected for rotation with the first shaft 32 a that, as mentioned above, is connected for rotation with the input shaft of the first pump/motor 34 . Similarly, the second high drive output gear 39 is connected for rotation with the second shaft 33 a that, as also mentioned above, is connected for rotation with the input shaft of the second pump/motor 35 . Thus, when both the main drive clutch 26 and the high drive clutch 36 are engaged, the output shaft 27 rotatably drives both the first pump/motor 34 and the second pump motor 35 . The low drive gears 31 , 32 , and 33 are selected to provide a relatively low gear ratio when the main drive clutch 26 and the low drive clutch 30 are engaged, in comparison with the relatively high gear ratio provided by the high drive gears 37 , 28 , and 39 when the main drive clutch 26 and the high drive clutch 36 are engaged.
The illustrated power drive unit 21 also includes an accumulator 40 or similar relatively high fluid pressure storage device. The accumulator 40 selectively communicates with a first port of the primary pump 25 through a primary pump valve 41 . The primary pump valve 41 is conventional in the art and can be operated in a first position (shown in FIG. 1 ), wherein fluid communication from the accumulator 40 to the first port of the primary pump 25 is prevented and fluid communication from the first port of the primary pump 25 to the accumulator 40 is permitted. However, the primary pump valve 41 can be operated in a second position (to the right when viewing FIG. 1 ), wherein fluid communication from the accumulator 40 to the first port of the primary pump 25 is permitted and fluid communication from the first port of the primary pump 25 to the accumulator 40 is permitted. For the purposes of this invention, the primary pump valve 41 is always maintained in the illustrated first position, wherein fluid communication from the accumulator 40 to the first port of the primary pump 25 is prevented and fluid communication from the first port of the primary pump 25 to the accumulator 40 is permitted.
The accumulator 40 also selectively communicates with a first port of the first pump/motor 34 through a first control valve 42 . The first control valve 42 is conventional in the art and can be operated in a first position (shown in FIG. 1 ), wherein fluid communication from the first port of the first pump/motor 34 to the accumulator 40 is permitted and fluid communication from the accumulator 40 to the first port of the first pump/motor 34 is prevented. However, the first control valve 42 can be operated in a second position (to the right when viewing FIG. 1 ), wherein fluid communication from the first port of the first pump/motor 34 to the accumulator 40 is permitted and fluid communication from the accumulator 40 to the first port of the first pump/motor 34 is permitted.
The accumulator 40 further selectively communicates with a first port of the second pump/motor 35 through a second control valve 43 . The second control valve 43 is conventional in the art and can be operated in a first position (shown in FIG. 1 ), wherein fluid communication from the first port of the second pump/motor 35 to the accumulator 40 is permitted and fluid communication from the accumulator 40 to the first port of the second pump/motor 35 is prevented. However, the second control valve 43 can be operated in a second position (to the right when viewing FIG. 1 ), wherein fluid communication from the first port of the second pump/motor 35 to the accumulator 40 is permitted and fluid communication from the accumulator 40 to the first port of the second pump/motor 35 is permitted.
The illustrated power drive unit 21 further includes a reservoir 44 or similar relatively low fluid pressure storage device. Each of the primary pump 25 , the first pump/motor 34 , and the second pump/motor 35 includes a second port, and all of such second ports communicate with the reservoir 44 to draw fluid therefrom when necessary, as described below.
The basic operation of the drive train system 10 will now be described. When the engine 11 of the drive train system 10 is initially started, the main drive clutch 26 , the low drive clutch 30 , and the high drive clutch 36 are all disengaged, and the valves 41 , 42 , and 43 are all in their first positions illustrated in FIG. 1 . In this initial condition, the engine 11 rotatably drives the primary pump 25 through the input shaft, the input gear 23 , and the primary pump drive gear 24 , as described above. As a result, the primary pump 25 draws fluid from the reservoir 44 through the second port thereof, and further supplies such fluid under pressure from the first port of the primary pump 25 through the primary pump valve 41 to the accumulator 40 . As discussed above, the first and second control valves 42 and 43 prevent the pressurized fluid from the primary pump 25 or the accumulator 40 from being supplied to the first ports of the first and second pump/motors 34 and 35 , respectively. Such initially operation continues until a sufficient amount of such pressurized fluid has been supplied to the accumulator 40 . Because the main drive clutch 26 , the low drive clutch 30 , and the high drive clutch 36 are all disengaged, the engine 11 does not rotatably drive the output shaft 27 or the axle assembly 12 in this initial operation of the drive train system 10 .
When it is desired to move the vehicle, the low drive clutch 30 is engaged, while the main drive clutch 26 and the high drive clutch 36 remain disengaged. As a result, the output shaft 27 is connected to the low drive clutch gear 31 for concurrent rotation. At the same time, the first control valve 42 and the second control valve 43 are each moved to their second positions. This permits pressurized fluid from the accumulator 40 to flow to the first ports of both the first pump/motor 34 and the second pump/motor 35 . Lastly, the first and second pump/motors 34 and 35 are each placed in a positive displacement mode, wherein they function as motors to use the pressurized fluid supplied by the accumulator 40 to rotatably drive the first and second shafts 32 a and 33 a . In turn, this causes the low drive gears 31 , 32 , and 33 and the output shaft 27 to be rotatably driven. As a result, the axle assembly 12 is rotatably driven at the relatively low gear ratio provided by the low drive gears 31 , 32 , and 33 . Such a relatively low gear ratio is well suited for providing the relatively high torque needed to accelerate the vehicle from a standstill.
Once it has begun to move, it may be desirable to move the vehicle at a higher speed that is suitable for the relatively low gear ratio provided by the low drive gears 31 , 32 , and 33 . In this instance, the power drive unit 21 can be operated to disengage the low drive clutch 30 and engage the high drive clutch 36 , while maintaining the main drive clutch 26 disengaged. As a result, the output shaft 27 is connected to the high drive clutch output gear 37 for concurrent rotation. The first control valve 42 and the second control valve 43 are each moved to (or maintained in) their second positions. As described above, this permits pressurized fluid from the accumulator 40 to flow to the first ports of both the first pump/motor 34 and the second pump/motor 35 . As also described above, the first and second pump/motors 34 and 35 are each placed (or maintained) in a positive displacement mode, wherein they function as motors to use the pressurized fluid supplied by the accumulator 40 to rotatably drive the first and second shafts 32 a and 33 a . In turn, this causes the high drive gears 37 , 38 , and 39 and the output shaft 27 to be rotatably driven. As a result, the axle assembly 12 is rotatably driven at the relatively low gear ratio provided by the high drive gears 37 , 38 , and 39 . Such a relatively high gear ratio is well suited for providing the relatively low torque needed to accelerate the vehicle to a relatively high speed.
If it is desired to operate the vehicle at a further higher speed, the power drive unit 21 can be operated to disengage the high drive clutch 36 and engage the main drive clutch 26 , while the low drive clutch 30 remains disengaged. As a result, the output shaft 27 is connected to the input shaft 22 for concurrent rotation. At the same time, the first control valve 42 and the second control valve 43 are each moved to their first positions. As described above, this prevents pressurized fluid from the accumulator 40 from flowing to the outputs of both the first pump/motor 34 and the second pump/motor 35 . As a result, the first and second pump/motors 34 and 35 are isolated from the drive train system 10 .
Under certain circumstances, the above-described components of the hybrid drive system 20 can also be used to slow or stop the movement of the vehicle. To accomplish this, the main drive clutch 26 and the low drive clutch 30 are disengaged, while the high drive clutch 36 is engaged (in some instances, it may be preferable that the main drive clutch 26 and the high drive clutch 36 be disengaged, while the low drive clutch 30 is engaged). Regardless, the first control valve 42 and the second control valve 43 are each moved to (or maintained in) their second positions. This permits pressurized fluid from the first ports of both the first pump/motor 34 and the second pump/motor 35 to flow to the accumulator 40 . Lastly, the first and second pump/motors 34 and 35 are each placed in a negative displacement mode, wherein they function as pumps to use the rotational energy of the rotating output shaft 27 to supply pressurized fluid to the accumulator 40 . As a result, the output shaft 27 rotates the high drive gears 37 , 38 , and 39 , which causes the first pump/motor 34 and the second pump/motor 35 to be rotatably driven. Consequently, the rotation of the axle assembly 12 is decelerated as the kinetic energy thereof is stored as fluid pressure in the accumulator 40 .
It is often desirable to provide a separate brake system to affirmatively slow or stop the rotation of the axle assembly 12 . As shown in FIG. 1 , such a separate brake system is provided within the axle assembly 12 of the illustrated drive train system 10 as a pair of friction brakes 45 associated with respective wheels of the vehicle. The friction brakes 45 are conventional in the art and may be actuated in any desired manner, such as pneumatically or hydraulically.
In the illustrated hybrid drive system 20 , pressurized fluid is used as the actuating mechanism. In such a hydraulic hybrid drive system, the accumulator 40 functions as the energy storage device, and the pump/motors 34 and 35 function as reversible hydraulic machines. Another commonly known hybrid drive system uses electricity as the actuating mechanism. In such an electric hybrid drive system, an electrical energy storage device (such as a capacitor or a battery) and a reversible electrical machine (such as generator/motor) are provided and function in a similar manner as described above. This invention is not intended to be limited to the specific structure of the hybrid drive system, but rather is intended to cover any similar structures.
The illustrated hybrid drive system 20 further includes an electro-hydraulic machine, indicated generally at 50 , in accordance with this invention. The illustrated electro-hydraulic machine 50 includes an input shaft 51 that is connected for rotation with the input shaft 22 of the power drive unit 21 that, as described above, can be rotatably driven by the engine 11 . In the illustrated embodiment, the input shaft 51 of the clutch 55 is connected for rotation with the input shaft 22 of the power drive unit 21 by a first pulley 52 a , a belt 52 b , and a second pulley 52 c . The first pulley 52 a is mounted on or otherwise connected for rotation with the input shaft 22 of the power drive unit 21 . The second pulley 52 c is mounted on or otherwise connected for rotation with the input shaft 51 of the electro-hydraulic machine 50 . The belt 52 b extends about the first pulley 52 a and the second pulley 52 c such that the first and second pulleys 52 a and 52 c are connected for rotation together. In this manner, the input shaft 51 of the electro-hydraulic machine 50 is connected for rotation with the input shaft 22 of the power drive unit 21 . However, the input shaft 51 of the clutch 55 can connected for rotation with the input shaft 22 of the power drive unit 21 by any desired structure including, for example, gears, shafts or a direct drive arrangement.
The input shaft 51 of the electro-hydraulic machine 50 is selectively connected through a clutch 53 to an output shaft 54 of the electro-hydraulic machine 50 . The clutch 53 is conventional in the art and is adapted to selectively connect the input shaft 51 for rotation with the output shaft 54 . When the clutch 53 is engaged, the input shaft 51 and the output shaft 54 are connected for rotation together. When the clutch 51 is disengaged, the input shaft 51 and the output shaft 54 are not connected for rotation together.
The output shaft 54 is connected for rotation with an electric generator/motor 55 that, in turn, is electrically connected to an electric energy storage device 56 . The electric generator/motor 55 is conventional in the art and is responsive to rotational power supplied from the output shaft 54 for generating electrical power to the electric energy storage device 56 . The electric energy storage device 56 is also conventional in the art and may be embodied as any desired device that can store electrical energy, such as a battery or a capacitor. The electric generator/motor 55 is also responsive to electrical power supplied from the electric energy storage device 56 for rotatably driving the output shaft 54 . The purpose for and manner of operation of the electric generator/motor 55 and the electric energy storage device 56 will be explained below.
The output shaft 54 is also connected for rotation with a hydraulic pump/motor 57 that, in turn, is hydraulically connected to a hydraulic energy storage device 58 . The hydraulic pump/motor 57 is conventional in the art and is responsive to rotational power supplied from the output shaft 54 for generating hydraulic power to the hydraulic energy storage device 58 . The hydraulic energy storage device 58 is also conventional in the art and may be embodied as any desired device that can store hydraulic energy, such as an accumulator. The hydraulic generator/motor 57 is also responsive to hydraulic power supplied from the hydraulic energy storage device 58 for rotatably driving the output shaft 54 . The purpose for and manner of operation of the hydraulic generator/motor 57 and the hydraulic energy storage device 58 will also be explained below.
The electric energy storage device 56 and the hydraulic energy storage device 58 are connected to operate one or more accessories 60 that are adapted for use in conjunction with the drive train system 10 . The electric energy storage device 56 is adapted to operated one or more electrically operated accessories 60 , such as lighting systems, navigation systems, audio systems, and the like. As shown in FIG. 1 , one or more of the electrically operated accessories 60 may be directly driven from the electric generator/motor 55 . The hydraulic energy storage device 58 is adapted to operated one or more hydraulically operated accessories 60 , such as such as steering systems, braking systems, air conditioning systems, and the like. As also shown in FIG. 1 , one or more of the hydraulically operated accessories 60 may be directly driven from the hydraulic pump/motor 57 . Lastly, as also shown in FIG. 1 , the engine 11 may be adapted to operate one or more of accessories 60 .
The electro-hydraulic machine 50 can be operated in a variety of modes that can improve the performance of the drive train system 10 . Each of the operating modes described below can be accomplished through the use of one or more electrical switches and/or other conventional electrical devices, one or more hydraulic valves and/or other conventional hydraulic devices, and one or more clutches and/or other mechanical devices. The specific arrangement of such electrical, hydraulic, and mechanical devices needed to accomplish each of the operating modes described below is easily within the realm of a person having ordinary skill in the art, and this invention is not intended to be limited to any specific arrangement of same. Additionally, one or more control devices (not shown), such as conventional microprocessors or programmable controllers, may be provided for operating the electro-hydraulic machine 50 in any or all of the various modes. The specific programming and manner of operation of such control devices is also easily within the realm of a person having ordinary skill in the art, and this invention is not intended to be limited to any specific programming or manner of operation of same.
In a first operating mode, the electro-hydraulic machine 50 can be operated as an electric starter to assist in starting the engine 11 after it has been turned off. To accomplish this, electric energy stored in the electric energy storage device 56 is supplied to the electric generator/motor 55 . In response thereto, the electric generator/motor 55 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be engaged. As a result, rotation of the output shaft 54 of the electro-hydraulic machine 50 causes concurrent rotation of the input shaft 53 of the electro-hydraulic machine 50 and, therefore, the input shaft 22 of the power drive unit 20 . As discussed above, the engine 11 rotatably drives the input shaft 22 of the power drive unit 20 . Thus, when the input shaft 22 of the power drive unit 20 , the engine 11 is rotatably driven in a manner similar to a conventional starter motor (not shown). Thus, in this first operating mode, the electro-hydraulic machine 50 can be operated as an electric starter to assist in starting the engine 11 .
In a second operating mode, the electro-hydraulic machine 50 can be operated as a hydraulic starter to assist in starting the engine 11 after it has been turned off. To accomplish this, hydraulic energy stored in the hydraulic energy storage device 58 is supplied to the hydraulic pump/motor 57 . In response thereto, the hydraulic pump/motor 57 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be engaged. As a result, rotation of the output shaft 54 of the electro-hydraulic machine 50 causes concurrent rotation of the input shaft 53 of the electro-hydraulic machine 50 and, therefore, the input shaft 22 of the power drive unit 20 . As discussed above, the engine 11 rotatably drives the input shaft 22 of the power drive unit 20 . Thus, when the input shaft 22 of the power drive unit 20 , the engine 11 is rotatably driven in a manner similar to a conventional starter motor (not shown). Thus, in this second operating mode, the electro-hydraulic machine 50 can be operated as a hydraulic starter to assist in starting the engine 11 .
In a third operating mode, the electro-hydraulic machine 50 can be operated as an electrically-oriented source of either electrical or hydraulic energy to some or all of the accessories 60 . Electrical energy stored in the electric energy storage device 56 can be supplied directly to one or more of the electrically operated accessories 60 , as mentioned above. Additionally, hydraulic energy stored in the hydraulic energy storage device 58 can be supplied directly to one or more of the hydraulically operated accessories 60 by supplying the electrical energy stored in the electric energy storage device 56 to the electric generator/motor 55 . In response thereto, the electric generator/motor 55 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be disengaged. Rotation of the output shaft 54 of the electro-hydraulic machine 50 rotatably drives the hydraulic pump/motor 57 . The hydraulic pump/motor 57 is thus operated as a pump to supply hydraulic energy to one or more of the hydraulically operated accessories 60 . Thus, in this third operating mode, the electro-hydraulic machine 50 can be operated as an electrically-oriented source of either electrical or hydraulic energy to some or all of the accessories 60 .
In a fourth operating mode, the electro-hydraulic machine 50 can be operated as a hydraulically-oriented source of either electrical or hydraulic energy to some or all of the accessories 60 . Hydraulic energy stored in the hydraulic energy storage device 58 can be supplied directly to one or more of the hydraulically operated accessories 60 , as mentioned above. Additionally, electric energy stored in the electric energy storage device 56 can be supplied directly to one or more of the electrically operated accessories 60 by supplying the hydraulic energy stored in the hydraulic energy storage device 58 to the hydraulic pump/motor 57 . In response thereto, the hydraulic pump/motor 57 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be disengaged. Rotation of the output shaft 54 of the electro-hydraulic machine 50 rotatably drives the electric generator/motor 55 . The electric generator/motor 55 is thus operated as a generator to supply electric energy to one or more of the electrically operated accessories 60 . Thus, in this fourth operating mode, the electro-hydraulic machine 50 can be operated as a hydraulically-oriented source of either electrical or hydraulic energy to some or all of the accessories 60 .
In a fifth operating mode, the electro-hydraulic machine 50 can be operated as a mechanical alternator to supply electrical energy to one or more of the electrically operated accessories 60 without the use of the electric energy storage device 56 . To accomplish this, the engine 11 is operated while the clutch 53 is engaged. As a result, the output shaft 54 of the electro-hydraulic machine 50 is rotatably driven by the engine 11 . Rotation of the output shaft 54 of the electro-hydraulic machine 50 rotatably drives the electric generator/motor 55 . The electric generator/motor 55 is thus operated as a generator to supply electric energy to one or more of the electrically operated accessories 60 . Thus, in this fifth operating mode, the electro-hydraulic machine 50 can be operated as a mechanical alternator to supply electrical energy to one or more of the electrically operated accessories 60 without the use of the electric energy storage device 56 .
In a sixth operating mode, the electro-hydraulic machine 50 can be operated as a mechanical pressure pump to supply hydraulic energy to one or more of the hydraulically operated accessories 60 without the use of the hydraulic energy storage device 58 . To accomplish this, the engine 11 is operated while the clutch 53 is engaged. As a result, the output shaft 54 of the electro-hydraulic machine 50 is rotatably driven by the engine 11 . Rotation of the output shaft 54 of the electro-hydraulic machine 50 rotatably drives the hydraulic pump/motor 57 . The hydraulic pump/motor 57 is thus operated as a pump to supply hydraulic energy to one or more of the hydraulically operated accessories 60 . Thus, in this sixth operating mode, the electro-hydraulic machine 50 can be operated as a mechanical pressure pump to supply hydraulic energy to one or more of the hydraulically operated accessories 60 without the use of the hydraulic energy storage device 58 .
In a seventh operating mode, the electro-hydraulic machine 50 can be operated as an electrically-oriented source of rotational power to supplement the amount of rotational power that is supplied from the engine 11 to the drive train system 10 . To accomplish this, the engine 11 is operated while the clutch 53 is engaged. At the same time, electric energy stored in the electric energy storage device 56 is supplied to the electric generator/motor 55 . In response thereto, the electric generator/motor 55 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be engaged. As a result, supplemental rotational power is supplied from the electro-hydraulic machine 50 to the input shaft 22 of the power drive unit 20 . Thus, in this seventh operating mode, the electro-hydraulic machine 50 can be operated as an electrically-oriented source of rotational power to supplement the amount of rotational power that is supplied from the engine 11 to the drive train system 10 .
In an eighth operating mode, the electro-hydraulic machine 50 can be operated as a hydraulically-oriented source of rotational power to supplement the amount of rotational power that is supplied from the engine 11 to the drive train system 10 . To accomplish this, the engine 11 is operated while the clutch 53 is engaged. At the same time, hydraulic energy stored in the hydraulic energy storage device 58 is supplied to the hydraulic pump/motor 57 . In response thereto, the hydraulic pump/motor 57 is operated as a motor to rotate the output shaft 54 of the electro-hydraulic machine 50 . At the same time, the clutch 53 is caused to be engaged. As a result, supplemental rotational power is supplied from the electro-hydraulic machine 50 to the input shaft 22 of the power drive unit 20 . Thus, in this eighth operating mode, the electro-hydraulic machine 50 can be operated as a hydraulically-oriented source of rotational power to supplement the amount of rotational power that is supplied from the engine 11 to the drive train system 10 .
In a ninth operating mode, the electro-hydraulic machine 50 can be operated as either an electrically-oriented torsional damper or a hydraulically-oriented torsional damper for the engine 11 . To accomplish this, supplemental rotational power is supplied from the electro-hydraulic machine 50 to the engine 11 of the drive train system 10 as described above in connection with the seventh or eighth operating modes. However, the application of such supplemental rotational power selected to be similar in magnitude and opposite in phase from any torque ripple that is generated in the input shaft 22 of the power drive unit 20 by the engine 11 . The detection and measurement of the magnitude and phase of such torque ripple can be made in any conventional manner, and the various components of the electro-hydraulic machine 50 (including the clutch 53 , the electric generator/motor 55 , and the hydraulic pump/motor 57 ) can be operated to achieve the desired reduction or cancelation of the torque ripple that is generated in the input shaft 22 of the power drive unit 20 by the engine 11 . Thus, in this ninth operating mode, the electro-hydraulic machine 50 can be operated as either an electrically-oriented torsional damper or a hydraulically-oriented torsional damper for the engine 11 .
In a tenth operating mode, the electro-hydraulic machine 50 can be operated as either an electrically-oriented brake or a hydraulically-oriented brake to selectively retard the rotation of the input shaft 22 of the power drive unit 20 . To accomplish this, the clutch 53 is caused to be engaged when it is desired to retard the rotation of the input shaft 22 of the power drive unit 20 . When the clutch 53 is engaged, the input shaft 22 of the power drive unit 20 rotatably drives the output shaft 54 of the electro-hydraulic machine 50 . As a result, both the electric generator/motor 55 and the hydraulic pump/motor 57 are rotatably driven. The loads imposed by the electric generator/motor 55 and the hydraulic pump/motor 57 retard the rotation of the output shaft 54 of the electro-hydraulic machine 50 and, therefore, the input shaft 22 of the power drive unit 20 . At the same time, the electric generator/motor 55 is operated as a generator to supply electrical energy to the electric energy storage device 56 , and the hydraulic pump/motor 57 is operated as a pump to supply hydraulic energy to the hydraulic energy storage device 58 . Thus, in this tenth operating mode, the electro-hydraulic machine 50 can be operated as either an electrically-oriented engine brake or a hydraulically-oriented engine brake to selectively retard the rotation of the input shaft 22 of the power drive unit 20 .
The principle and mode of operation of this invention have been explained and illustrated in its preferred embodiment. However, it must be understood that this invention may be practiced otherwise than as specifically explained and illustrated without departing from its spirit or scope. | A combined hybrid drive system and electro-hydraulic machine includes a hybrid drive system that is adapted to decelerate a rotatably driven mechanism, accumulate the energy resulting from such deceleration, and use the accumulated energy to subsequently accelerate the rotatably driven mechanism. An electro-hydraulic machine is operatively connected to the hybrid drive system and is adapted to be operated in one or more of a plurality of modes to improve the performance of the hybrid drive system. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of our earlier co-pending application, Ser. No. 632,012, filed Nov. 14, 1975, now U.S. Pat. No. 4,036,843.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to a novel class of antibacterial compounds and more specifically, the present invention is directed to a novel class of antibacterial compounds which are termed soft N-chloramino alcohol derivatives as described later. The term "antibacterial" as employed in this application, includes both "antifungal" and "antibacterial" activity.
2. Description of the Prior Art
N-chloramines such as the N-chlorinated naturally occurring amino acids as well as their derivatives are presently known. However, in the main, these compounds have not been isolated, or if isolated, can undergo rapid and often explosive decomposition. Illustrative of such a compound undergoing explosive decomposition upon isolation is methyl N-chlorosarcosinoate. James J. Kaminski, Nicolae Bodor and Takeru Higuchi; J. Pharm. Sci., 64, 0000 (1975).
Similarly, simple chloramines (e.g., chloramine per se) can undergo disproportionation, providing as one by-product NCl 3 , a well-known toxic material.
Due to the low water solubility and low boiling point of simple chloramines, they simply evaporate too quickly from an aqueous solution, and as such, a sterilizing aqueous solution containing a simple chloramine is characterized by extremely low persistency.
Moreover, the simple chloramines (e.g., NH 2 Cl, NHCl 2 ) are known to be readily deactivated by denaturing agents (e.g., horse serum), thus quickly diminishing the antibacterial activity of such compounds.
Methyl-α-N,N-dichloroaminoisobutyrate is also known, but only to the extent that it has been used to study the mechanism and kinetics of the dimerization of N,N-dichloro derivatives in strong bases. As such, no known antibacterial utility has been recognized for this compound. See, A. M. Pinchuk, L. N. Markovskii and G. K. Bespalko, Zh. Org. Khim., 7, 2263 (1971) and Julius J. Fuchs, U.S. Pat. No. 3,530,162 (1970).
SUMMARY OF THE INVENTION
Accordingly, it is one object of the present invention to provide a novel class of compounds exhibiting substantial antibacterial and antifungal activity.
It is another object of the present invention to provide a novel class of antibacterial compounds which will exhibit enhanced stability in the "neat" state.
Still, it is another object of the present invention to provide a novel class of antibacterial compounds which will exhibit enhanced stability in the "neat" state, in addition to further exhibiting substantial antibacterial activity over varying pH conditions.
Still further, it is another object of the present invention to provide a novel class of antibacterial compounds which remain stable in the "neat" state, remain active over varying pH conditions and yet fail to be inactivated as antibacterial agents by conventional denaturants, such as blood serum.
Finally, it is the last object of the present invention to provide a novel class of antibacterial compounds as heretofore described which are biodegraded into nontoxic products.
Accordingly, all the above objects of the present invention can be satisfied with a novel class of antibacterial compounds having the formula: ##STR5## wherein X and Y each represent a member which may be the same or different selected from the group consisting of H and Cl with the proviso that X and Y cannot represent H simultaneously; R 1 and R 2 each represent a member which may be the same or different selected from the group consisting of an n- or branched alkyl group of from 1 to 20 carbon atoms, an aryl group (phenyl, naphthyl, etc.) and ##STR6## wherein m represents an integer of from 2 to 5; n represents an integer of 1 to 8; and Z represents a member selected from the group consisting of an --OOCR 3 group, an --OR 3 group and an OCH 2 OR 3 group, wherein R 3 represents a member selected from the group consisting of an n- or branched alkyl group of 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a benzyl group, ##STR7## wherein X is a halogen atom (Cl, Br, I), ##STR8## wherein R 4 represents a member selected from the group consisting of H, an n- or branched alkyl group, a benzyl group, an O atom, and a --(CH 2 ) p COOH group, wherein p represents an integer of 1 to 4, and wherein W.sup.θ represents a nontoxic pharmaceutically acceptable inorganic or organic anion.
DETAILED DESCRIPTION OF THE INVENTION
In the above formula, when each of R 1 , R 2 and R 3 represent an alkyl group, a carbon range of from 1 - 5 carbon atoms is preferred. When R 1 and R 2 represent an aryl group or ##STR9## respectively, phenyl is the aryl group of choice and 4 is the integer of choice for m.
The phrase, "nontoxic pharmaceutically acceptable inorganic or organic anion" as used herein generally includes the nontoxic acid addition salts of the compounds of formula (I), formed with nontoxic inorganic or organic acids. For example, the salts include those derived from inorganic acids such as hydrochloric, hydrobromic, sulfuric, phosphoric, nitric and the like; and the salts prepared from organic acids such as acetic, propionic, succinic, stearic, malonic, pamoic, phenylacetic, glutaric, benzoic, toluene-sulfonic, methanesulfonic and the like.
While all the compounds encompassed within the above-described generic formula will satisfy the objectives of the present invention, nevertheless, certain compounds are preferred as set out below:
1. 2-N-Chloroamino-2-methyl-1-propyl acetate.
2. 2-N-Chloroamino-2-methyl-1-propyl propionate.
3. 2-N-Chloroamino-2-methyl-1-propyl butyrate.
4. 2-N-Chloroamino-2-methyl-1-propyl isobutyrate.
5. 2-N-Chloroamino-2-methyl-1-propyl valerate.
6. 2-N-Chloroamino-2-methyl-1-propyl isovalerate.
7. 2-N-Chloroamino-2-methyl-1-propyl hexanoate.
8. 2-N-Chloroamino-2-methyl-1-propyl octanoate.
9. 2-N-Chloroamino-2-methyl-1-propyl decanoate.
10. 2-N-Chloroamino-2-methyl-1-propyl dodecanoate.
11. 2-N-Chloroamino-2-methyl-1-propyl tetradecanoate.
12. 2-N-Chloroamino-2-methyl-1-propyl hexadecanoate.
13. 2-N-Chloroamino-2-methyl-1-propyl octadecanoate.
14. 2-N-Chloroamino-2-methyl-1-propyl 2,2-dimethylpropionate.
15. 2-N-Chloroamino-2-methyl-1-propyl benzoate.
16. 2-N-Chloroamino-2-methyl-1-propyl nicotinoate.
17. 2-N-Chloroamino-2-methyl-1-propyl isonicotinoate.
18. 2-N-Chloroamino-2-methyl-1-propyl nicotinate N-oxide.
19. 2-N-Chloroamino-2-methyl-1-propyl isonicotinate N-oxide.
20. 2-N-Chloroamino-2-methyl-1-propyl nicotinate hydrochloride.
21. 2-N-Chloroamino-2-methyl-1-propyl nicotinate methylsulfonate.
22. 2-N-Chloroamino-2-methyl-1-propyl nicotinate methylsulfate.
23. 2-N-Chloroamino-2-methyl-1-propyl isonicotinate hydrochloride.
24. 2-N-Chloroamino-2-methyl-1-propyl isonicotinate methylsulfonate.
25. 2-N-Chloroamino-2-methyl-1-propyl isonicotinate methylsulfate.
26. 2-N,N-Dichloroamino-2-methyl-1-propyl acetate.
27. 2-N,N-Dichloroamino-2-methyl-1-propyl propionate.
28. 2-N,N-Dichloroamino-2-methyl-1-propyl butyrate.
29. 2-N,N-Dichloroamino-2-methyl-1-propyl isobutyrate.
30. 2-N,N-Dichloroamino-2-methyl-1-propyl valerate.
31. 2-N,N-Dichloroamino-2-methyl-1-propyl isovalerate.
32. 2-N,N-Dichloroamino-2-methyl-1-propyl hexanoate.
33. 2-N,N-Dichloroamino-2-methyl-1-propyl octanoate.
34. 2-N,N-Dichloroamino-2-methyl-1-propyl decanoate.
35. 2-N,N-Dichloroamino-2-methyl-1-propyl dodecanoate.
36. 2-N,N-Dichloroamino-2-methyl-1-propyl tetradecanoate.
37. 2-N,N-Dichloroamino-2-methyl-1-propyl hexadecanoate.
38. 2-N,N-Dichloroamino-2-methyl-1-propyl octadecanoate.
39. 2-N,N-Dichloroamino-2-methyl-1-propyl 2,2-dimethylpropionate.
40. 2-N,N-Dichloroamino-2-methyl-1-propyl benzoate.
41. 2-N,N-Dichloroamino-2-methyl-1-propyl nicotinoate.
42. 2-N,N-Dichloroamino-2-methyl-1-propyl isonicotinoate.
43. 2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate N-oxide.
44. 2-N,N-Dichloroamino-2-methyl-1-propyl isonicotinate N-oxide.
45. 2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate hydrochloride.
46. 2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate methylsulfonate.
47. 2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate methylsulfate.
48. 2-N,N-Dichloroamino-2-methyl-1-propyl isonicotinate hydrochloride.
49. 2-N,N-Dichloroamino-2-methyl-1-propyl isonicotinate methylsulfonate.
50. 2-N,N-Dichloroamino-2-methyl-1-propyl isonicotinate methylsulfate.
51. 2-N-Chloroamino-2-methyl-1-propyl methyl ether.
52. 2-N-Chloroamino-2-methyl-1-propyl ethyl ether.
53. 2-N-Chloroamino-2-methyl-1-propyl propyl ether.
54. 2-N-Chloroamino-2-methyl-1-propyl butyl ether.
55. 2-N,N-Dichloroamino-2-methyl-1-propyl methyl ether.
56. 2-N,N-Dichloroamino-2-methyl-1-propyl ethyl ether.
57. 2-N,N-Dichloroamino-2-methyl-1-propyl propyl ether.
58. 2-N,N-Dichloroamino-2-methyl-1-propyl butyl ether.
59. Formaldehyde 2-N-Chloroamino-2-methyl-1-propyl methyl acetal.
60. Formaldehyde 2-N-Chloroamino-2-methyl-1-propyl ethyl acetal.
61. Formaldehyde 2-N,N-dichloroamino-2-methyl-1-propyl methyl acetal.
62. Formaldehyde 2-N,N-dichloroamino-2-methyl-1-propyl ethyl acetal.
The compounds of the present invention can be prepared by simple stepwise procedures as outlined below.
GENERAL REACTION SCHEME
(1) The N-Chloramine precursors for the ester derivatives of formula (I) are prepared by (a) N-- to O-- acyl transfer in the corresponding N-acylated amino alcohol via ethanolic hydrogen chloride 1 , Scheme I, (b) hydrolysis of the corresponding Δ 2 -1,3-oxazoline in acidic tetrahydrofuran solution containing an equivalent of water based on the Δ 2 -1,3-oxazoline 2 , Scheme II, or (c) O-acylation of the N-protected amino alcohol with subsequent removal of the N-protective group, Scheme III 3 . All reactions are run at standard temperature and pressure. ##STR10##
(2) The ether derivative precursors are prepared as follows 4 : ##STR11##
(3) The acetal derivative precursors are prepared as follows 4 : ##STR12##
In the above reaction schemes (I) through (III), R 1 , R 2 , R 3 , X and n are as defined earlier.
Chlorination for all the precursor compounds is easily carried out essentially under the same conditions described above using conventional chlorinating agents, e.g., chlorine, NaOCl, t-BuOCl, N-chlorosuccinimide, etc. The skilled artisan will readily appreciate the fact that the above-mentioned chlorinating agents are only illustrative and nonlimitative as other equivalent chlorinating agents can be employed as well.
Chlorination is normally carried out in a homogeneous solution or suspension at atmospheric pressure and at a temperature of from 0° to 25° C, over a period of time, ranging from 0.5 to 5.0 hours.
Chlorination will normally be carried out in a water solvent, except in the case of t-BuOCl. In this situation, anhydrous organic solvents can be employed (e.g., benzene and/or t-Butyl alcohol).
Following chlorination, the chlorinated compound is isolated normally by filtration or extraction in a non-water miscible solvent such as ether, dichloromethane, petroleum ether, or the like. The final compound is purified by conventional methods such as vacuum distillation, sublimation, crystallization, or conventional chromatographic procedures.
Under the above chlorinating conditions, the compounds of formula (I) are normally obtained; however, the monochloro species can also be obtained in certain instances, and namely, when the pH of the reaction mixture is equal to or greater than 9.0.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as simply illustrative, and not limitative of the remainder of the specification and claims in any way whatsoever. Reference to temperature, in all instances, refers to Centigrade unless otherwise indicated.
EXAMPLE A
2-Amino-2-methyl-1-propyl acetate hydrochloride (IIIa):
To a dichloromethane solution containing 17.1 g (0.1 mol) carbobenzoxychloride at 0° was added dropwise with stirring 18.4 g (0.2 mol) 2-amino-2-methyl-1-propanol. The reaction mixture was stirred at room temperature overnight and the 2-amino-2-methyl-1-propanol hydrochloride which formed was removed by filtration. Removal of the dichloromethane under reduced pressure afforded a colorless, viscous liquid. Distillation gave 14.9 g (0.07 mol), 70%, 2-carbobenzoxyamino-2-methyl-1-propanol, bp 144°-148° (0.3 mm); ir (neat) 3400, 3020, 2980, 1710, 1510, 1455, 1270, 1070, 730 and 680 cm -1 ; pmr (CDCl 3 ) δ 7.2 (s, 5H), 5.4 (bs, 1H), 4.9 (s, 2H), 4.2 (bs, 1H), 3.4 (s, 2H) and 1.2 (s, 6H) ppm.
To a dichloromethane solution containing 2.52 g (0.011 mol) 2-carbobenzoxyamino-2-methyl-1-propanol and 1.17 g (0.015 mol) acetyl chloride was added dropwise with stirring 1.11 g (0.011 mol) triethylamine. The reaction was stirred at ambient temperature overnight and the dichloromethane was removed under reduced pressure. The triethylamine hydrochloride residue was triturated in anhydrous ether. Following filtration, the ether was removed under reduced pressure to afford 2.38 g (0.009 mol), 82%, crude 2-carbobenzoxyamino-2-methyl-1-propyl acetate as a pale yellow liquid, pmr (CDCl 3 ) δ 7.2 (s, 5H), 5.4 (bs, 1H), 5.0 (s, 2H), 2.0 (s, 3H) and 1.2 (s, 6H) ppm.
2.38 g (0.009 mol) 2-Carbobenzoxyamino-2-methyl-1-propyl acetate was dissolved in 100 ml anhydrous hydrogen chloride in tetrahydrofuran (2M). 1.0 g of 10% Pd/C was added to the solution and the resulting mixture was hydrogenated under a hydrogen pressure of 50 psi for 2 hours. The catalyst was removed by filtration and thoroughly washed with tetrahydrofuran. Removal of the tetrahydrofuran under reduced pressure gave an off-white solid. Recrystallization from acetone-hexane afforded 1.0 g (0.006 mol), IIIa, as a hygroscopic white solid, mp 146°-149°; pmr (D 2 O) δ 4.0 (s, 2H), 2.0 (s, 3H) and 1.2 (s, 6H) ppm.
Anal. Calcd for C 6 H 14 ClNO 2 .1/2 H 2 O: C, 40.79; H, 8.56; N, 7.93. Found: C, 40.31; H, 8.36; N, 8.28.
EXAMPLE B
2-Amino-2-methyl-1-propyl butyrate hydrochloride (IIIb):
To 65 ml of a solution of anhydrous hydrogen chloride in tetrahydrofuran (1M) containing 1 ml of water was added 7.3 g (0.052 mol) 2-n-propyl-4,4-dimethyl-Δ 2 -1,3-oxazoline which was prepared using the method of Allen and Ginos (2). The solution was heated under reflux with stirring for 1 hour. The tetrahydrofuran was removed under reduced pressure to afford a semi-solid residue which crystallized at 0° upon the addition of anhydrous ether. The solid was triturated in anhydrous ether overnight and isolated by filtration under a nitrogen atmosphere. After drying in vacuo over calcium sulfate, 7.0 g (0.036 mol), 70%, IIIb, was obtained mp 104°-107°; ir (KBr) 2900, 1740 and 1160 cm -1 ; pmr ((CD 3 ) 2 CO.D 2 O) δ 4.2 (s, 2H), 3.8 (bs, 3H), 2.5 (t, 2H), 1.6 (m, 2H), 1.5 (s, 6H) and 1.0 (t, 3H) ppm.
Anal. Calcd for C 8 H 18 ClNO 2 : C, 49.10; H, 9.27; N, 7.16. Found: C, 50.01; H, 9.62; N, 7.54.
Using the procedure described for the preparation of IIIb, the following 2-amino-2-methyl-1-propyl carboxylate hydrochlorides were prepared:
EXAMPLE C
2-Amino-2-methyl-1-propyl 2,2-dimethylproprionate hydrochloride (IIIc)
mp 113°-118°; ir (KBr) 3430, 2980, 1735, 1520, 1470, 1270 and 1150 cm -1 ; Pmr (D 2 O) δ 4.10 (s, 2H), 1.40 (s, 6H) and 1.23 (s, 9H) ppm.
Anal. Calcd for C 9 H 20 ClNO 2 .H 2 O: C, 47.46; H, 9.74; N, 6.15. Found: C, 47.86; H, 9.34; N, 6.06.
EXAMPLE D
2-Amino-2-methyl-1-propyl hexanoate hydrochloride (IIId):
mp 100°-101°; ir (KBr) 2900, 1745 and 1165 cm -1 ; pmr ((CD 3 ) 2 CO.D 2 O) δ 4.3 (s, 2H), 3.7 (bs, 3H), 2.5 (t, 2H), 1.2-1.8 (m, 6H), 1.5 (s, 6H) and 0.9 (t, 3H) ppm.
Anal. Calcd for C 10 H 22 ClNO 2 : C, 53.68; H, 9.91; N, 6.26. Found: C, 53.02; H, 10.21; N, 6.71.
EXAMPLE E
2-Amino-2-methyl-1-propyl octanoate hydrochloride (IIIe):
mp 106°-108°, ir (KBr) 2900, 1750 and 1175 cm -1 ; pmr (D 2 O) δ 4.2 (s, 2H), 2.5 (t, 2H), 1.5 (s, 6H), 1.2 - 1.8 (m, 10H) and 0.9 (t, 3H) ppm.
Anal. Calcd for C 12 H 26 ClNO 2 : C, 57.24; H, 10.41; N, 5.56. Found: C, 57.29; H, 10.52; N, 5.28.
EXAMPLE F
2-Amino-2-methyl-1-propyl nicotinate dihydrochloride (IIIf):
100 g (0.66 mol) Ethyl nicotinate and 88g (0.99 mol) 2-amino-2-methyl-1-propanol were mixed and heated together under reflux for 2 hours. The excess amino alcohol was removed by distillation, bp 50°-60° (1 mm). The yellow residue was recrystallized from ether-acetone to give 87.3 g (0.45 mol), 68%, N-(1-hydroxy-2-methyl-2-propyl) nicotinamide, mp 91°-93°; ir (KBr) 3385, 3200, 1665, and 1590 cm -1 ; pmr (CDCl 3 ) δ 8.8 - 7.3 (m, 4H), 6.7 (bs, 1H), 5.0 (s, 1H), 3.7 (s, 2H) and 1.4 (s, 6H) ppm.
Anal. Calcd for C 10 H 14 N 2 O 4 : C, 61.90; H, 7.23; N, 14.50. Found: C, 61.87; H, 7.26; N, 14.55.
A suspension of 73.3 g (0.38 mol) N-(1-hydroxy-2-methyl-2-propyl) nicotinamide in 300 ml of anhydrous hydrogen chloride in absolute ethanol (4 M) was heated under reflux for 2 hours. The ethanol was removed under reduced pressure to afford a semi-solid residue which crystallized from acetone on standing. The solid was isolated by filtration under a nitrogen atmosphere and was thoroughly washed with acetone. After drying in vacuo over calcium sulfate, 74 g (0.28 mol), 74%, IIIf, was obtained mp 215°-216° (dec); ir (KBr) 3200-2500, 1735, 1630 and 1600 cm -1 ; pmr (D 2 O) δ 9.5 (bs, 1H), 9.4-9.1 (m, 2H), 8.3 (q, 1H), 4.6 (s, 2H) and 1.6 (s, 6H) ppm.
Anal. Calcd for C 10 H 16 Cl 2 N 2 O 2 : C, 44.98; H, 5.99; N, 10.49. Found: C, 45.29; H, 6.15; N, 10.06.
EXAMPLE G
2-N,N-Dichloroamino-2-methyl-1-propyl acetate (IVa):
To 50 ml of 0.75 M sodium hypochlorite at 0° was added in portions over 5 minutes 3.19 g (0.019 mol) IIIa. The reaction mixture was adjusted to pH 4-6 by the addition of 1M HCl and the suspension was vigorously stirred at 0° for 1 hour. The N-chloramine was extracted into dichloromethane and the extracts combined and dried over anhydrous sodium sulfate. Following filtration, the dichloromethane was removed under reduced pressure to afford a dark yellow liquid. Distillation gave 2.0 g (0.010 mol), 55%, IVa, bp 55°-60° (0.4 mm), ir (neat) 1750, 1230 and 1040 cm -1 ; pmr (CDCl 3 ) δ 4.2 (s, 2H), 2.1 (s, 3H) and 1.4 (s, 6H) ppm.
Anal. Calcd for C 6 H 11 Cl 2 NO 2 : C, 36.02; H, 5.54; N, 7.00. Found: C, 36.40, H, 5.63; N, 6.90.
Using the procedure described for the preparation of IVa, the following 2-N,N-dichloroamino-2-methyl-1-propyl carboxylates were prepared:
EXAMPLE H
2-N,N-Dichloroamino-2-methyl-1-propyl butyrate (IVf):
bp 70°-75° (0.4 mm), ir (neat) 2940, 1740 and 1160 cm -1 ; pmr (CDCl 3 ) δ 4.3 (s, 2H), 2.4 (t, 2H), 1.7 (m, 2H), 1.4 (s, 6H) and 1.0 (t, 3H) ppm.
Anal. Calcd for C 8 H 15 Cl 2 NO 2 : C, 42.12; H, 6.63; N, 6.14. Found: C, 42.30; H, 6.60; N, 6.04.
EXAMPLE I
2-N,N-Dichloroamino-2-methyl-1-propyl 2,2-dimethylproprionate (IVg):
bp 67.5° - 68.5° (0.45 mm); ir (neat) 2990, 1740, 1475, 1360, 1270, and 1140 cm -1 ; pmr (CDCl 3 ) δ 4.3 (s, 2H), 1.4 (s, 6H) and 1.2 (s, 9H) ppm.
Anal. Calcd for C 9 H 17 Cl 2 NO 2 : c, 44.64; H, 7.08; N, 5.70. Found: C, 44.51; H, 7.11; N, 5.58.
EXAMPLE J
2-N,N-Dichloroamino-2-methyl-1-propyl hexanoate (IVh):
ir (neat) 2930, 2910, 2840, 1745 and 1155 cm -1 ; pmr (CDCl 3 ) δ 4.2 (s, 2H), 2.3 (t, 2H), 1.2-1.8 (m, 6H), 1.4 (s, 6H) and 0.9 (t, 3H) ppm.
Anal. Calcd for C 10 H 19 Cl 2 NO 2 : C, 46.88; H, 7.48; 5.47. Found: C, 46.90; H, 7.49; N, 5.22.
EXAMPLE K
2-N,N-Dichloroamino-2-methyl-1-propyloctanoate (IVi):
ir (neat) 2940, 2860, 1750 and 1150 cm -1 ; pmr (CDCl 3 ) δ 4.2 (s, 2H), 2.3 (t, 2H), 1.1-2.0 (m, 8H), 1.4 (s, 6H) and 0.9 (t, 3H) ppm.
Anal. Calcd for C 12 H 23 Cl 2 NO 2 : C, 50.71; H, 8.16; N, 4.93. Found: C, 50.38; H, 8.00; N, 4.70.
EXAMPLE L
2-N-Chloroamino-2-methyl-1-propyl butyrate (IVb):
To 50 ml of 0.75 M sodium hypochlorite at 0° was added in portions over 5 minutes 7.41 g (0.038 mol) IIIb. The suspension was vigorously stirred at 0° for 1 hour. The N-chloramine was extracted into dichloromethane and the extracts were combined and dried over anhydrous sodium sulfate. Following filtration, the dichloromethane was removed under reduced pressure to afford a pale yellow liquid. Distillation gave 5.2 g (0.027 mol) IVb, bp 60°-65° (0.4 mm); ir (neat) 3230, 2930, 1740 and 1160 cm -1 ; pmr (CDCl 3 ) δ 4.2 (s, 2H), 2.4 (t, 2H), 1.7 (m, 2H), 1.4 (s, 6H) and 1.0 (t, 3H) ppm.
Anal. Calcd for C 8 H 16 ClNO 2 : C, 49.61; H, 8.33; N, 7.23. Found: C, 49.00; H, 8.47; N, 6.94.
Using the procedure described for the preparation of IVb, the following 2-N-chloroamino-2-methyl-1-propyl carboxylates were prepared:
EXAMPLE M
2-N-Chloroamino-2-methyl-1-propyl 2,2-dimethylproprionate (IVc):
bp 61.5°-63° (0.45 mm); ir (neat) 3280, 2990, 1730, 1475, 1275 and 1140 cm -1 ; pmr (CDCl 3 ) δ 4.6 (bs, 1H), 4.0 (s, 2H), 1.3 (s, 9H) and 1.2 (s, 6H) ppm.
Anal. Calcd for C 9 H 18 ClNO 2 : C, 52.04; H, 8.73; N, 6.75. Found: C, 52.04; H, 8.70; N, 6.37.
EXAMPLE N
2-N-Chloroamino-2-methyl-1-propyl hexanoate (IVd):
ir (neat) 3240, 1745 and 1160 cm -1 ; pmr (CDCl 3 ) δ 4.5 (bs, 1H), 4.1 (s, 2H), 2.2 (t, 2H), 1.1-2.0 (m, 6H), 1.3 (s, 6H) and 1.0 (t, 3H) ppm.
Anal. Calcd for C 10 H 20 ClNO 2 : C, 54.16; H, 9.09; N, 6.32. Found: C, 55.04; H, 9.82; N, 6.70.
EXAMPLE O
2-N-Chloroamino-2-methyl-1-propyl octanoate (IVe):
ir (neat) 3260, 2920, 1740 and 1150 cm -1 ; pmr (CDCl 3 ) δ 4.5 (bs, 1H), 4.1 (s, 2H), 2.4 (t, 2H), 1.1-2.0 (m, 8H), 1.3 (s, 6H) and 0.9 (t, 3H) ppm.
Anal. Calcd for C 12 H 24 ClNO 2 : C, 57.70; H, 9.68; N, 5.61. Found: C, 57.14; H, 9.72; N, 5.39.
EXAMPLE P
2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate (IVj):
To 58 ml of 0.7 M sodium hypochlorite at 0° was added in portions over 10 minutes 5.32 g (0.02 mol) IIIf. After 0.5 hour at 0°, the pale yellow solid was isolated by filtration and thoroughly washed with cold water. The solid was dried in vacuo over calcium sulfate to give 3.7 g (0.014 mol), 70%, IVj, mp 53°-55°, sublimation at 50° (0.25 mm), ir (KBr) 3020, 3000, 1720, 1580, 1280, 1110, 720 and 670 cm -1 ; pmr (CDCl 3 ) δ 9.3 (s, 1H), 8.9 (d, 1H), 7.6-8.2 (m, 2H), 4.6 (s, 2H) and 1.5 (s, 6H) ppm.
Anal. Calcd for C 10 H 12 Cl 2 N 2 O 2 : C, 45.64; H, 4.60; N, 10.65. Found: C, 45.69; H, 4.71; N, 10.46.
EXAMPLE Q
2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate methylsulfate (IVk):
To 1.3 g (0.005 mol) IVj was added 0.63 g (0.005 mol) dimethyl sulfate. The mixture was heated at 60° under a nitrogen atmosphere for 2.5 hours. The solid mass was triturated with anhydrous ether. The solid was isolated by filtration under a nitrogen atmosphere and thoroughly washed with anhydrous ether. After drying in vacuo over calcium sulfate, 1.87 g (0.0048 mol), 93%, IVk was obtained mp 95°-100° (dec): ir (KBr) 3020, 2980, 1730, 1240, 1200, 1000 and 7.30 cm -1 ; pmr (D 2 O) δ 9.5 (s, 1H), 9.2 (d, 2H), 8.3 (t, 1H), 4.6 (s, 2H), 3.8 (s, 3H) and 1.6 (s, 6H) ppm; uv (H 2 O) λmax 303 nm, ε = 263 M -1 cm -1 .
Anal. Calcd for C 12 H 18 Cl 2 N 2 O 6 S: C, 37.02; H, 4.66; N, 7.20. Found: C, 36.84; H, 4.75; N, 6.92.
EXAMPLE R
2-N,N-Dichloroamino-2-methyl-1-propyl nicotinate methylfluorosulfonate (IVl):
To an ethereal solution containing 1.3 g (0.005 mol) IVj at 0° was added dropwise with stirring 0.57 g (0.005 mol) methylfluorosulfonate in 25 ml anhydrous ether. After stirring at room temperature 4 days, the yellow gummy mass was crystallized by repeated scratching at ambient temperature to a white solid. The solid was triturated with anhydrous ether and isolated by filtration under a nitrogen atmosphere. 1.32 g (0.0035 mol), 70%, IVl was obtained as an extremely hygroscopic white solid, mp (sealed) 112°-118° (dec); pmr (D 2 O) δ 9.4 (s, 1H), 9.0 (d, 2H), 8.2 (t, 1H), 4.6 (s, 2H), 4.5 (s, 3H) and 1.6 (s, 6H) ppm.
EXAMPLE S
2-Benzoylamino-2-methyl-1-propanol (1):
To a 250 ml dichloromethane solution containing 89 g (1.0 mol) 2-amino-2-methyl-1-propanol at 0° was added dropwise with stirring 70 g (0.5 mol) benzoyl chloride in 250 ml dichloromethane. The reaction mixture was warmed to room temperature and stirred for several hours. The 2-amino-2-methyl-1-propanol hydrochloride was removed from the reaction mixture by filtration and was thoroughly washed with dichloromethane. The filtrate and washings were combined and the dichloromethane removed under reduced pressure to afford 67.55 g (0.35 mol), 70%, 2-benzoylamino-2-methyl-1-propanol as a white solid, mp 80°-82°, sublimation at 75° (0.2 mm); ir (KBr) 1630 (c=o) cm -1 ; pmr (CDCl 3 ) δ 1.50 (s, 6H), 3.67 (s, 2H), 5.27 (bs, 1H), 6.92 (bs, 1H) and 7.1 - 8.3 (m, 5H) ppm.
Anal. Calcd for C 11 H 15 NO 2 : C, 68.37; H, 7.82; N, 7.25. Found: C, 68.47; H, 7.96; N, 7.20.
EXAMPLE T
2-Phenyl-4,4-dimethyl-1,3-oxazoline hydrochloride (2):
To 40 ml of freshly distilled thionyl chloride at 0° was added in portions over 15 minutes with stirring 3.86 g (0.02 mol) 2-benzoylamino-2-methyl-1-propanol. The solution was warmed to room temperature and heated under reflux for 2 hours. The thionyl chloride was removed under reduced pressure to afford a yellow oil which crystallized at 0° following the addition of anhydrous ether. The solid was triturated in anhydrous ether overnight and isolated by filtration under a nitrogen atmosphere. After drying in vacuo over calcium sulfate, 2.00 g (0.009 mol), 45%, 2-phenyl-4,4-dimethyl-1,3-oxazoline hydrochloride was obtained as a white solid, mp 149°-151°; ir (KBr) 1640 (c=N) cm -1 , pmr (D 2 O) δ 1.60 (s, 6H), 4.70 (s, 2H) and 7.3-8.2 (m, 5H) ppm.
Anal. Calcd for C 11 H 14 ClNO: C, 62.40; H, 6.68; N, 6.62. Found: C, 62.58; H, 6.53; N, 6.44.
EXAMPLE U
2-Amino-2-methyl-1-propyl benzoate hydrochloride (3):
To 8.7 g (0.041 mol) 2-phenyl-4,4-dimethyl-1,3-oxazoline hydrochloride suspended in 120 ml anhydrous hydrogen chloride in tetrahydrofuran (1M) was added 3.6 ml (0.20 mol) water. The mixture was warmed to cause solution and heated under reflux with stirring for 1 hour. The tetrahydrofuran was removed under reduced pressure to afford a nearly colorless oil which crystallized at 0° following the addition of anhydrous ether. The solid was triturated with anhydrous ether overnight and isolated by filtration under a nitrogen atmosphere. After drying in vacuo over calcium sulfate, 6.9 g (0.30 mol), 73%, 2-amino-2-methyl-1-propyl benzoate hydrochloride was obtained as a white solid, mp 225°-228° (dec.) acetone:hexane, ir (KBr) 1725 (c=o) cm -1 , pmr (D 2 O) δ 1.50 (s, 6H), 4.4 (s, 2H) and 7.0-8.3 (m, 5H) ppm.
Anal. Calcd for C 11 H 16 ClNO 2 : C, 57.51; H, 7.02; N, 6.10. Found: C, 57.73; H, 6.77; N, 6.05.
EXAMPLE V__________________________________________________________________________MINIMAL INHIBITORY CONCENTRATION OF 2-AMINO-2-METHYL-1-PROPYLCARBOXYLATESCompound S. aureus S. pyogenes E. coli K. pneumoniae P. aeruginosa A. niger C. albicans T.__________________________________________________________________________ mentagrophytesIV a > 62.5.sup.b 62.5 > 62.5 > 62.5 62.5 > 62.5 > 62.5 62.5III b > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5IV b > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5IV f > 62.5 62.5 > 62.5 > 62.5 62.5 > 62.5 > 62.5 > 62.5IV c >250 >125 >250 >250 >250 >250 >250 >250IV g 250 250 >125 >125 250 >125 >125 >125III d > 62.5 62.5 > 62.5 > 62.5 62.5 > 62.5 > 62.5 > 62.5IV d > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5IV h > 62.5 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 62.5III e > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5IV e > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5IV i 62.5 62.5 > 62.5 > 62.5 > 62.5 > 62.5 > 62.5 62.5IV k >250 >250 >250 >250 >250 125 >250 125__________________________________________________________________________ .sup.a Minimal inhibitory concentration expressed in parts per million (ppm) of compound. .sup.b Greater than (>) indicates that the solvent content in the dilutio sequence inhibited the test organism at the higher concentrations.
EXAMPLE W__________________________________________________________________________CONTACT GERMICIDAL EFFICIENCY OF2-AMINO-2-METHYL-1-PROPYL CARBOXYLATESConcentration.sup.b Sterilization Time.sup.a (Minutes)Compound PPM, PMCl.sup.+ S. aureus S. pyogenes E. coli S. typhimurium B. subtilis__________________________________________________________________________IV a 1292, 458 5 2.5 0.5 2.5 2.5III b 1070, >60 >60 >60 >60 >60IV b 2078, 380 2.5 0.5 0.5 2.5 2.5IV f 979, 304 2.5 0.5 0.5 2.5 0.5IV c 1886, 323 5 0.5 0.5 2.5 2.5IV g 409, 120 5 2.5 2.5 5 2.5III d 1037 >60 >60 >60 >60 >60IV d 1319, 211 2.5 0.5 2.5 5 2.5IV h 95, 26 10 2.5 10 10 2.5III e 1040 >60 30 15 30 5IV e 300, 43 10 2.5 5 10 0.5IV i 85, 21 15 5 10 10 2.5__________________________________________________________________________ .sup.a Time intervals screened 0.5, 2.5, 5, 10, 15, 30, 45 and 60 minutes .sup.b Solubility in 30% methanol: 0.1 M sodium dihydrogen phosphate, pH 7.0.
EXAMPLE X__________________________________________________________________________CONTACT GERMICIDAL EFFICIENCY OF N-CHLORAMINES AS A FUNCTIONOF THE SOLUTION pH IN THE ABSENCE OF HORSE SERUMConcentration Sterilization Time.sup.a (Minutes)Compound PPM PPMCl.sup.+ pH S. epidermidis S. aureus E. coli K. pneumoniae P. aeruginosa B. bronchiseptica__________________________________________________________________________ 404 69 4.6 0.5 1 0.5 0.5 0.5 0.5IV c 1886 323 7.0 3 4 0.5 2 1 1 1704 292 9.3 4 3 1 2 1 1 489 143 4.6 0.5 2 0.5 0.5 0.5 1IV g 409 120 7.0 2 4 1 3 0.5 2 319 94 9.3 2 2 1 2 0.5 2__________________________________________________________________________ .sup.a Time intervals screened 0.5, 1, 2, 3, 4 and 5 minutes.
EXAMPLE Y__________________________________________________________________________CONTACT GERMICIDAL EFFICIENCY OF N-CHLORAMINES AS A FUNCTION OFTHE SOLUTION pH IN THE PRESENCE OF HORSE SERUMConcentration Sterilization Time.sup.a (Minutes)Compound PPM PPMCl.sup.+ pH S. epidermidis S. aureus E. coli K. pneumoniae P. aeruginosa B. bronchiseptica__________________________________________________________________________IV c 468 80 4.6 >10 >10 >10 >10 >10 >10__________________________________________________________________________ .sup.a Time intervals screened 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 minutes unless otherwise noted.
EXAMPLE Z__________________________________________________________________________CONTACT GERMICIDAL EFFICIENCY OF N-CHLORAMINESCONTAINING A POSITIVE CHARGECom- Sterilization Time (Minutes)pound Concentration S. pidermidis S. aureus E. coli K. pneumoniae P. aeruginosa B. bronchiseptica__________________________________________________________________________In the Absence of Horse Serum:.sup.a PPM PPMCl.sup.+ pHIV j 79 21 4.6 3 5 2 1 2 4IV k 5800 1057 4.6 4 5 1 2 2 1IV l 1112 209 4.6 3 5 1 5 3 5In the Presence of Horse Serum:.sup.b PPM PPMCl.sup.+ pHIV k 5800 1057 4.6 4 6 0.5 2 2 2__________________________________________________________________________ .sup.a Time intervals screened 0.5, 1, 2, 3, 4, and 5 minutes. .sup.b Time intervals screened 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 minutes.
THE ANTIBACTERIAL SCREEN - EXAMPLE V
Test Solution
Immediately preceding the screen, the compound is weighed and diluted with a buffer or other solvent to give the final concentration desired. The buffer or solvent chosen depends on the conditions of the screen and could be one of the following: 0.1 M NaOAc, pH 4.6; 0.1 M NaH 2 PO 4 , pH 7.0; 0.1 M Na 2 B 4 O 7 , pH 8.8; 35% methanol in one of the aforementioned buffers; 10% Triton × 100 in buffer, etc.
The positive chlorine concentration of the test solution is then determined iodometrically.
Cultures and Media
Media used for the Screen are Nutrient Broth, BBL# 11479 and Nutrient Agar, BBL# 11472 prepared according to label directions. The broth is dispensed in 75 ml amounts of flasks for overnight cultures and in 5 ml amounts to culture tubes for subculturing during the Screen. Agar plates are prepared as usual.
Overnight cultures are prepared by inoculating from stock cultures into the 75 ml flasks of nutrient broth and incubating for 15 hours at 37° C.
The organisms ordinarily screened are:
______________________________________Streptococcus pyogenes ATCC# 19615Aspergillus niger ATCC# 6538Candida albicans ATCC# 10231Pseudomonas aeruginosa ATCC# 9027Klebsiella pneumoniae ATCC# 10031Escherichia coli ATCC# 10536Trichophyton mentagrophytes ATCC# 9129______________________________________
The organisms are maintained as stock cultures on nutrient agar at 4° C. They are transferred and checked for purity monthly.
Procedure
The iodometrically characterized test solution is dispensed in 5 ml amounts to seven small stoppered flasks. The organisms are screened one at a time as follows:
A 0.2 ml portion of the overnight culture is inoculated into 5 ml of 0.9% NaCl for use in controls. A 0.2 ml portion of the overnight culture is inoculated into a flask containing 5 ml of the test solution, an automatic timer is simultaneously triggered and the solution mixed. At time intervals of 30 seconds, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 minutes a loopful of the inoculated solution is subcultured into 5 ml of sterile nutrient broth and mixed by a Vortex Genie Mixer, the high dilution serving to stop the action of the compound. At the end of the ten minute screen, the entire procedure is repeated for each of the remaining six organisms. All of the subculture tubes are incubated at 37° C and checked for signs of growth by turbidity at 24 hr., 48 hr., 3, 5, and 7 days. The earliest subculture time at which no growth is present in the subculture tube is considered the endpoint and is recorded as that time, e.g., 7 minutes.
Controls
Viability of Stock Cultures
0.2 ml of the stock culture is transferred to 5 ml of saline (to simulate 0.2 ml in 5 ml test solution). A loopful of this mixture is subcultured to 5 ml of nutrient broth as in the Screen and incubated at 37° C for 24 hr. Turbidity indicates that the organism would grow when not in the presence of the test solution.
Purity of Stock Cultures
A loopful of the stock culture in saline is streaked onto nutrient agar to insure the purity and identity of each culture (the cultures are also checked biochemically each month for this purpose).
Dilution of the Test Solution
A loopful of the test solution is diluted in a 5 ml amount of nutrient broth. A loopful of the organism in saline is inoculated into this tube. Turbidity after 24 hr. at 37° C indicates that the dilution of the test solution in the nutrient broth subculture during the Screen is great enough to stop the action of the compound.
Purity of Organisms in Test Solution
At the end of the Screen a loopful of the organism-test solution mixture is streaked onto nutrient agar to insure that contamination has not occurred during the 10 minute period of the Screen. Often there is no growth at this time if the compound has effectively inhibited all the organisms.
Lack of Bacteriacidal Activity of Buffers and Other Solvents
Before a buffer or other solvent is used as the diluent, it is screened against the organisms Staphylococcus aureus, ATCC# 6538 and Escherichia coli ATCC# 10536 (the `strongest` and `weakest` of the organisms) to insure that the buffer or solvent has no antibacterial activity in itself. Subculture times of 10, 20 and 30 minutes are used. Incubation conditions are the same.
Variations
Serum as a Denaturant of the Compound
The test solution is prepared and characterized as above but is made up at twice the concentration desired. The solution is diluted 1:1 with Rehydrated Tissue Culture Dessicated Horse Serum, Difco #5357-72 and dispensed in a 5 ml amount to a small flask. The mixture is incubated at Room Temperature for 30 minutes to allow denaturation of the compound by the serum and then screened as above.
The 5 ml mixture of serum and test solution are prepared in sequence to allow as close to 30 minutes as possible before the beginning of the screen of each organism.
Variation of Conditions
Each new compound is generally screened several times at different concentrations, different pH's, in different solvents and at each of those conditions with and without serum as a denaturant.
THE ANTIBACTERIAL SCREEN - EXAMPLES W - Z (Autotiter IV)
Program I. In vitro antimicrobial screen
1. Methodologies
(a) Compounds. All compounds to be screened are weighed (approx. 10 mg) on the day preceding the test date. Each compound is solubilized on the day of assay in appropriate solvent and diluted automatically in the Autotiter IV with distilled water (buffer can be employed here also).
(b) Organisms.
Bacteria: Staphylococcus aureas Smith (or 209), Escherichia coli AB 1932-1, 1100/B22 and Vogel, Streptococcus pyogenes C203 Salmonella typhimurium 14028, Bacillus subtilis 6051-1, Klebsiella pneumoniae 10031, Pseudomonas aeruginosa 9027, Bordetella bronchiseptica 4617 and Staphylococcus epidermidis 12228.
(c) Inocula. Prior to utilization in the Autotiter IV, all bacteria are cultured for 18-20 hr. (37° C) in tryptose phosphate broth (TP), except, S. pyogenes C203, which is cultured in Brain Heart Infusion broth plus 10% normal horse serum. Immediately prior to testing, each culture is adjusted to an optical density of 0.10 (650 nm), employing a Bausch & Lomb Spectronic 20, and diluted subsequently into double strength medium to approximately 2 × 10 5 viable organisms per ml.
(d) Program for Routine Testing.
1. An automated injector system dispenses 0.05 ml of diluent (sterile H 2 O or buffer) to all cups of the autotiter trays from rows 2 through 7.
2. The loops (for sequential dilutions of the compounds are moistened by immersion into 70% ethyl alcohol. After removal of excess alcohol by blotting, the loops are moved to the first row of cups in the autotray containing 0.10 ml of the compound to be diluted and tested (usually, this initial concentration is 500 to 1000 mcg/ml, but can be varied upward or downward). The loops are lowered and sequentially transfer the diluted solutions of the compound through row 7.
Immediately after each dilution is made, each cup is automatically inoculated with 0.05 ml of the appropriate test organism. This inoculation derives from a second injector system containing the organism in double-strength medium. The total operation consists of the automatic dilution of a single compound in each of 8 rows of the Autotiter try.
After these operations, we reverse the tray and a second compound is diluted over the other one-half of the tray and inoculated, subsequently, with 8 organisms. Thus, for each Autotiter Tray, two compounds are screened against 8 different organisms at dilutions ranging from 1:2 to 1:128.
(e) Incubation. The inoculated Autotiter trays are incubated at 37° C for 18 - 20 hr. At the end of this period, each tray is examined for the presence or absence of growth (turbidity). The lowest concentration of the compound inhibiting growth is recorded as the minimal inhibitory concentration (MIC).
Yeast and fungi are tested in the same manner except that (i) Maltose Peptone broth is employed and (ii) the Autotiter trays are sealed with plastic tape during the incubation period (25° C/5 days) to prevent evaporation.
The compounds of the present invention find wide application as antibacterial agents per se, in aqueous solution, or in such preparations as mouthwashes, shampoos, soaps, cosmetic bases and the like. Such formulations can be prepared in accordance with any of the described procedures disclosed in "REMINGTON's PHARMACEUTICAL SCIENCES" (Fourteenth Edition) 1970. Naturally, the antibacterial effective amount required for a compound of this invention will vary with the microorganism in question.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. As such, such changes and modifications are properly, equitably, and intended to be, within the rull range of equivalence of the following claims. | There is provided, a novel class of compounds exhibiting antibacterial activity and having the formula: ##STR1## wherein X and Y each represent a member which may be the same or different selected from the group consisting of H and Cl with the proviso that X and Y cannot represent H simultaneously; R 1 and R 2 each represent a member which may be the same or different selected from the group consisting of an n- or branched alkyl group of from 1 to 20 carbon atoms, an aryl group (phenyl, naphthyl, etc.) and a ##STR2## WHEREIN M REPRESENTS AN INTEGER OF FROM 2 TO 5; N REPRESENTS AN INTEGER OF 1 TO 8; AND Z represents a member selected from the group consisting of an --OOCR 3 group, an --OR 3 group and an --OCH 2 OR 3 group, wherein R 3 represents a member selected from the group consisting of an n- or branched alkyl group of 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a benzyl group, ##STR3## WHEREIN X is a halogen atom (Cl, Br, I), ##STR4## WHEREIN R 4 represents a member selected from the group consisting of H, an n- or branched alkyl group, a benzyl group, and a --(CH 2 ) p COOH group, wherein p represents an integer of 1 to 4, and wherein W.sup.θ represents a non-toxic pharmaceutically acceptable inorganic or organic anion. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a United States National Phase application of International Application PCT/EP2011/067544 filed Oct. 7, 2011, and claims the benefit of priority under 35 U.S.C. §119 of German Utility Model DE 20 2010 008 748.1 filed Oct. 7, 2010, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention pertains to a laying device and a laying method for a material to be laid, especially a fibrous formed web with a prevailing fiber orientation, wherein the laying device has a material feeding means, a laying unit and a discharge device.
BACKGROUND OF THE INVENTION
[0003] Nonwoven laying devices for forming a multilayered nonwoven on a discharge belt are known from practice, wherein the nonwoven laying unit lays formed web being fed continuously in mutually overlapping layers on the discharge belt. Such a laying device is designed as a nonwoven laying device, wherein the discharge belt is moving during the laying of the formed web, with the consequence that the laid formed web layers show mutually crossing oblique alignments with layer formation in a zigzag pattern. The fibers may have a prevailing alignment in the formed web being fed, and they have, e.g., a prevailing direction component in the longitudinal extension and direction of run of the formed web being fed. These fiber orientations cross each other in the nonwoven, and the crossing angle is an obtuse angle greater than 90° because of the narrow closure of the layers.
[0004] It is known from U.S. Pat. No. 5,476,703 A that this crossing angle of the fiber orientations and also of the longitudinal extension of the laid formed web layers can be changed by a stretching means arranged downstream of the nonwoven laying device, which stretches the nonwoven and reduces the crossing angle in the process.
[0005] It is, furthermore, known from U.S. Pat. No. 5,454,145 A that the stretched nonwoven can be fed to another nonwoven laying device and another, new nonwoven material with multiply crossed fiber orientation can be formed on the discharge belt thereof by laying in a zigzag and scale-like pattern.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide an improved laying device and technique.
[0007] According to the invention, a laying device is provided for a material to be laid, especially a fibrous formed web with a prevailing fiber orientation. The laying device has a material feeding means, a laying unit and a discharge device. The laying device lays material layers, especially formed web layers, in the discharge direction separately from each other or overlapping each other to form a single-layer or multilayered nonwoven material on the discharge device. The laying device lays the material layers with constant alignment and fiber orientation on the discharge device.
[0008] The laying technique according to the invention has the advantage that nonwoven materials with a more uniform fiber orientation can be formed. Such nonwoven materials can have special strength properties that depend on the fiber orientation. It is favorable for this if the layers of the material or formed web to be laid have the same alignment of the layers and the same prevailing fiber orientations in the nonwoven material. The alignment of the prevailing fiber orientation can be adapted to the needs and set, with the alignment angle between the direction of laying or direction of feed and the direction of discharge being set correspondingly.
[0009] It is favorable for this form of material laying, especially formed web laying, and the formation of the nonwoven material if the material or formed web layers to be laid are separated from each other. This separation may take place before the laying on the discharge device, preferably in the area of the laying unit. A contiguous material or formed web can be fed on the inlet side and possibly stored in front of or within the laying unit. It is favorable for a constant alignment of the material or formed web layers to be laid if the discharge device is not moving during this laying operation. Laying may then be a defined one-dimensional transfer motion. A lifting means may now shorten the distance.
[0010] The laying technique being claimed has the advantage that highly sensitive material and formed web layers are handled especially gently. Disturbances in these layers during the transportation and deposition or transfer operation and corresponding adverse effects on the type and alignment of the laid material and formed web layers can be avoided.
[0011] Special advantages are offered by a laying technique with a nonwoven laying device and with an intermediate carrier arranged downstream, wherein said nonwoven laying device can ensure the intermediate storage of the material fed to it. The intermediate carrier may have a take-up side and a discharge side located opposite, wherein the cutting of a material or formed web being fed possibly continuously into individual pieces of material or formed web layers can take place in the area of the intermediate carrier, which is especially favorable for the accurate positioning and laying of the individual material or formed web layers. The intermediate carrier makes it possible to take up material or formed web already cut into individual pieces with a rolling motion on the feed or take-up side, to accurately position same on the discharge side and to transfer them by a one-dimensional laying motion at the discharge device with little need for aiming and little disturbance. The deposited material or fibrous formed web can be held in the intermediate carrier in a suitable manner in a controlled manner, for which a suction means is favorable. The material or formed web layers discharged and the single-layer or multilayered nonwoven material formed hereby can likewise be fixed in a suitable matter on the discharge device, especially by suction.
[0012] The laying technique being claimed has the advantage of high precision of laying in conjunction with a high level of freedom from disturbance. The construction and control effort is comparatively low. In addition, the possibility of handling different materials to be laid, especially fibrous formed webs, and to lay them to form a nonwoven material, is favorable. The desired fiber orientation can be set due to a variable alignment of the discharge device.
[0013] Furthermore, a plurality of laying units can be arranged one after another at a common discharge device, and these devices may also have different alignment angles. As a result, crosswise fiber orientations that may be desired can be set especially accurately. In addition, other materials to be laid, e.g., a reinforcing means in the form of webs, grids or the like, or other structure layers for building up the nonwoven material, can be inserted here in a specific manner and with little effort.
[0014] The laying technique being claimed meets the requirements imposed by modern, high-performance materials, especially carbon fibers or the like, and of technical nonwovens formed herefrom, which possess defined properties, in terms of precision especially well. In particular, such nonwovens can have, thanks to their exactly defined properties, especially their strength characteristics, a lower thickness than nonwoven materials used previously, which have more or less unordered fiber orientations, and the corresponding weight is reduced as well. This broadens and improves the possibilities of using such nonwoven materials, e.g., in the manufacture of automobiles and aircraft. Such nonwoven materials are also especially suitable for composites, in which case the nonwoven material is, e.g., bonded, especially impregnated with a synthetic resin or another suitable material before or during the process.
[0015] The laying device being claimed may be used as an individual device or as part of a fiber plant and in connection with an upstream formed web generator and a downstream bonding means for the nonwoven material.
[0016] The present invention is schematically shown in the drawings as an example. The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which preferred embodiments of the invention are illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In the drawings:
[0018] FIG. 1 is a schematic top view of a fiber plant with a laying device, a formed web generator and a bonding means;
[0019] FIG. 2 is a schematic side view showing a laying device with a nonwoven laying unit with an intermediate carrier in one of different operating positions;
[0020] FIG. 3 is a schematic side view showing a laying device with a nonwoven laying unit with an intermediate carrier in another of different operating positions;
[0021] FIG. 4 is an enlarged and cut-away view of the intermediate carrier according to FIG. 2 ;
[0022] FIG. 5 is an enlarged and cut-away view of the intermediate carrier according to FIG. 3 ; and
[0023] FIG. 6 is a top view of a laying device with representation of a prevailing fiber orientation and different crossing angles.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring to the drawings in particular, the present invention pertains to a laying device ( 2 ) for a material ( 5 ) to be laid as well as a fiber plant ( 1 ) with such a laying device ( 2 ). The present invention pertains, furthermore, to a method for laying materials to be laid ( 5 ), especially fibrous formed webs, and for setting fiber orientations in a nonwoven material ( 8 ).
[0025] FIG. 1 schematically shows a fiber plant ( 1 ) with a laying device ( 2 ), with a plurality of material generators ( 3 ), especially formed web generators, and with a bonding means ( 4 ). The laying device ( 2 ) may have one or more laying units ( 16 , 17 ) and one or more discharge device ( 18 ). Two laying units ( 16 , 17 ) for identical or different materials ( 5 , 37 ) to be laid are connected to a common discharge device ( 18 ) in the embodiment being shown. Furthermore, a feeding means ( 14 ), with which the material ( 5 , 37 ) to be laid, which is arriving from the material or formed web generator ( 3 ) is fed in the direction of run ( 7 ), is associated with each laying unit ( 16 , 17 ). The discharge device ( 18 ) has a preferably straight extension and a discharge direction ( 13 ) directed along its course.
[0026] The material to be laid ( 5 , 37 ) is fed preferably continuously and in a running or closed or contiguous material web. As an alternative, intermittent and, e.g., piece-by-piece feed is possible.
[0027] The laying unit ( 16 , 17 ) is used to lay the material to be laid ( 5 , 37 ) at the discharge device ( 18 ) and to form a nonwoven material ( 8 ) in the process. For this, the laying unit ( 16 , 17 ) places a plurality of material layers, especially formed web layers ( 9 ), on the discharge device ( 18 ) one after the other in the discharge direction ( 13 ). The nonwoven material ( 8 ) may be a multilayered material, and a plurality of these material or formed web layers are arranged one on top of another with overlap and with a longitudinal offset. Scale-like laying with closure of the layers is obtained hereby. As an alternative, the material layers ( 9 ) may be arranged individually and one after another and optionally at an axially spaced location to form a single-layer nonwoven material ( 8 ).
[0028] The laying unit ( 16 , 17 ) has a laying direction ( 7 ), in which it lays the material or formed web layer ( 9 ) on the discharge device ( 18 ). The laying direction preferably coincides with the direction of feed ( 7 ). There may be a selectable alignment angle (α, β) between the laying direction ( 7 ) and the discharge direction ( 13 ) as well as between the laying unit ( 16 , 17 ) and the discharge device ( 18 ). As is illustrated in FIG. 6 , the devices ( 16 , 17 , 18 ) may optionally be rotated about an axis relative to one another. The alignment angle (α, β) may equal, e.g., 90°. The alignment angle (α, β) differs from 90° in the embodiments being shown, so that the material or formed web layers to be laid are aligned obliquely to the discharge device ( 8 ).
[0029] The material or formed web layers ( 9 ) may be separated from one another and isolated from one another prior to laying. A cutting means ( 19 ) may be present for this at a suitable location and have a suitable design. The material to be laid ( 5 , 37 ), which is fed on the inlet side, may form a contiguous web, especially a formed web, from which said material or formed web layers ( 9 ) are separated while forming individual pieces. This separation may take place in front of the laying unit ( 16 , 17 ) or within the laying unit ( 16 , 17 ).
[0030] The material to be laid ( 5 , 37 ) may have the same design or different designs. In the exemplary embodiment being shown, the material to be laid ( 5 ), which is arriving from a first formed web generator ( 3 ), especially from a carder, is a fibrous formed web, which has a cotton wool-like form and consists of short-cut fibers, so-called stable fibers. The fibrous materials can be selected as desired. They may be, e.g., industrial fibers, especially carbon fibers, fibers made of plastics or natural fibers from cotton or the like. The fibrous formed web ( 5 ) may also contain other additional materials, e.g., metal filaments or the like.
[0031] As is illustrated in FIGS. 1 and 6 , there may be a prevailing fiber orientation ( 6 ) in the material to be laid ( 5 ), especially the fibrous formed web. For example, the majority of fibers have here essentially the same direction component, which is directed, e.g., along the direction of feed ( 7 ) or in the longitudinal direction of the formed web. It is not necessary for all fibers to have the same alignment to be in parallel to one another. They may assume oblique positions and mutually hook into one another. There also may be some transversely directed fibers.
[0032] Another material to be laid ( 37 ), indicated in FIG. 1 , may be, e.g., a web or a grid, which possibly also has a prevailing structure direction or orientation. Such a web ( 37 ) or grid may consist of textile fiber materials, metal, plastic or other materials. The material to be laid ( 37 ) may reinforce for this, e.g., a nonwoven material ( 8 ) consisting mainly of fibers or it may confer desired physical properties on it in another manner. The material generator ( 3 ) may have a corresponding design. A material or formed web generator is defined such that it also includes, besides means for producing said material to be laid ( 5 , 37 ), feeding means, with which, e.g., a material to be deposited, which is produced in another manner, is prepared and fed in.
[0033] In a variant of FIG. 1 shown, the second or any further material to be laid ( 37 ) that is fed in may also be an identical fibrous formed web or a different fibrous formed web, which may have the same prevailing fiber orientation ( 6 ) or a different prevailing fiber orientation ( 6 ).
[0034] As is illustrated in FIGS. 1 and 6 , the laying unit ( 16 , 17 ) lays the material or formed web layers ( 9 ) with constant alignment and fiber orientation ( 6 ) on the discharge device ( 18 ). The material or formed web layers ( 9 ) thus have consistently the same alignment within the nonwoven material ( 8 ) being laid here. Furthermore, the laid nonwoven ( 8 ) and its material or formed web layers ( 9 ) may have the same prevailing fiber orientation ( 6 ). A selectable angle, which can be set by the above-mentioned alignment angle (α, β), may be present between the longitudinal extension of the nonwoven material ( 8 ) and the fiber orientation ( 6 ).
[0035] If a plurality of laying units ( 16 , 17 ) lay material and formed web layers ( 9 ) one after another on the discharge device ( 18 ), the alignment of these layers and the fiber orientation ( 6 ) may be the same. FIG. 1 shows a variant, in which the first laying unit ( 16 ) has an alignment angle (α) and the second laying unit ( 17 ) has a different alignment angle (β). Layer alignments and fiber orientations ( 6 ) that cross each other can be set as a result with a selectable angle correlation.
[0036] The discharge device ( 18 ) may have any desired and suitable design. In the exemplary embodiment being shown, it has a frame with a suitable conveying means ( 32 ), e.g., an endlessly running discharge belt. The discharge device ( 18 ) may have a controllable drive, which is preferably stopped during the material and formed web laying. The material or formed web laying by the laying device or laying units ( 16 , 17 ) may take place intermittently and especially cyclically, and during the pauses between layings, when a new material and formed web layer ( 9 ) is formed or made ready, the discharge device ( 18 ) performed a delivering motion in the discharge direction ( 13 ). FIG. 2 shows the discharge device ( 18 ) in an oblique alignment in relation to the nonwoven laying unit ( 21 ) or the laying unit ( 16 , 17 ). FIG. 3 shows, in a variation hereto, a transverse direction with an alignment angle (α, β) of 90°.
[0037] The discharge device ( 18 ) may have, furthermore, a holding means ( 38 ) for the material and formed web layers ( 9 ) as well as the nonwoven material ( 8 ). This may have any desired and suitable design, e.g., in the form of a suction means, wherein suction takes place under the conveying means or discharge belt ( 32 ), which is correspondingly permeable to air. Furthermore, a cutting means for trimming the edges of the nonwoven material may be present at the discharge device ( 18 ).
[0038] The laying unit ( 16 , 17 ) may have various designs. FIGS. 2 and 3 show a preferred embodiment with a design as a nonwoven laying unit ( 21 ). This may have a plurality of carriages ( 24 , 25 , 26 ) and a plurality of, especially two conveyor belts ( 22 , 23 ) driven to run endlessly, which are each arranged in a closed loop and which extend, at least in some areas, closely adjacent to one another, and they take up and guide the material to be laid ( 5 , 37 ) that is fed in between them in that area. The conveyor belts ( 22 , 23 ) are guided via drivable rollers at the carriages ( 24 , 25 , 26 ).
[0039] At least one part of the carriages ( 24 , 25 , 26 ) is mounted displaceably on a machine frame and suitable guides in the direction of feed and laying direction ( 7 ). The nonwoven laying unit ( 21 ) is designed as a so-called belt type nonwoven laying unit and has a traveling upper carriage ( 24 ), at which the conveyor belts ( 22 , 23 ), arriving from different directions, are merged. The material to be laid ( 5 , 37 ), arriving from the feeding means ( 14 ), is taken up on one conveyor belt ( 22 ). The conveyor belts ( 22 , 23 ) may be guided via one or more, especially two auxiliary carriages ( 26 ), which are likewise displaceable in direction ( 7 ), and with which differences in length are compensated in the belt loops formed. The conveying or laying belts ( 22 , 23 ) are led in a parallel position with the material to be laid ( 5 ), which is being guided between them, to an adjacent lower carriage or laying carriage ( 25 ), at which the conveying or laying belts ( 22 , 23 ) are again separated from each other and led away on both sides, with the material to be laid ( 5 ), which is released, exits downwardly at the laying carriage ( 25 ). The laying carriage ( 25 ) may likewise be displaceable in direction ( 7 ). As an alternative, it may be arranged stationarily.
[0040] The nonwoven laying unit ( 21 ) discharges the material to be laid ( 5 , 37 ) intermittently and cyclically, and the discharge device ( 18 ) performs a delivery motion during the pauses between layings and discharges. If the material to be laid ( 5 ) is being fed constantly on the inlet side, the laying device ( 2 ) has a storage means ( 15 ), which intermediately stores the material to be laid ( 5 ) during said pauses between layings. The material storage means ( 15 ) is formed in the embodiment shown by a conveyor belt section ( 27 ), which has a variable length. A first partial section is formed by the conveyor belt ( 22 ) between the upper carriage ( 24 ) and the material input site or the connection site to the feeding means ( 14 ). The second variable partial section is formed between the two main carriages ( 24 , 25 ). FIGS. 2 and 3 illustrate that the length of the belt section ( 27 ) and hence the size of the material storage means ( 17 ) is changed by the travel of the upper carriage ( 24 ), and the auxiliary carriage or carriages ( 26 ) takes (take) up the correspondingly varying remaining belt loop length. The carriages ( 24 , 25 , 26 ) and the laying belts ( 22 , 23 ) have suitable controllable drives.
[0041] In another embodiment, not shown, a material or formed web storage means may be arranged in front of the laying unit ( 16 , 17 ), e.g., in the area of feed unit ( 14 ).
[0042] In one embodiment, not shown, the nonwoven laying unit ( 21 ) can lay the material to be laid ( 5 , 37 ), which is being discharged at a traveling laying carriage ( 25 ), directly onto the discharge device. A cutting means ( 19 ) may be arranged here in the area of the laying carriage ( 25 ) or at another location within or in front of the laying unit ( 16 , 17 ). Laying carriage ( 25 ) travels back and forth in the laying direction ( 7 ) via the discharge device ( 18 ), stopping at the ends of its travel path, and the discharge of material at the laying carriage ( 25 ) is stopped, and a material to be laid ( 5 , 37 ), which is being fed continuously, is taken up in the storage means ( 15 ) and then emptied during the next motion of the laying carriage. Laying carriage ( 25 ) can lay material or formed web layers ( 9 ) during forward and reverse travel. As an alternative, it can lay in one direction of travel only, and the material storage means ( 15 ) is being filled during travel in the opposite direction. Intermittent or cyclic laying takes place on the discharge device ( 18 ) in the different variants.
[0043] FIGS. 2 and 3 show a variant of the laying unit ( 16 , 17 ), in which an intermediate carrier ( 20 ), which takes up the material to be laid ( 5 , 37 ) exiting at the laying carriage ( 25 ), which is stationary here, in a take-up area ( 35 ) located at the top and releases same to the discharge device ( 18 ) in a discharge area ( 36 ) located at the bottom, is arranged between the nonwoven laying unit ( 21 ) and the discharge device ( 18 ). A lifting means ( 31 ), which is associated, e.g., with the discharge device ( 18 ), may be present here for mutually approaching the intermediate carrier ( 20 ) and the discharge device ( 18 ).
[0044] FIGS. 4 and 5 show details of the intermediate carrier ( 20 ) in different operating positions and in a cut-away and shortened front view.
[0045] Intermediate carrier ( 20 ) may be arranged stationarily or in a vertically adjustable manner by means of said lifting means ( 31 ). It comprises a frame ( 28 ) with a conveying means ( 29 ) for taking up and for conveying the material to be laid ( 5 , 37 ) or a material or formed web layer ( 9 ). Conveying means ( 29 ) may be designed, e.g., as a conveyor belt running endlessly around the box-shaped frame ( 28 ) on the outside and have a controllable drive. An upper and a lower deflection means ( 34 , 35 ) may be present for the conveying means ( 29 ) on one side of the frame, on which the material to be laid ( 5 , 37 ) is led around, with the lower deflection means ( 34 ) projecting farther radially than the upper deflecting means ( 33 ), as a result of which a conveyor belt section dropping obliquely towards the outside is formed.
[0046] Intermediate carrier ( 20 ) may have a holding means ( 30 ), which is arranged, e.g., in frame ( 22 ) and can fix and release the material to be laid ( 5 , 37 ) in a controlled manner. Holding means ( 30 ) may be designed, e.g., as a controllable suction means, in which case conveying means ( 29 ) and possibly also deflecting means ( 33 , 34 ) are designed as means that are permeable to air. It may also be a multipart or variable means in order to be able to act differently on different areas of the intermediate carrier.
[0047] A cutting means ( 19 ), which forms a separated material or formed web layer ( 9 ) from the fed web-like material to be laid ( 5 , 37 ), is arranged at the intermediate carrier ( 20 ) in this exemplary embodiment. Cutting means ( 19 ) may have various designs, e.g., it may be designed as a cutting means or as a tearing means. FIGS. 4 and 5 show both variants.
[0048] FIG. 4 shows one variant of a cutting means, wherein said cutting means ( 19 ) is located at the above-mentioned oblique belt section between the deflecting means ( 33 , 34 ). The cutting means lifts off the material to be laid ( 5 , 37 ) here from the conveyor belt section, forming a loop or a buckle, in which a cutting tool, e.g., a rotating knife, can cut through the material web ( 5 ) lying free. A pulling cut may take place here, as a result of which the material or formed web layer ( 9 ) will have an oblique edge. The cutting operation may happen during the conveying of the material.
[0049] In the variant according to FIG. 5 , the cutting means ( 19 ) is designed as a tearing means and is located on the underside of the intermediate carrier ( 20 ). It may comprise, e.g., two clamping bars or other clamping or gripping means, which grip the material to be laid ( 5 ) and move apart from one another, while the material web is stretched and torn apart. The bars or the like may be directed in the alignment angle (α, β).
[0050] The above-mentioned clamping bars, clamping rollers or other similar fixing means may also be present in the first variant with the cutting means. They are used here to fix and position the front area of the material web ( 36 ) remaining on the conveying means ( 29 ). They can also assume the same function in the second variant according to FIG. 5 .
[0051] The laying carriage ( 25 ) is positioned at an edge area of the intermediate carrier ( 20 ) in FIGS. 2 and 3 . FIGS. 4 and 5 show a variant of this with a laying carriage position shifted into the middle area of the intermediate carrier.
[0052] In all embodiments, the material to be laid ( 5 , 37 ), which is exiting at the laying unit ( 16 , 17 ), especially at the laying carriage ( 25 ), is taken up on the running conveying means ( 29 ), with the running velocity essentially corresponding to the velocity of discharge at the laying unit ( 16 , 17 ) or laying carriage ( 25 ). The material to be laid ( 5 , 37 ), which is taken up, is now fixed by the holding or suction means ( 30 ) during conveying.
[0053] The separation of the material web ( 5 , 37 ) with the cutting means ( 19 ) takes place in an area of the intermediate carrier between the take-up area ( 35 ) and the lower discharge area ( 36 ). The material or formed web layer ( 9 ) now separated is then brought into a position suitable for discharge at the lower discharge area ( 36 ) by a corresponding conveying motion of conveying means ( 32 ). The starting area of the remaining material web ( 5 , 37 ) can now follow.
[0054] The layer is subsequently transferred from the stopped position of the conveying means ( 29 ) and of the discharge device ( 18 ), possibly with the cooperation of lifting means ( 31 ). With the holding means ( 30 ) switched off, the intermediate carrier ( 20 ) releases the material or formed web layer ( 9 ), which will fall as a result on the rear area of the nonwoven and is possibly fixed here by the holding means ( 38 ). The formed web storage means ( 15 ) is being filled during this time. The discharge device ( 18 ) subsequently advances cyclically, and the conveying means ( 29 ) of the intermediate carrier ( 20 ) is again set into motion and material to be laid ( 5 ) is again laid on the take-up area ( 35 ) while the formed web storage means ( 15 ) is being emptied. The cycle is then repeated from the beginning
[0055] As is illustrated in FIG. 6 , the material or formed web layers ( 9 ) have a trapezoidal shape in case of an alignment angle (α, β) differing from 90° and are cut off correspondingly obliquely for this. As a result, they have lateral layer edges ( 12 ) that are aligned in parallel to the discharge direction ( 13 ) and have front and rear parallel edges ( 10 , 11 ) that extend obliquely to the discharge direction ( 13 ). The conveying cycle is coordinated in case of the closure of the layers mentioned in the beginning such that said edges ( 10 , 11 ) overlap each one on top of another in scale-like layers ( 9 ).
[0056] Various variants of the embodiments shown and described are possible. A laying unit ( 16 , 17 ) may also have a different design, e.g., it may be designed as a carriage nonwoven laying unit, camelback nonwoven laying unit or the like. The intermediate carrier ( 20 ) may also be combined with other variants of the laying unit ( 16 , 17 ). Furthermore, the above-described features of the different exemplary embodiments may be combined with one another and mutually replaced with one another.
[0057] While specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles. | A laying method and a laying device ( 2 ) are provided for laying a fibrous web ( 5, 37 ) with a prevailing fibre orientation ( 6 ). The laying device ( 2 ) has a material feed means ( 14 ), a laying unit ( 16, 17 ) and a discharging device ( 18 ), the laying unit ( 16, 17 ) laying the supplied fibrous web on the discharging device in material layers ( 9 ) with a consistent alignment and fibre orientation ( 6 ). | 3 |
BACKGROUND OF THE INVENTION
Diamond has many anticipated superiorities for various technological applications and therefore the diamond growth has been a forefront of material research in recent decades. There has been some progress in areas such as the rate of growth and the physical size of the polycrystals. These crystals can be oriented from each other. However, they are disjointed macroscopically or joined with multiple grain boundaries and a realization of a large single crystal diamond does not seem to be in sight. The present invention represents a drastically different synthesis approach by growing of diamond on liquids surface. The current prevailing practice of growing diamond is on solid substrate. A hindrance to grow a large area, single crystal diamond for many technological applications is a low mobility of the carbon species on the surface of a solid substrate. Another deficiency of a solid surface is the structural imperfection, such as the dislocation and the grain boundary, which could induce a prolific and random growth of diamond crystallites. Furthermore, these crystallites on the solid surface are immobile, and once after they are formed, they cannot organize among the neighbors to form jointly a single crystal.
A growth of diamond on a solid substrate is referred to as a solid epitaxy or simply, epitaxy. When the substrate during the crystal growth is a liquid, which is the case in the present invention, the process will be a rheotaxy. In rheotaxy, the substrate surface will have a perfect smoothness and no structural defects, such as the grain boundaries. A conceptual advantage of the liquid surface to grow diamond is the high mobility on two levels:
(1) On the atomic level, a carbon atom has a higher mobility on a liquid surface than on a solid surface. This mobility would facilitate an aggregation of the carbon atoms to form diamond crystallites, and
(2) On the macroscopic level, diamond crystallites adhere comparatively weakly to the surface of liquid than a solid.
A combination of (1) and (2) produces the following benefits: In the liquid, due to a lower specific gravity of diamond than that of liquid to be adapted in the present invention, the diamond crystallites would float on the liquid. These floating islets could be mobile and could coalesce due to several mechanisms such as electric field, thermal fluctuations, gas turbulence from the carbon impact, and mechanical vibration from surroundings. With a manipulation of these sources, the crystallites could be aligned crystallographically and morphologically from each other to form a large single crystal. This will be the basis of the present invention.
BRIEF DESCRIPTION OF THE INVENTION
A prevailing method to prepare the carbon precursor for diamond syntheses is by a dissociation of hydrocarbons such as methane pyrolytically with an assistance of hot filament or a microwave plasma and known as a chemical vapor deposition (CVD).
Other methods, such as solid source to replace the vapor is a variation based on a similar principle of rheotaxy. One solid source of the present invention is fullerene. Fullerene is a molecule consisting of a large number of carbon atoms. For example, C 60 has sixty carbon atoms and C 70 has seventy carbon atoms. These atoms are held together with a weak binding energy and therefore can become an atomic carbon source by a thermal dissociation. Furthermore, these carbons have the right bond configuration to form diamond.
Another solid carbon source of the present invention is rare earth carbide. When these carbides come into contact with the rheotaxial liquid, an alloy from the rare earth with part of the rheotaxial substrate material and the carbon atoms are liberated and under a proper condition, aggregate among the carbons to form diamond.
In the solid source case, the materials are usually in a powder form. They can be pressed into a thin plate or deposited on another plate, such as graphite or quartz. The formed plate is placed on the surface of the rheotaxial liquid to proceed with the diamond synthesis.
Similar to the chemical vapor deposition, hydrogen ambient is necessary to prohibit a graphite formation in the solid source case as well.
Once the principle of the rheotaxial operation is understood, the diamond synthesis method, based on rheotaxy with a vapor or solid source of carbon is the same. Therefore, in the following, the vapor case, that is, CVD will be used in a generic sense to replace a redundant description for the solid case.
To establish the rheotaxy for diamond crystal growth, some criteria of the rheotaxial material are: (i) The material does not react with carbon, the element of diamond, to form a compound, (ii) The material is liquids at the temperature for diamond formation, and (iii) The material has low vapor pressure during the diamond deposition. Some substrate materials are listed in Table 1. All materials in this table satisfy (i) except Al which forms a compound with C, but at a low temperature and low carbon concentration as in the CVD condition, the reaction will neither be efficient nor detrimental. According to the table, Ge and Cu do not become liquid at the typical CVD temperature of 900° C. Above their melting temperature, the vapor pressure becomes too high. On the other hand, the melting temperature of Sn, Ga, In and Al are very low, and therefore satisfy (ii). However, they do not satisfy (iii), that is, their vapor pressure is too high at 900° C. Since these materials melt at much lower temperature, if the CVD temperature can be reduced, the vapor pressure of these materials would be reduced and this will be a part of the strategy of the present invention.
TABLE 1______________________________________Some substrate materialsMaterial Density Melting point (° C.) Vapor pressure @900° C.______________________________________ (torr)Ge 5.35 937 3 × 10.sup.-6 @melting pointCu 1083 8 × 10.sup.-4 @melting pointSn 232 5 × 10.sup.-5Ga 30 7 × 10.sup.-4In 157 8 × 10.sup.-3Al 660 1 × 10.sup.-5______________________________________
2) In order to grow diamond with planar morphology, evidently the substrate itself should be planar. All materials in Table 1 tend to form a solid blob due to their strong surface tension. When these materials are melted on some refractory metals, single crystal silicon, graphite and boron nitride, they do not produce a uniformly spread liquid layer. Consequently, a macroscopic planar diamond layer would not be formed. However, when transition metals such as nickel are employed as a support base on which to coat the substrate material, there is a wet action between the substrate material and the supporting base and a planar flat substrate is obtained.
An alternative to a template to produce a planar morphology is to use the pre-existing diamond as the substrate for epitaxy, which becomes homo-epitaxy. A limitation is that pre-existing diamond single crystal has a practical size limitation of several mm in dimension. Furthermore, it is not economical for practical applications.
An important aspect of rheotaxy is that in solid epitaxy, generally a diamond seed is required to apply on the substrate. On the liquid substrate, no diamond seeding is necessary and the growth is spontaneous. Apparently due to a high mobility of carbon on the liquid surfaces, an aggregation of carbon to form diamond is facilitated, and in this respect, liquid also acts as a catalytic agent.
DETAILED DESCRIPTION OF THE INVENTION
The method to grow diamond crystal by rheotaxy consists of three parts: stable liquid substrate, planar base support, and diamond deposition.
1) Stable liquid substrate.--The criteria for the substrate are (i) it does not react with carbon, (ii) it melts at the temperature of diamond deposition, and (iii) the vapor pressure of the substrate material should be low. The materials listed in Table 1 can be divided into two groups according to their melting temperature: Group 1: Ga, In, Sn and Al are liquid at the typical diamond deposition temperature of 900° C. However, their vapor pressure at this temperature is very high and diamond crystallites would be poorly formed. For example, Sn has a vapor pressure of 5×10 -5 torr and the diamond forms only marginally. Therefore, a material with vapor pressure to be much lower than 5×10 -5 torr is suggested.
A strategy for lowering of the vapor pressure is to lower the diamond deposition temperature. Since the vapor pressure is sensitively dependent on the temperature, a drastic pressure reduction can be obtained when the CVD temperature can be reduced. According to Table 2, for example, when the substrate temperature is reduced from 900 to 600° C., Al, Sn and Ga would have excellently low vapor pressure. If the temperature can be further reduced to 500° C., In would also be an excellent substrate material. It remains that an arbitrary temperature reduction could effect the quality of the diamond growth and this aspect, in combination with the dependence on the substrate material, have to be taken into a consideration for a right combination. Here an enrichment of a catalog of substrate material would provide a possibility of other physical parameter selections such as viscosity of the liquid which could effect the dynamics of the crystal growth.
TABLE 2______________________________________Vapor pressure at different temperature of some substrate materials Vapor Pressure (torr) atMaterial Melting Point (° C.) 500° C. 600° C. 700° C.______________________________________Sn 232 1 × 10.sup.-10 1 × 10.sup.-9 1 × 10.sup.-8Ga 30 1 × 10.sup.-8 1 × 10.sup.-7 2 × 10.sup.-6In 157 5 × 10.sup.-8 1 × 10.sup.-6 5 × 10.sup.-5Al 600 1 × 10.sup.-11 .sup. 3 × 10.sup.-10 3 × 10.sup.-8______________________________________
Group 2. According to Table 1, due to a requirement of an in situ liquids state, the low temperature strategy is not be applicable to the case of Cu and Ge due to their solidification at high temperature. For a rheotaxy, the temperature of Ge has to be higher than 937° C., the melting temperature of Ge. Consequently, the vapor pressure would be higher than 3×10 -6 torr. For Cu, a temperature exceeding 1083° C., the melting temperature of Cu, would be required. At this temperature, the vapor pressure would be 1×10 -5 torr, too high for the growth of a continuous diamond film.
In this invention, an indirect strategy is invented: when Ge and Cu are combined, in an atomic ratio of Ge:Cu=36.5:63.5, the binary system has an eutectic temperature of 644° C. (T. B. Massaltskii, Binary Alloy Phase Diagrams, 1995). Therefore, this alloy could be rheotaxial material with remarkably low vapor pressure. For example, at a typical CVD temperature of 900° C., the vapor pressure of Ge and Cu will be 6×10 -7 and 7×10 -6 torr, respectively. When the deposition temperature is slightly above the eutectic temperature, the substrate work remains in a liquid state and the pressure would be unprecedentedly low, therefore, a vastly improved diamond film can be expected.
In addition to the Ge and Cu eutectic system, Ge with Al also has an eutectic with a lower eutectic temperature of 420° C. at 28.4 atomic % of Ge and 71.6 atomic % of Al. (T. B. Massaltskii, Binary Alloy Phase Diagrams, 1995) Although Al does form a compound with C, but at a low temperature and low C concentration under CVD condition, the reaction between Al and C would not be detrimental
2) Planar Base Support.--A planar template is mandatory in order to form a planar diamond morphology for many device applications. In the case of solid substrate, this requirement is naturally satisfied. In the case of liquid substrate, due to a high surface tension, all candidate materials show the same tendency to form a blob when they are melted on various supporting plates, such as graphite, silicon, boron nitride, and many refractory metals. A phenomenological description is that these materials do not wet the supporting body. One possible mechanism is an existence of an oxide film in the case of silicon and refractory metals. On the surface of oxide free surfaces, such as that of Au and Pt, and substrate materials do wet and a flat surface substrate can be made. However, due to high mutual solubility of these precious metals with the substrate materials, once they are completely dissolved to each other, the planar morphology is again destroyed. In a continuous search for supporting body materials, we have found nickel is a satisfactory substance.
Based on nickel, a composite template structure can be made on the nickel plate, a thin layer of substrate material is coated. There is a critical thickness of the substrate material: if it is too thin, the microscopic structure of the film is discontinuous and if it is too thick, it tends to break up to form small individual blobs. In the case of In on glass, the critical thickness is about 100 nanometer. A substrate structure consisting of Ni or other transition metals with a layer of the substrate material of Table 1 will form a composite substrate for rheotaxy and for the planar supporting body.
3) Diamond Deposition.--A method for diamond deposition referred to in the present invention is a hot filament chemical vapor deposition, as used in the majority of diamond synthesis since the original work of Derjaguin (B. V. Derjaguin and J. V. Fedoseer, New Diamond Sci. and Tech. Material Research Society, Proc. 1990). Two particular aspects in the invention are (i) low temperature deposition system combined with (ii) organized growth. They will be described below.
(i) Deposition system.--The principle is to deposit carbon on a selected substrate. Carbon is derived from a decomposition of hydrocarbon gas in a rich hydrogen ambient with an assistance of hot filament. A particular aspect is the following incorporation. In order to reduce the vapor pressure of the substrate, thus to maintain the substrate surface integrity, an effectively low substrate temperature will be utilized. One low temperature CVD method is to incorporate microwave with the CVD. (Y. Saito et al. J. Mater. Sci. 23, 842 (1988)). A difficulty to incorporate this method with the present invention is a possible interference between the microwave field with the biased field and the field for electrophoreses to be made in the present invention. A more practical method for the present purpose is to add a minute amount of oxygen and an adjustment of the temperature of substrate and of filament. A low substrate temperature of 450° C. to grow diamond has been reported (Z. Li Tolt et al. J. Mater. Res. 12, 13344 (1997)). With this approach, the high vapor pressure deficiency of the substrate material would be eliminated.
(ii) Organized diamond crystal growth.--The organized diamond crystal growth consists of two processes, orientation and coalescence. The oriented aggregation of diamond crystal will be induced by an application of a biased field. In the work of Stoner and Glass, the bias is applied between the hot filament and the substrate (B. R. Stoner and J. T. Glass, Appl. Phys. Lett. 60, 698 (1992)). They are parallel to each other with a specified orientation, thus the field is longitudinal. In the present invention, an additional transverse field will be applied across the substrate. The aim of this transverse field is to create an electrophoresis of the diamond islets in the liquid for rheotaxy. This process will aid in the alignment of the islets through a translational motion to form a single crystal. The longitudinal and the translational field can be combined and produced with an unsymmetrical electrode configuration. In the case of hot filament CVD, with the filament as one electrode and the substrate as a counter electrode, unsymmetry can be created by reducing overall area of the hot filament, such that the field line between the two electrode has both longitudinal and transverse components.
An alternative approach is to maintain the longitudinal symmetrical field configuration and simultaneously an additional electrode pair is attached perpendicularly with respect to the surface of the rheotaxial liquid.
The above field configurations are applicable to the CVD system. In the solid carbon precursor system, the atomic carbon will be generated by a thermal pyrolysis. In the case of dispersing the carbon as a powder on the rheotaxial liquid, in principle, the hot-filament approach can still be applied even if the purpose was not to dissociate the hydrocarbon, rather as a source to create heat and electrons.
When the solid carbon is compressed into plate form, the plate can be an electrode with the substrate as a counter electrode. The plate can be electroded symmetrically or unsymmetrically as the hot filament in the CVD case.
An utility of the top plate of the solid carbon source is based on which a compression can be applied for two purposes: (i) to maintain an intimate contact between the carbon source and the rheotaxial liquid such that vastly more carbon atoms will be participating in diamond synthesis sumltaneously. In comparison, in the CVD case, the participating carbon atoms will be approximately the carbon density in a vapor. Therefore, the ratio of the synthesis efficacy between the solid and the vapor will be approximately the carbon atomic density in solid versus gas. This ratio will be an astronomical 10 10 times. This effect will increase the growth rate and an improvement of the diamond film continuity.
Still another utility of the top plate with exerted compression is to maintain the substrate liquid in a flat form instead of a blob form and, without a reliance on a wetting supporting base.
One important aspect of the present invention is an introduction of a mechanism for diamond coalescence through a translational motion of the diamond crystallites through an electrophoresis. Electrophoresis is a classical process widely used in liquid chemistry and biology (David M. Hawcroft, Electrophoreses (Oxford Univ. Press, N.Y. 1997)) but this will be the first time in diamond growth. This process becomes possible because of an involvement of a liquid medium in the present invention involving rheotaxy. In an elaborate scheme consisting of C, Ni and H, Yang et al. have successfully oriented diamond crystals through a rotation in an eutectic (Ni, C) liquid (P. C. Yang, W. Zhu and J. T. Glass, J. Mat. Res. 8, 1773 (1993)), however, these crystals are individually localized and pinned to the solid substrate of Ni and Si, and there is no provision for a coalescence to form a large single crystal. In the present invention, both rotational and translational motions become possible because of the movement is on a liquid substrate, and thus a formation of large single crystal diamond is provided. | A method to grow diamond crystal by an utilization of liquid template on which carbon precursor is deposited. The liquid template is to replace the conventional solid template to improve the quality and the size of the diamond crystal through the inherent property of the liquid. Its ideal smoothness, its amorphosity and therefore, an absence of the grain boundary, and its high surface mobility for carbon aggregation to form diamond crystal, thus to grow diamond crystal. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This is a 371 of PCT/DE02/04302, filed Nov. 22, 2002, and published as WO 03/045895 on Jun. 5, 2003.
The invention relates to a process for obtaining 5-bromo levulinic acid methyl ester from a bromination mixture, which is obtained by bromination of levulinic acid or levulinic acid methyl ester and which contains 5-bromolevulinic acid methyl ester, and to a process for obtaining 5-chlorolevulinic acid alkyl esters.
The bromination of levulinic acid in methanol with one mol equivalent of bromine yields
1. 3-bromolevulinic acid methyl ester 2. 5-bromolevulinic acid methyl ester 3. 3,5-bromolevulinic acid methyl ester
and as a result of the consumption of further bromine equivalents for the formation of 3,5-bromolevulinic acid methyl ester from (1) and/or (2)
4. the not brominated levulinic acid methyl ester.
The quantity ratio of the products within the bromination mixture behaves like (1):(2):(3):(4)=28:56:8:8, whereas insignificant variations may occur according to the reaction conditions. In general, however, the selectivity of the formation of the bromination products, especially the 5-bromolevulinic acid methyl ester, can not decisively be changed. The bromination of levulinic acid methyl ester (4) instead of levulinic acid with one equivalent of bromine in methanol leads approximately to the same result.
2. Description of the Prior Art
Therefore, the production of 5-bromolevulinic acid methyl ester depends on the mentioned bromination mixture. According to the latest development of the technology, several processes for the isolation of the 5-bromolevulinic acid methyl ester from the bromination mixture are known.
S. F. McDonald in Can. J. Chem. 1974, 52, 3257–3258 describes a process, from which the mentioned bromine compound is obtained from the bromination mixture by double fractional high vacuo distillation. In this way the 5-bromolevulinic acid methyl ester is obtained (relating to the starting compound levulinic acid) in 30% yield and about 2% of the 3,5-dibromolevulinic acid methyl ester as an impurity.
To prevent an acid catalysed change of the ratio of the isomers, the destination should proceed quickly and the thermal stress of the bromination mixture should be kept as low as possible. A higher thermal strain particularly has a problematic effect if traces of hydrogen bromide are present, which cause an unfavourable change of the yield to the disadvantage of the 5-bromolevulinic acid methyl ester. The experience also showed, that the amount of the 5-bromolevulinic acid methyl ester obtained by fractional distillation, considerably decreases, if small amounts of the 3,5-dibromolevulinic acid methyl ester are present.
The requirements for the careful production of the desired ester connected with an optimal yield are met only unsufficiently, since the double fractional distillation causes a comparable high expenditure of time resulting in a high thermal strain of the distillation mixture.
Moreover, if the range of pressure needed for the distillation is not reached within a short period of time, the destination time is lengthend and on top the thermal strain of the bromination mixture increases.
On top of that, it especially has to be considered as a disadvantage, that the separation of the brominated products by distillation according to the available process all in all is very expensive, because for this a double fractional distillation using a vacuum jacketed vigreux column is necessary. Because of the high technical expense, this process is ruled out for a large-scale application.
H.-J. Ha, S.-K. Lee, Y.-J. Ha, J. W. Park, Synth. Comm. 1994, 24(18), 2557–2562 describe a process for obtaining 5-bromolevulinic acid methyl ester, which provides the desired ester from the bromination mixture by means of column chromatography. High costs are connected in an unfavourable manner to this process and therefore a purification using liquid chromatography is out of question when you consider a technical application.
With regard to the use of 5-bromolevulinic acid methyl ester, production processes for the preparation of 5-aminolevulinic acid hydrochloride must be mentioned in the latest development of the technology.
American patent U.S. Pat. No. 5,907,058 shows a process in which 5-aminolevulinic acid hydrochloride is prepared by processing 5-bromolevulinic acid methyl ester with sodium diformylamide in water-free acetonitrile and the following acid catalysed hydrolysis of the resulting 5-diformylamino levulinic acid methyl ester.
In the Z. Naturforsch. 1986, 41b, 1593–1594 a process is described by E. Benedikt and H.-P. Köst, which is characterised by the following steps: Processing of 5-bromolevulinic acid methyl ester together with potassium phthalimide in dimethylforamide yielding 5-phthalimido levulinic acid methyl ester, which is then hydrolised by an acid.
Finally, in the above mentioned publication of H.-J. Ha, S.-K. Lee, Y.-J. Ha, J. W. Park, Synth. Comm. 1994, 24(18), 2557–2562, a process for the preparation of 5-aminolevulinic acid hydrochloride is described. This process starts with 5-bromolevulinic acid methyl ester, which is prepared from levulinic acid by bromination, and which is characterised by the following process steps: Processing of 5-bromolevulinic acid methyl ester together with sodium azide in dimethyl formamide to 5-azidolevulinic acid methyl ester and followed by the catalytic hydrogenation and the subsequent ester hydrolysis of the formed 5-aminolevulinic acid methyl ester hydrochloride.
The disadvantage of these processes is, that they require the starting material in high purity. The herewith connected high technical expense and the high costs for the preparation of this product lead to the fact, that a large-scale production of 5-aminolevulinic acid hydrochloride like mentioned above is unprofitable so far.
SUMMARY OF THE INVENTION
Considering this background, an object of the present invention is to provide a process for the preparation of 5-bromolevulinic acid methyl ester, which avoids the mentioned disadvantages, and which allows for the production of the mentioned substance in high purity and therefore is suitable for a large-scale application, which leads to a cost-effective preparation of the mentioned substance and which, therefore, meets the requirement for a cost-effective preparation of 5-aminolevulinic acid methyl ester hydrochloride and 5-aminolevulinic acid hydrochloride. Further, inventive process includes the recycling of the resulting undesirable byproducts.
According to the invention the problem is solved by a process, which intends to use the following process steps:
dissolving the bromination mixture in an organic solvent or solvent mixture cooling down the solution to low temperatures, preferably to temperatures which are lower than −20° C., especially in the temperature range between −20° C. to −40° C. crystallisation of the 5-bromolevulinic acid methyl ester out of the solution isolation of the crystalline 5-bromolevulinic acid methyl ester by draining off the solution with the remaining bromination mixture.
The suggested process starts from known processes for the preparation of 5-bromolevulinic acid methyl ester, which yields a mixture of 3-bromolevulinic acid methyl ester, 5-bromolevulinic methyl ester, 3,5-bromolevulinic acid methyl ester and levulinic acid methyl ester by means of bromination of levulinic acid and levulinic acid methyl ester.
To isolate the 5-bromolevulinic acid methyl ester from a mixture according to the present invention, the mixture will be dissolved in an organic solvent or solvent mixture first and cooled down in the following process step. During this procedure, temperatures in the range of −20° C. and −40° C. must be kept. Thereby, the 5-bromolevulinic acid methyl ester crystallises in the form of colorless needles or plates, whereas the other parts of the bromination mixture remain in the solution. To seperate the crystallised ester from the rest of the bromination mixture, the remaining solution is simply drained off.
The basis of the invention is essentially the finding, that the single parts of the bromination mixture in solution show a completely different crystallisation behavior. This behavior proved to be extremely selective, where in the given temperature range between −20° C. and −40° C. only the 5-bromolevulinic acid methyl ester crystallises. By cooling the mixture down to this temperatures it is made secure that only the before mentioned bromination compound precipitates. The suggested procedure shows a yield of 35% to 38% in relation to the quantity of levulinic acid, whereby the produced bromination product has a high purity of 99%. Impurities consist after the isolation of the 5-bromolevulinic acid methyl ester of levulinic acid methyl ester and 3-bromolevulinic acid methyl ester. These two compounds dont't disturb further synthesis steps, whereas the 5-bromolevulinic acid methyl ester gained according to the procedure of McDonald as mentioned above contains 3,5-dibromolevulinic acid methyl ester as an impurity. This compound affects the further reaction steps extremly unfavourable and makes complicated purification procedures of the final product necessary! The production process according to the given invention must be considered as extremely gentle, since the bromination mixture and the ester to be isolated are not exposed to thermal strain by the crystallisation process. The danger of the acid catalysed change of the ratio of the isomers is thus excluded in a favourable manner. An essential advantage of the procedure according to the invention are its extremely simple courses in the production of the 5-bromolevulinic acid methyl ester, which can accordingly be carried out quickly. The mentioned procedure steps may be applied not only in the laboratory but in large-scale installations just in the same. The costs for the technical process installations in relation to the produced amount of the ester and the production costs are much lower than the corresponding expenses for the procedure according to the latest development of the technology using liquid chromatography or high vacuo distillations.
Several organic solvents or solvent mixtures are suitable for carrying out the selective crystallisation. According to the present invention are recommended:
the solvents
ethanol
2-propanol
diisopropyl ether
or the solvent mixtures
diethyl ether plus lower or higher boiling petroleum ether fractions and/or
t-butyl methyl ether plus petroleum ether and/or
diethyl ether plus cyclohexane and/or
t-butyl methyl ether plus cyclohexane.
In the laboratory experiments mixtures of petroleum ether (30–50° C.) and diethyl ether or tert-butyl methyl ether in a ratio of 1:1 proved to be reliable. The amount of solvents necessary for the carrying out of the process are relatively low.
A further advantage of the procedure according to the invention shows when the respective byproducts must be disposed of. According to a feature of the invention it is planned to recycle the remaining bromination mixture after the crystallisation of the 5-bromolevulinic acid methyl ester. The remaining mixture contains
1. 3-bromolevulinic acid methyl ester 2. rests of 5-bromolevulinic acid methyl ester 3. 3,5-bromolevulinic acid methyl ester 4. and levulinic acid methyl ester.
By this the products 1.–3. can be converted to levulinic acid methyl ester by catalytic hydrogenation with hydrogen. For this purpose the mixture is dissolved in methanol and reduced in the presence of a hydrogenation catalyst by passing in hydrogen at a pressure of 20 bar.
The levulinic acid methyl ester recovered in this way can then be used as a starting product for the production of the mentioned bromination mixture. For this purpose the levulinic acid methyl ester is dissolved in methanol and is converted like in the above mentioned bromination of levulinic acid methyl ester with elemental bromine into the bromination mixture. This conversion nearly yields the same mixture of isomers as the bromination of levulinic acid. The mixture contains especially 5-bromolevulinic acid methyl ester in a high concentration and can so be used with advantage as a starting product for the procedure according to the invention.
As a catalyst palladium on carbon is suggested according to the given invention. The advantage of this catalyst is that it can be regenerated after the hydrogenation reaction.
When the hydrogenation of the remaining bromination mixture is made hydrogen bromide is the only byproduct. This product can be disposed of without problems when it is converted to carbon dioxide, water and sodium bromide by sodium hydrogen carbonate. The given invention shows respective steps for the procedure. A cost-intensive and/or the environmentally harmful disposal of byproducts is not necessary at all in the production of 5-bromolevulinic acid methyl ester according to the procedure invented.
The low-cost production of 5-bromolevulinic acid methyl ester according to the given invention opens up a wide range of application possibilities of the given ester. According to the invention especially the use for the production of 5-aminolevulinic acid methyl ester hydrochloride and the thereof gained 5-aminolevulinic acid hydrochloride is intended. The last mentioned compound is used for the cancer diagnosis and for the therapy of carcinomas as well, especially for bladder cancer carcinomas. On top, 5-aminolevulinic acid hydrochloride is used as a broad spectrum herbicide in the agricultural sector. Since this substance occurs in nature itself, this herbicide has the advantageous characteristic that it is biodegredable and doesn't provide unnatural and problematic metabolites.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A large-scale production of 5-aminolevulinic acid hydrochloride failed until now, inspite of intensive efforts because the costs for the production of the starting product were to high. Up to the present moment the substance is therefore produced only in small quantities which results in the disadvantage of high prices. One gram of the substance costs today on the chemical market about 30 to 50 ∈ and in medical quality 75 ∈. A broad application of 5-aminolevulinic acid hydrochloride in agriculture is not possible because the prices are to high. The low-cost production of 5-bromolevulinic acid methyl ester according to the given invention therefore provides the conditions for a large-scale production of 5-aminolevulinic acid hydrochloride. The use according to the invention according to the proposed procedure produced 5-bromolevulinic acid methyl ester for the production of 5-aminolevulinic acid hydrochloride also contains the use of procedures described in the latest developments of the technology.
When using 5-bromolevulinic acid methyl ester for the production of 5-aminolevulinic acid hydrochloride it is according to the invention especially suggested, that the last process step for the production of 5-bromolevulinic acid methyl ester is directly connected to the first process step for the production of 5-aminolevulinic acid hydrochloride without changing the reaction vessel.
In the usual synthesis of 5-aminolevulinic acid hydrochloride 5-bromolevulinic acid methyl ester is a liquid. In this form it shows strongly lachrymatory and skin irritating properties, every contact with the substance must therefore be avoided. The crystalline form of the bromination product however shows less irritating features. If the product is left in the reaction vessel after crystallisation for the carrying out of the following processes a contact with people is avoided a priori. The danger of eye and skin irritations is so completely excluded.
By the proposed procedure a further advantage is obtained which is based in the omission of a storing of the 5-bromolevulinic acid methyl ester and the problems connected. The brominated compound tends in the presence of traces of acid—for example hydrogen bromide—to an acid catalised isomerisation in the compounds 3-bromo-, 3,5-dibromo- and levulinic acid methyl ester. It therefore usually requires a careful storing, which, however, is excluded in the given procedure.
On top, the two following steps from 5-bromolevulinic acid methyl ester to 5-aminolevulinic acid hydrochloride run at already 20° C. to 25° C. (from time to time even exotherm) so that no energy is required and the reaction mixtures must only be stirred.
In an alternative, preferred embodiment, a further production procedure is mentioned. 5-bromolevulinic acid methyl ester and 5-chlorolevulinic acid esters are starting compounds for the production of the pharmacologically important substance 5-aminolevulinic acid hydrochloride.
According to the latest developments in the technology the production of the 5-bromolevulinic acid methyl ester is considered difficult because of the cost-intensive work-up of the production mixture by means of distillation and chromatography. Hereby, especially the strongly lachrymatory properties of the liquid 5-bromolevulinic acid methyl ester proved to be disadvantageous. The lachrymatory feature is hereby a result of the bromo methyl ketone moiety in the compound and is valid in general for compounds containing such a moiety as a structural element in the molecule (comp. for example M. Gaudry, A. Marquet, Organic Syntheses, Coll. Vol. 6, 193–195).
To exclude the declared disadvantages of the 5-bromo compounds and to produce more stable, not lachrymatory, storable—at the C-5 position halogen substituted derivates—instead of the 5-bromo compounds the 5-chloro or 5-iodo compounds are suitable. The 5-chloro compounds don't possess lachrymatory properties in comparison to the 5-bromo compounds, because they have a chloro methyl ketone moiety instead of a bromo methyl ketone moiety. On top, they are thermically much more stable in comparison to the bromo compounds and don't tend under the conditions of the distillation to acid catalised isomerisations. This feature is also valid for other chloro methyl ketones (comp. E. Warnhoff, M. Rampersad, P. S. Raman, F. W. Yerhoff, Tetrahedron Lett. 1978, 19, 1659–1662).
The production of chloro esters of the levulinc acid, which are substituted at the C-5 position by direct chlorination of levulinic acid or esters thereof with or without an organic thinner by passing in chlorine gas has the disadvantage that you receive—in comparison to the bromination with elemental bromine—a strongly reduced selectivity of the halogenation to the disadvantage of the desired 5-chloro compounds. For example the chlorination of levulinic acid leads to such a strongly reduced selectivity that you receive as a main product 3-chloro levulinic acid. Besides not desired poly chlorination products as 3,3-dichloro-, 3,5-dichloro-, 5,5-dichlorolevulinic acid emerge as well as further unknown products together with the not converted levulinic acid (comp. EP 0397048). In analogy to this you receive substance mixtures approximately corresponding to the above mentioned when you try to chlorinate levulinic acid esters under the most different conditions. It is very difficult to separate these substance mixtures, the yields are bad and they are therefore not usual for further conversions. When you chlorinate levulinic acid ethyl ester without thinners you receive for example mainly the 3-chlorolevulinic acid ethyl ester. The chlorination of levulinic acid ethyl ester with sulphuryl chloride in an unpolar organic solvent yields with the reverse selectivity mainly the 3-chlorolevulinic acid derivative (comp. EP 0397048).
In EP 58392 a procedure for the production of 5-chlorolevulinic acid ethyl ester is described that starts from succinic acid mono ethyl ester mono chloride. This compound is converted with diazo methane at −5° C. and is after that worked up by passing in hydrogen chloride. You receive so the desired compound in pure form and in a high yield but the difficult handling of explosive diazo methane makes this method for the large-scale use not suitable. The same procedure is described in PL 136454. Instead of the succinic acid mono ethyl ester mono chloride the respective methyl ester derivative is used and results in the formation of 5-chlorolevulinic acid methyl ester.
The 5-chlorolevulinic acid alkyl esters are starting compounds for the production of other substances and are further converted by the nucleophilic substitution of the halogen atom.
Besides alkali imides and alkali azides tertiary amines are suitable nucleophiles. The tertiary amine hexamethylene tetramine(urotropine) is described as a cheap and commercially available nucleophilic reagent for the introduction of the amino group, for example in bromo methyl ketones (comp. N. Blazevic, D. Kolbah, B. Berlin, V. {hacek over (S)}unjic, F. Kajfez, Synthesis, 1979, 161–176).
The conversion of 5-chlorolevulinic acid methyl ester with urotropine results in 5-urotropiniumlevulinic methyl ester chloride, a quarternary ammonium salt of the levulinic acid methyl ester that in connection with this invention has been produced for the first time and directly been converted to 5-aminolevulinic acid hydrochloride. In WO 02/32852A2 the production of 5-urotropiniumlevulinic esters from 5-bromolevulinic acid esters (chain lengths of the ester alkyl groups C1–C5) and their conversion to 5-aminolevulinic acid hydrochloride by acid catalysed hydrolysis is described. As a disadvantage of this procedure description you must consider, that in the final product ammonium chloride and ammonium bromide exist as inorganic impurities and the 5-aminolevulinic acid might occur as the hydrochloride as well as the hydrobromide. Ammonium salts as impurities are only difficult to seperate from the final product—5-aminolevulinic acid hydrochloride/5-aminolevulinic acid hydrobromide—so the task to gain 5-aminolevulinic acid hydrochloride in a purity necessary for medical purposes might be only difficult to solve according to this procedure description.
Behind this background, the procedure proposed for the preparation of 5-chlorolevulinic acid alkyl ester is described.
The proposed procedure starts from known procedures for the production of 5-bromolevulinic acid esters, where by bromination of levulinic acid or levulinic acid methyl ester a mixture of 5-bromo-, 3-bromo-, 3,5-dibromo- and the not brominated levulinic acid ester is the result.
The bromination products are extracted with an organic solvent from an alcohol/water mixture, which you receive after the work-up of the bromination step with water and the extract is stirred after that at temperatures between 20–25° C. and the boiling temperatures of the respective solvents with sodium chloride or saturated aqueous sodium chloride, suitably in the presence of an phase-transfer catalyst. In this reaction step the bromine atoms in the brominated esters are exchanged by chlorine atoms. This exchange takes place within a relatively short time, in a careful manner and quantitative. The mixture of chlorolevulinic esters produced here doesn't show any lachrymatory properties. The exchange of chlorine and bromine by a halogen in the produced pure bromolevulinic alkyl esters or chlorolevulinic alkyl esters can be made in principal also with fluorine and iodine. The exchange of chlorine or bromine can under the conditions of the phase-transfer catalysis also be made with the neat bromination mixture.
Non-toxic and harmless ethyl acetate proved to be a very suitable organic solvent for the bromine/chlorine exchange, which is on top regenerable and can be lead back to the synthesis cycle. As with water only with difficulty or not mixable solvents for the phase-transfer catalysed halogen exchange are also suitable:
ester like:
butylacetate amylacetate
alcohols like.
butanol pentanol isobutanol
ethers like:
di-n-buthyl ether diisopropyl ether diisoamyl ether tert-butyl methyl ether
aliphatic and aromatic hydrogen halides like (this solvents are only suitable for the exchange of bromine/chlorine but not for the bromine or chlorine/iodine or fluorine exchange):
dichloromethane tetrachloroethylene tetrachloromethane 1,1-dichloroethane.
As phase-transfer catalysts the following quarternary ammonium salts and quarternary phosphonium compounds can be listed as examples:
tetrabutyl ammonium bromide tetrabutyl ammonium chloride tetrabutyl ammonium iodide benzyltrimethyl ammonium bromide tetrabutyl ammonium hydrogen sulfate benzyldimethyl-n-dodecyl ammonium bromide trioctylmethyl ammonium chloride (adogen 464) ethyltrioctyl phosphonium bromide hexadecyltributyl phosphonium bromide phase-transfer catalysts which bases on polymers.
With regard to the large-scale production of 5-chlorolevulinic acid alkyl esters the decribed process is superior to all previous processes. The proportion of the produced 5-chlorolevulinic acid alkyl ester in the mixture is equal or higher than 56%. Byproducts are merely 3-chlorolevulinic acid esters (<28%), the 3,5-dichlorolevulinic acid esters (about 8%) and the not converted levulinic acid esters (about 8%).
While doing this the bromination step and the following bromine/chlorine exchange are carried out without changing the reaction vessel.
After the drying and distillation off of the solvent from the chlorination mixtures the residue is purified by means of fractional distillation. In comparison with the brominated products the corresponding chlorinated products have essentially lower boiling points. The 3-chlorolevulinic esters together with the not converted levulinic acid esters always form the first fraction of the distillation followed by the 5-chlorolevulinic esters in the second fraction. The higher chlorinated products have a higher boiling point compared with the mono-chlorinated products and form the third fraction. The mass balance sheet of the distillate in relation to the starting distillation good is always >90%. The fractional distillation is carried out in vacuo, which according to the present invention means, that it is worked with a negative pressure. The yield (in relation to the starting quantity of levulinic acid or levulinic acid methyl ester) of 5-chlorolevulinic acid methyl ester after the distillation is at least 50% (purity>98%).
On the one hand the sequence of the halogenation reactions takes into consideration, that the bromination of the starting compound is more selective than their chlorination. On the other hand the mixture of the chlorinated levulinic acid compounds, which is present after the quantitative halogen exchange, behaves in comparison to the present bromination mixture more stable towards acid catalysed isomerisation because the chlorination products have clearly lower boiling points and therefore the activation of a thermal caused production of hydrogen chloride from the 3,5-dichloro compound is avoided.
In view of a synthesis of the 5-aminolevulinic acid hydrochloride starting from 5-chlorolevulinic acid methylester there is in comparison with the homologue bromine compound an essential advantage, that you produce only sodium chloride as an inorganic by-product when it is converted with sodium azide or other nitrogen nucleophiles, which are used as their sodium salts (for example imides). In organic solvents sodium chloride is practically unsolulable. That means, that this by-product may be removed in a simple manner by filtration and the produced product may be lead directly to the following step practically without the presence of any inorganic impurity. In view of the use of 5-aminolevulinic acid hydrochloride in the medical field this fact is in so far of great importance as in the so produced product only sodium chloride and no other inorganic impurities can be present, which for example in the case of the present sodium chloride would cause a more expensive analytics.
In connection with this it is remarkable, that the 5-chlorolevulinic acid methyl ester can be also selectively produced by means of low temperature crystallisation from the chlorination mixture, which you get from the bromination mixture of levulinic acid or levulinic acid methyl ester in methanol and the subsequent bromine/chlorine exchange, in a gentle manner as already described for the 5-bromolevulinic acid methyl ester. As in the case of the 5-bromolevulinic methyl ester you proceed in the same way by using the same solvents and solvent mixtures and temperatures between −20° C. and −40° C. You get the 5-chlorolevulinic acid methyl ester in 35–38% yield and >98 purity. Impurities are the 3-chlorolevulinic acid methyl ester and the unconverted levulinic acid methyl ester. The 5-chlorolevulinic acid esters of the alcohols with chain lengths of C2–C4 can not be produced by low-temperature crystallisation because no crystallisation occurs under these conditions. The same is valid for the corresponding bromination mixtures of the 5-bromolevulinic acid esters which are produced from alcohols with chain lengths of C2–C4.
The first fraction of the distillation always consists of small amounts of the 5-chlorolevulinic acid ester, the 3-chlorolevulinic acid ester and the unconverted levulinic acid ester. These compounds can be converted in the levulinic acid esters by catalytic hydrogenation in the presence of an hydrogenation catalyst and a non-nucleophilic tertiary amine (for the purpose of catching the generated hydrogen chloride) and can therefore be quantitatively lead back to the bromination step. The used hydrogenation catalyst, preferably palladium on carbon according to the invention, may be regenerated. As solvent suitably the respective alcohol is used, which forms the rest of the ester. Only amine hydrochloride is formed as by-product The used solvents are regenerable. The catalytic hydrogenation of the by-products yields the levulinic acid esters and opens a possibility to regenerate the starting materials and to lead them back into the synthesis cycle. Alternatively, the 3-chloro compounds can be transferred into other synthetic pathways, so that a cost-intensive disposal of the byproducts can be avoided. The solvents and the catalyst are regenerable, only the hydrochloride of a tertiary amine has to be disposed of. The synthesis starts with cheap levulinic acid or the esters thereof, which are available in large quantities on the market and which can be produced on a large scale, for example from waste paper (comp. E. S. Oson, M. R. Kjelden, A. J. Schlag, R. K. Shamma, ACS Symposium Series 2001, 784, 51–63). The 5-chlorolevulinic acid esters which contain ester alkyl groups>C2 can be produced unproblematically and in nearly quantitative yield by means of transesterification of the 5-chlorolevulinic methyl- and ethyl ester using the concerning alcohols according to standard procedures. The 5-chlorolevulinic acid can be produced by means of ester hydrolysis of the 5-chloro levulinic esters according to standard procedures in a high yield.
EXAMPLES
Further details, features and advantages of the present invention can be drawn from the following part of the description. In this part of the description examples are described, which were carried out in the laboratory.
EXAMPLE 1
Preparation of 5-bromolevulinic Acid Methyl Ester from Levulinic Acid
In a threee-necked flask equipped with a mechanical stirrer, a reflux condenser, an internal thermometer and a dropping funnel, to a solution of levulinic acid (600 g, 5.17 mol) in 2400 ml bulk grade methanol bromine (826.2 g, 5.17 mol) was dropped at 20–25° C. during 15 min. Within 1.5 h the reaction temperature rised to 60° C. Afterwards, the color of the solution changed from dark-red to orange within 2 min. At this time the reaction was finished ( 1 H-NMR control). Water was added (2500 ml), which caused the precipitation of a yellowish oil. The oil was separated and the remaining solution was extracted with dichloromethane (3×300 ml). The combined organic extracts were combined with the oil and the resulting mixture was washed with saturated aqueous sodium hydrogen carbonate (3×200 ml) and saturated aqueous sodium chloride (3×200 ml). Drying of the organic layer with Na 2 SO 4 and distillation of the solvent in vacuo yielded a pale yellow oil consisting of 3-bromolevulinic acid methyl ester (1) (28%), 5-bromolevulinic acid methyl ester (2) (56%), 3,5-dibromolevulinic acid methyl ester (3) (8%) and levulinic acid methyl ester (4) (8%). The composition of the resulting product mixture was monitored by the NMR-spectrum, and the product ratio was calculated from the sum of the integrations of the 5-CH 2 (2, 3) and the 5-CH 3 (1, 4) signals of the compounds, whereas the sum of the single proton integrations was set to 100%.
Diethyl ether, t-butyl methyl ether and trichloromethane are also suitable organic solvents for the isolation of the products by means of extraction. Best results were otained by the use of trichloromethane, dichloromethane and ethyl acetate.
Diethyl ether/petroleum ether (30–50° C.) 1:1 (4000 ml) was added to the mixture. The resulting solution was cooled down to temperatures between −20 and −40° C. for 2 h while colorless needles or plates crystallised out of the solution. Removal of the mother liquor, subsequent swirling of the remaining crystals with precooled (−20° C.) diethyl ether/petroleum ether (30–50° C.) 1:1 (1000 ml) and removal of the solution yielded 5-bromo levulinic acid methyl ester (400 g, 37%) as colorless crystals, m. p. 12–15° C.
Ethanol, 2-propanol, diisopropyl ether and t-butyl methyl ether/petroleum ether (30–50° C.) 1:1 are also suitable solvents for the preparation of pure 5-bromo levulinic acid methyl ester by means of low-temperature crystallisation. Cyclohexane and the higher-boiling petroleum ether fractions instead of the low-boiling petroleum ether fractions in combination with the ethers mentioned above may also be used as solvents for the purpose of crystallisation. The best results were obtained by using the solvent mixture described according to Example 1.
EXAMPLE 2
Preparation of 5-bromolevulinic Acid Methyl Ester from Levulinic Acid Methyl Ester
In a threee-necked flask equipped with a mechanical stirrer, a reflux condenser, an internal thermometer and a dropping funnel, to a mixture of levulinic acid methyl ester (5 g, 38.4 mmol) and bulk grade methanol (30 ml) bromine (6.14 g, 38.4 mmol) was dropped at 20–25° C. during 15 min. Stirring was continued at 20–25° C. After 1.5 h the reaction temperature rised to 35° C. and the color of the solution changed from dark-red to orange within 2 min followed by the decrease of the inner temperature to 20–25° C. At this time the reaction was finished. Water was added (100 ml), which caused the precipitation of a yellowish oil. The oil was separated and the remaining aqueous solution was extracted with dichloromethane (2×30 ml). The combined organic extracts were added to the oil and the resulting mixture was washed with saturated aqueous sodium hydrogen carbonate (2×20 ml) and saturated aqueous sodium chloride (2×20 ml). Drying of the organic layer with Na 2 SO 4 and distillation of the solvent in vacuo yielded a pale yellow oil (7.56 g) consisting of 3-bromolevulinic acid methyl ester (1) (28%), 5-bromolevulinic acid methyl ester (2) (56%), 3,5-dibromolevulinic acid methyl ester (3) (8%) and levulinic acid methyl ester (4) (8%). Diethyl ether/petroleum ether (30–50° C.) 1:1 (50 ml) was added to the mixture. The resulting solution was then cooled down to temperatures between −20 and −40° C., and within 2 h colorless needles or plates crystallised out of the solution. Removal of the mother liquor, subsequent swirling of the remaining crystals with precooled (−20° C.) diethyl ether/petroleum ether (30–50° C.) 1:1 (20 ml) and removal of the solution yielded 5-bromolevulinic acid methyl ester (2.9 g, 36%) as colorless crystals, m. p. 12–15° C.
EXAMPLE 3
Preparation of Levulinic Acid Methyl Ester from the Remaining Mother Liquors, Which were Obtained by Low-Temperature Crystallisation of 5-bromolevulinic Acid Methyl Ester According to Example 1, Consisting of 3-bromolevulinic Acid Methyl Ester, 5-bromolevulinic Acid Methyl Ester, 3,5-dibromolevulinic Acid Methyl Ester and Levulinic Acid Methyl Ester
Distillation of the solvent from the combined mother liquors obtained from the low-temperature crystallisation of 5-bromolevulinic acid methyl ester according to Example 1 in vacuo afforded a mixture consisting of 3-bromolevulinic acid methyl ester (61%), 5-bromolevulinic acid methyl ester (23%), 3,5-dibromolevulinic acid methyl ester (8%) and levulinic acid methyl ester (8%). The mixture (5 g) was dissolved in bulk grade methanol (20 ml), a hydrogen catalyst (palladium on carbon) was then added and the mixture was hydrogenated for 5 h while passing in hydrogen at a pressure of 20 bar at 20–25° C. By monitoring the hydrogenation, it was found that the reaction was completed after 5 h ( 1 H-NMR, 13 C-NMR) and besides hydrogen bromide only levulinic acid methyl ester has been formed. Water was added (20 ml) and the resulting mixture was extracted with dichloro methane (3×20 ml). The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate (3×10 ml) and saturated aqueous sodium chloride. Drying of the organic layer with Na 2 SO 4 , followed by distillation of the solvent in vacuo yielded 2.5 g (80%) levulinic acid methyl ester. The obtained product may be used for the preparation of 5-bromolevulinic acid methyl ester according to Example 2. The further purification of the obtained levulinic acid methyl ester by distillation is not necessary, so that the raw-product may be directly lead back to the bromination step after removing the hydrogen bromide for the most part.
EXAMPLE 4
Preparation of 5-chlorolevulinic Acid Methyl Ester, 5-chlorolevulinic Acid Ethyl Ester, 5-chlorolevulinic Acid Propyl Ester and 5-chlorolevulinic Acid n-butyl Ester from Bromination Mixtures of the Corresponding Bromination Products by Phase-transfer Catalysed Bromine/chlorine Exchange. General Method for the Preparation of the 5-chlorolevulinic Acid methyl-, -ethyl-, -propyl- and -n-butyl Esters
In a threee-necked flask equipped with a mechanical stirrer, a reflux condenser, an internal thermometer and a dropping funnel, to a pre-cooled solution (10° C.) of levulinic acid (1 mol) or levulinic acid methyl ester (1 mol) and the corresponding alcohol (400 ml) which forms the alkyl chain of the prepared ester, bromine (1 mol) was added. Stirring was continued until the initial color of the mixture changed from dark-red to orange or yellow. While stirring, the mixture was allowed to attain 20–25° C. The reaction was finished when decolorisation of the mixture occured. Water was added (400 ml) which caused precipitation of an oil. The oil was separated and the remaining aqueous solution was extracted with a total of 200 ml of ethyl acetate. The aqueous layer was separated and to the organic layer were added saturated aqueous sodium chloride (1000 ml) and trioctyl methy ammonium chloride (10 g). Stirring was continued at 20–25° C. or under reflux until the reaction was virtually complete (DC, 1 H-NMR). If necessary, the aqueous sodium chloride was replaced by a freshly prepared solution. The organic layer was separated, washed with water (100 ml), dried with Na 2 SO 4 , and subsequently the solvent was distilled in vacuo. In a claisen apparatus, the residue was distilled in vacuo (10 mm, except the 5-chlorolevulinic acid n-butyl ether, b.p. 158° C. at 10 mm). In all cases a first fraction was taken, which contained the unconverted levulinic acid alkyl ester, the 3-chlorolevulinic acid alkyl ester and small amounts of the desired 5-chlorolevulinic acid alkyl ester. The residue of the distillation consisted of small amounts of both 5-chlorolevulinic acid alkyl ester and 3,5-dichlorolevulinic acid alkyl ester.
Differing from the general method, the 5-chlorolevulinic acid n-butyl ester was prepared by washing the bromination mixture acid-free with water. The resulting solution of the bromination mixture in n-butanol was supplied to the bromine/chlorine exchange step by phase-transfer catalysis. Afterwards, the process was continued as described according to the general method. The distillation was carried out at 5·10 −2 mm.
EXAMPLE 5
Preparation of 5-chlorolevulinic acid methyl ester from a mixture of 3-chloro-, 5-chloro-, 3,5-dichlorolevulinic acid ethyl ester and levulinic acid methyl ester consisting of the same product ratio, which is obtained by the bromination of both levulinic acid and levulinic acid methyl ester according to the Examples 1 and 2.
According to Example 4, a chlorination mixture of levulinic acid methyl ester was prepared. After the work-up as described, the solvent was distilled in vacuo. The product ratio of 5-chlorolevulinic acid methyl ester: 3,5-dichlorolevulinic acid methyl ester:3-chlorolevulinic acid methyl ester:levulinic acid methyl ester agreed with that found for the corresponding bromination products according to Example 1 and was calculated by means of the integration of the characteristic NMR proton signals.
Diethyl ether/petroleum ether (30–50° C.) 1:1 (800 ml) was added to the mixture of the raw-products and the mixture was kept at temperatures between −20° C. and −40° C. for 4 h while the desired product crystallised out of the solution as colorless needles. Removal of the mother liquor, subsequent swirling of the remaining crystals with pre-cooled (−20° C.) diethyl ether/petroleum ether (30–50° C.) 1:1 (200 ml) and removal of the solution yielded 5-chlorolevulinic acid methyl ester (62 g, 38%) as colorless crystals, m. p. 8–13° C. The crystallisation may also occur successfully using the additional listed solvents described in Example 1.
The NMR data of the product agree with the data of the 5-chlorolevulinic acid methyl ester obtained according to Example 4. The product, which is prepared by this method is obtained in >98% purity.
EXAMPLE 6
Catalytic Hydrogenation of the Residue of the Low-Temperature Crystallisation According to Example 5—Recycling of the Levulinic Acid Methyl Ester
Distillation of the solvent from the combined mother liquors obtained from the low-temperature crystallisation of 5-bromo levulinic acid methyl ester according to Example 1 in vacuo afforded a mixture consisting of 3-bromolevulinic acid methyl ester (61%), 5-bromolevulinic acid methyl ester (23%), 3,5-dibromolevulinic acid methyl ester (8%) and levulinic acid methyl ester (8%). The mixture (5 g) was dissolved in bulk grade methanol (20 ml), a hydrogen catalyst (palladium on carbon) and 2.45 g of triethyl amine were added and the mixture was hydrogenated for 5 h while passing in hydrogen at a pressure of 20 bar at 20–25° C. The reaction was completed after 5 h ( 1 H-NMR). The catalyst was then filtered off from the reaction mixture, and after the distillation of the solvent in vacuo, ethyl acetate was added and the solid was filtered off. Distillation of the sovent and the residue in vacuo afforded 2.96 g (95%) levulinic acid methyl ester.
EXAMPLE 7
Examplary Transesterification of 5-chlorolevulinic Acid Methyl Ester with 1-propanol
To a solution of 5-chlorolevulinic acid methyl ester (10 g) in 1-propanol (50 ml) and concentrated sulfuric acid was added (0.5 ml) and the reaction mixture was refluxed for 3 h. Thereafter, the methanol and the excess 1-propanol were distilled in vacuo. Dichloromethane was added to the residue and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. Drying of the organic layer with Na 2 SO 4 followed by distillation of the solvent in vacuo yielded 5.4 g (quant.) 5-chlorolevulinic acid propyl ester. The NMR data agreed with the data for the product obtained according to Example 4.
EXAMPLE 8
Examplary conversion of the 5-chlorolevulinic acid alkyl esters with sodium azide to the 5-azidolevulinic acid alkyl esters. General method for the preparation of the 5-azido levulinic acid methyl-, -ethyl-, -propyl- and n-butyl esters.
The 5-chlorolevulinic acid alkyl esters (1 g) were dissoled in bulk grade acetone (3 ml), the stoechiometric amount of sodium azide was added and the reaction mixture was stirred at 20–25° C. for 10 h. Filtration of the separated sodium chloride from the reaction mixture and distillation of the solvent in vacuo afforded the desired 5-azidolevulinic acid alkyl esters as yellow to dark-yellow oils in quantitative yield (purity>99%). No byproducts were formed.
EXAMPLE 9
Examplary conversion of 5-aminolevulinic acid hydrochloride by catalytic reduction of the 5-azidolevulinic acid alkyl esters and subsequent hydrolysis of the intermediate 5-aminolevulinic acid alkyl ester hydrochlorides. General method for the preparation and the hydrolysis of the intermediate 5-aminolevulinic acid alkyl ester hydrochlorides, which contain ester alkyl chains C1–C3 by catalytic hydrogenation of the alkyl esters and subsequent acid catalysed hydrolysis with formation of 5-aminolevulinic acid hydrochloride.
5-Azidolevulinic acid alkyl ester (1 g) was dissolved in a mixture of the alcohol (10 ml), which represents the alkyl chain in the final ester and aqueous hydrochloric acid (2 mol/l). A hydrogenation catalyst (palladium on carbon) was added and the mixture was hydrogenated for 3 h while passing in hydrogen at a pressure of 1–6 bar. By monitoring the hydrogenation, it was found that the hydrogenation was completed quantitatively after 3 h ( 1 H-NMR). The hydrogenation is accompanied by an increase of the reaction temperature to 35° C. The reaction is complete, when the reaction temperature reaches 20–25° C. again ( 1 H-NMR). The catalyst was then filtered off from the reaction mixture, and the alcohol was distilled in vacuo. A small amount of activated charcoal and aqueous hydrochloric acid (10 ml, 6 mol/l) were added and subsequently the reaction mixture was refluxed for 5 h. The activated charcoal was then filtered off, and both the water and the alcohol were removed by distillation in vacuo. While stirring, to the nearly colorless and viscous residue 2-propanol (20 ml) was added. After one minute a white and crystalline solid abruptly precipitated. The solid was filtered off using a glass frit Washing of the solid with little 2-propanol and drying of the crystals in vacuo yielded colorless crystals (85–90%, m. p. 150–151° C.) consisting of pure 5-aminolevulinic acid hydrochloride
When the batch size was increased starting from 75 g of 5-azidolevulinic acid alkyl ester the same result was obtained. The physical and spectroscopical data agree with those found in the literature (H.-J. Ha, S.-K. Lee, Y.-J. Ha, J. W. Park, Synth. Comm. 1994, 24(18), 2557–2562).
EXAMPLE 10
Examplary reaction of 5-chlorolevulinic acid alkyl esters with hexamethylene tetramine (urotropine) to the corresponding 5-urotropiniumlevulinic acid alkyl esters. Subsequent acid catalysed hydrolysis of the 5-urotropiniumlevulinic acid alkyl esters resulting in the formation of 5-amino levulinic acid hydrochloride.
5-Chlorolevulinic acid alkyl ester (5 g) was dissolved in ethanol (50 ml) and the calculated stoechiometric amount of hexamethylene tetramine(urotropine) was added. Afterwards, the reaction mixture was refluxed for 2 h. Filtration of the precipitated ammonium chloride and evaporation of the alcohol and the volatile formaldehyde diacetale in vacuo afforded a yellow to brown residue. The residue was dissolved in methanol and subsequently, the 5-aminolevulinic acid hydrochloride was precipitated as a white and microcrystalline solid by addition of diethyl ether. Filtration and subsequent drying of the solid in vacuo yielded pure 5-aminolevulinic acid hydrochloride (75–85%, m p. 150–151° C.). The NMR data of the obtained product agree with those found in the literature (H.-J. Ha, S.-K. Lee, Y.-J. Ha, J. W. Park, Synth. Comm. 1994, 24(18), 2557–2562). | A method for obtaining a 5-bromolevulinic acid methyl ester or a 5-chlorolevulinic acid methyl ester from either a bromination mixture or a chlorination mixture, containing either a 5-bromo-levulinic acid methyl ester or a 5-chlorolevulinic acid methyl ester, respectively, produced by either brominating or chlorinating levulinic acid or a levulinic acid methyl ester, and further including the steps of dissolving the bromination or chlorination mixture in an organic solvent or solvent mixture and cooling the solution, preferably to −20° C.–−40° C., with the 5-bromolevulinic acid methyl ester or 5-chlorolaevulinic acid methyl ester being crystallized out of the solution. The 5-bromolevulinic acid methyl ester or 5-chlorolevulinic acid is then isolated by draining off the solution with the remaining bromination mixture or chlorination mixture, as appropriate. | 2 |
This application is the U.S. national phase of International Application No. PCT/EP2014/064208 filed 3 Jul. 2014 which designated the U.S. and claims priority to EP Patent Application No. 13175330.3 filed 5 Jul. 2013, the entire contents of each of which are hereby incorporated by reference.
TECHNICAL FIELD
The present invention relates to the field of the synthesis of tocopherols and tocotrienols.
BACKGROUND OF THE INVENTION
Chromane compounds represent an important class of chiral natural products and bioactive compounds. An important class of chromane compounds are vitamin E and its esters. Often vitamin E is commercialized in the form of its esters because the latter show an enhanced stability.
On the one hand the typical technical synthesis of vitamin E leads to mixtures of isomers. On the other hand higher bioactivity (biopotency) has been shown to occur in general by tocopherols and tocotrienols having the R-configuration at the chiral centre situated next to the ether atom in the ring of the molecule (indicated by * in the formulas used later on in the present document) (i.e. 2R-configuration), as compared to the corresponding isomers having S-configuration. Particularly active are the isomers of tocopherols having the natural configuration at all chiral centres, for example (R,R,R)-tocopherols, as has been disclosed for example by H. Weiser et al. in J. Nutr. 1996, 126(10), 2539-49. This leads to a strong desire for an efficient process for separating the isomers. Hence, the isomer separation not only of vitamin E, but also of their esters, particularly their acetates, as well as of their precursors is of prime interest.
Separation of all the isomers by chromatographic methods is extremely difficult and costly.
To overcome these inherent problems, it has been tried to offer stereospecific synthesis allowing the preferential formation of the desired isomers only. However, these methods are very expensive, complex and/or exotic as compared to the traditional industrial synthesis leading to isomer mixtures.
Therefore, there exists a large interest in providing stereospecific synthesis routes leading to the desired isomer.
Particular difficult is to achieve specifically the desired chirality at the chiral carbon centre in the 2-position of the chromane ring.
A synthetic pathway for chromanes is via their corresponding chromanones. It is known from Kabbe and Heitzer, Synthesis 1978; (12): 888-889 that α-tocopherol can be synthesized via α-tocotrienol from 4-oxo-α-tocotrienol which is accessible from 2-acetyl-3,5,6-trimethylhydroquinone and farnesylacetone in the presence of pyrrolidine. However, this procedure leads to a racemic mixture in view of the configuration at the 2-position of the chromane respectively chromanone ring.
SUMMARY OF THE INVENTION
Therefore, the problem to be solved by the present invention is to offer a method for the synthesis of chromanones or chromanes, i.e. of compounds of formula (I) or (V) in a stereospecific matter in view of the 2-position in the chromanone or chromane ring.
Surprisingly, it has been found that a process for the manufacturing according to claim 1 is able to solve this problem.
It has been particularly found that the combination of a specific chiral compound and at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B) leads to the formation of the desired product and a desired stereoselective formation. Particularly, the desired isomer is formed in preference over the non-desired isomer yielding to an enantiomeric ratio being larger than zero, or a ratio of [2R]-stereoisomers to [2S]-stereoisomers being larger than one.
Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.
DETAILED DESCRIPTION OF THE INVENTION
In a first aspect the present invention relates to a process for the manufacturing of a compound of formula (I)
comprising the step of reacting compound of formula (II-A) and compound of formula (II-B) in the presence of
at least one chiral compound of formula (II-C) and of
at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B)
wherein R 1 , R 3 and R 4 are independently from each other hydrogen or methyl groups;
R 2 and R 2′ represents hydrogen or a phenol protection group;
R 5 represents either a linear or branched completely saturated C 6-25 -alkyl group or a linear or branched C 6-25 -alkyl group comprising at least one carbon-carbon double bond;
Y 1 represents either CH 2 Y 2 or
wherein R 6 represents a linear or branched C 1-12 -alkyl group which optionally further comprises at least one aromatic group and/or C═O and/or NH and/or NH 2 group;
Y 2 represents either OH or OR 7 or NHR 7 or NHCOOR 7 or
wherein R 7 represents either
a linear or branched C 1-12 -alkyl group which optionally further comprises at least one aromatic group and/or C═O and/or NH and/or NH 2 group
or
an aryl group or a substituted aryl group or a heteroaryl group or a substituted heteroaryl group
and the dotted line(s) represents the bond(s) by which the corresponding substituent is bound to the rest of formula (II-C);
and wherein * represents the chiral centre of the chiral isomer of formula (I) and wherein
Z 1 represents either H or a group CH 2 Z 4 or an aryl group;
Z 2 represents either H or a group CH 2 Z 4 or an aryl group;
Z 3 represents either H or a group CH 2 Z 4 or an aryl group;
wherein Z 4 represents H or an C 1 -C 6 alkyl group;
with the proviso that if Z 1 is different from H, that Z 2 represents H.
The term “independently from each other” in this document means, in the context of substituents, moieties, or groups, that identically designated substituents, moieties, or groups can occur simultaneously with a different meaning in the same molecule.
A “C x-y -alkyl”, resp. “C x-y -acyl” group, is an alkyl resp. an acyl group comprising x to y carbon atoms, i.e. for example an C 1-3 -alkyl group, is an alkyl group comprising 1 to 3 carbon atoms. The alkyl resp. the acyl group can be linear or branched. For example —CH(CH 3 )—CH 2 —CH 3 is considered as a C 4 -alkyl group.
A “C x-y -alkylene” group is an alkylene group comprising x to y carbon atoms, i.e., for example C 2 -C 6 alkylene group is an alkyl group comprising 2 to 6 carbon atoms. The alkylene group can be linear or branched. For example the group —CH(CH 3 )—CH 2 — is considered as a C 3 -alkylene group.
The term “hydrogen” means in the present document H and not H 2 .
The sign * in formulae of molecules represents in this document a chiral centre in said molecule.
In the present document any single dotted line represents the bond by which a substituent is bound to the rest of a molecule.
The chirality of an individual chiral carbon centre is indicated by the label R or S according to the rules defined by R. S. Cahn, C. K. Ingold and V. Prelog. This R/S-concept and rules for the determination of the absolute configuration in stereochemistry is known to the person skilled in the art.
The residue R 5 represents either a linear or branched completely saturated C 6-25 -alkyl group or a linear or branched C 6-25 -alkyl group comprising at least one carbon-carbon double bond.
Preferably the group R 5 is of formula (III).
In formula (III) m and p stand independently from each other for a value of 0 to 5 provided that the sum of m and p is 1 to 5. Furthermore, the substructures in formula (III) represented by s1 and s2 can be in any sequence. The dotted line represents the bond by which the substituent of formula (III) is bound to the rest of the compound of formula (II-B) or formula (I). Furthermore, # represents a chiral centre, obviously except in case where said centre is linked to two methyl groups.
It is preferred that group R 5 is of formula (III-x).
As mentioned above the substructures in formula (III) represented by s1 and s2 can be in any sequence. It is, therefore, obvious that in case that the terminal group is having the substructure s2, this terminal substructure has no chiral centre.
In one preferred embodiment m stands for 3 and p for 0.
In another preferred embodiment p stands for 3 and m for 0.
Therefore, R 5 is preferably of formula (III-A), particularly (III-ARR), or (III-B).
Preferred are the following combinations of R 1 , R 3 and R 4 :
R 1 =R 3 =R 4 =CH 3
or
R 1 =R 4 =CH 3 , R 3 =H
or
R 1 =H, R 3 =R 4 =CH 3
or
R 1 =R 3 =H, R 4 =CH 3
R 2 and R 2′ represents either hydrogen or a phenol protection group.
A phenol protection group is a group which protects the phenolic group (OH in formula (I) or (II-A)) and can be deprotected easily, i.e. by state-of-the-art methods, to the phenolic group again.
The phenol protection group forms with the rest of the molecule a chemical functionality which is particularly selected from the group consisting of ester, ether or acetal. The protection group can be easily removed by standard methods known to the person skilled in the art.
In case where the phenol protection group forms with the rest of the molecule an ether, the substituent R 2 or R 2′ is particularly a linear or branched C 1-10 -alkyl or cycloalkyl or aralkyl group. Preferably the substituent R 2 or R 2′ is a benzyl group or a substituted benzyl group, particularly preferred a benzyl group.
In case where the phenol protection group forms with the rest of the molecule an ester, the ester is an ester of an organic or inorganic acid.
If the ester is an ester of an organic acid, the organic acid can be a monocarboxylic acid or a polycarboxylic acid, i.e. an acid having two or more COOH-groups. Polycarboxylic acids are preferably malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid or fumaric acid.
Preferably the organic acid is a monocarboxylic acid.
Hence, the substituent R 2 or R 2′ is preferably an acyl group. The acyl group is particularly a C 1-7 -acyl, preferably acetyl, trifluoroacetyl, propionyl or benzoyl group, or a substituted benzoyl group.
If the ester is an ester of an inorganic acid, the inorganic acid is preferably nitric acid or a polyprotic acid, i.e. an acid able to donate more than one proton per acid molecule, particularly selected from the group consisting of phosphoric acid, pyrophosphoric acid, phosphorous acid, sulphuric acid and sulphurous acid.
In case where the phenol protection group forms with the rest of the molecule an acetal, the substituent R 2 or R 2′ is preferably
with n=0 or 1.
Hence, the acetals formed so are preferably methoxymethyl ether (MOM-ether), β-methoxyethoxymethyl ether (MEM-ether) or tetrahydropyranyl ether (THP-ether). The protection group can easily be removed by acid.
The protecting group is introduced by reaction of the corresponding molecule having an R 2 resp. R 2′ being H with a protecting agent.
The protecting agents leading to the corresponding phenol protection groups are known to the person skilled in the art, as well as the chemical process and conditions for this reaction. If, for example, the phenol protection group forms with the rest of the molecule an ester, the suitable protecting agent is for example an acid, an anhydride or an acyl halide.
In the case that an ester is formed by the above reaction with the protecting agent, and that said ester is an ester of an organic polycarboxylic acid or an inorganic polyprotic acid, not necessarily all acid groups are esterified to qualify as protected in the sense of this document. Preferable esters of inorganic polyprotic acids are phosphates.
It is preferred that the protection group R 2 resp. R 2′ is a benzoyl group or a C 1-4 -acyl group, particularly acetyl or trifluoroacetyl group. The molecules in which R 2 resp. R 2′ represents an acyl group, particularly an acetyl group, can be easily prepared from the corresponding unprotected molecule by esterification, respectively the phenolic compound can be obtained from the corresponding ester by ester hydrolysis.
It is important to realize that the step of reacting with the protecting agent can occur at different stages of manufacture of compound of formula (I) or of formula (V), the preparation of which is described later in this document in more detail, i.e. the reaction can occur for example at the level of compound of formula (II-A) or before or after preparation of compound (I) or compound (V).
It is particularly preferred that R 2 and R 2′ is H.
The process of the present invention comprises the steps of reacting compound of formula (II-A) and compound of formula (II-B).
The corresponding compounds of (II-A) and compound of formula (II-B) are easily accessible. For example compounds of (II-A) can be synthesized from the method disclosed in G. Manecke, G. Bourwieg, Chem. Ber. 1962, 95, 1413-1416.
The mentioned reaction between compound of formula (II-A) and compound of formula (II-B) is done in the presence of at least one chiral compound of formula (II-C) and of at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B).
The group Y 1 represents either CH 2 Y 2 or
R 6 represents in first instance a linear or branched C 1-12 -alkyl group. Particularly suitable linear or branched C 1-12 -alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl groups.
R 6 represents in second instance a linear or branched C 1-12 -alkyl group which comprises further at least one aromatic group and/or C═O and/or NH and/or NH 2 group. Examples of suitable compounds of formula (II-C) for this embodiment are
Y 2 represents either OH or OR 7 or NHR 7 or NHCOOR 7 or
R 7 represents in a first instance a linear or branched C 1-12 -alkyl group. Particularly suitable linear or branched C 1-12 -alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl groups.
R 7 represents in a second instance a linear or branched C 1-12 -alkyl group which further comprises at least one aromatic group and/or C═O and/or NH and/or NH 2 group.
R 7 represents in a third instance an aryl group or a substituted aryl group or a heteroaryl group or a substituted heteroaryl group. The aryl group or a substituted aryl group or a heteroaryl group or a substituted heteroaryl group is particularly
It is preferred that the compound of formula (II-C) is selected from the group consisting of
The compounds of formula (II-B) can be synthesized from corresponding precursors, for example the compound (E,E)-farnesylacetone from nerolidol by a chain-elongation reaction, as described in WO 2009/019132.
In one preferred embodiment the group R 5 does not comprise any chiral centres. The compound of formula (II-B) is preferred from the group consisting of (E)-6,10-dimethylundeca-5,9-dien-2-one, (5E,9E)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one and (5E,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, particularly (5E,9E)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one.
When the group R 5 comprises chiral centres, it is preferred that the compound of formula (II-B) is in a form of pure chiral isomers.
This can be either achieved by stereospecific synthesis routes or by isolation of naturally occurring compounds or derived thereof or by separation from a mixture of the chiral stereoisomers.
For example (6R,10R)-6,10,14-trimethylpentadecan-2-one can be obtained from naturally occurring (R,R)-phytol by oxidation with NaIO 4 and a catalytic amount of RuCl 3 as disclosed by Thomas Eltz et al. in J. Chem. Ecol. (2010) 36:1322-1326.
In another preferred embodiment the compound of formula (II-B) is a methyl ketone having at least a carbon-carbon double bond in the γ,δ-position to the keto group. Preferably it is selected from the group consisting of 6-methylhept-5-en-2-one, (E)-6,10-dimethylundec-5-en-2-one, (Z)-6,10-dimethylundec-5-en-2-one, (E)-6,10-dimethylundeca-5,9-dien-2-one, (Z)-6,10-dimethylundeca-5,9-dien-2-one, (E)-6,10,14-trimethylpentadec-5-en-2-one, (Z)-6,10,14-trimethylpentadec-5-en-2-one; (5E,9E)-6,10,14-trimethylpentadeca-5,9-dien-2-one, (5E,9Z)-6,10,14-trimethylpentadeca-5,9-dien-2-one, (5Z,9E)-6,10,14-trimethylpentadeca-5,9-dien-2-one, (5Z,9Z)-6,10,14-trimethylpentadeca-5,9-dien-2-one; (E)-6,10,14-trimethylpentadeca-5,13-dien-2-one, (Z)-6,10,14-trimethylpentadeca-5,13-dien-2-one; (5E,9E)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one, (5E,9Z)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one, (5Z,9E)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one, (5Z,9Z)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one; (E)-6,10,14,18-tetramethylnonadec-5-en-2-one, (Z)-6,10,14,18-tetramethylnonadec-5-en-2-one; (5E,9E)-6,10,14,18-tetramethylnonadeca-5,9-dien-2-one, (5E,9Z)-6,10,14,18-tetramethylnonadeca-5,9-dien-2-one, (5Z,9E)-6,10,14,18-tetramethylnonadeca-5,9-dien-2-one, (5Z,9Z)-6,10,14,18-tetramethylnonadeca-5,9-dien-2-one; (5E,13E)-6,10,14,18-tetramethylnonadeca-5,13-dien-2-one, (5E,13Z)-6,10,14,18-tetramethylnonadeca-5,13-dien-2-one, (5Z,13E)-6,10,14,18-tetramethylnonadeca-5,13-dien-2-one, (5Z,13Z)-6,10,14,18-tetramethylnonadeca-5,13-dien-2-one; (E)-6,10,14,18-tetramethylnonadeca-5,17-dien-2-one, (Z)-6,10,14,18-tetramethylnonadeca-5,17-dien-2-one; (5E,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5E,9E,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5E,9Z,13E)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5E,9Z,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5Z,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5Z,9E,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5Z,9Z,13E)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one, (5Z,9Z,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one; (5E,13E)-6,10,14,18-tetramethylnonadeca-5,13,17-trien-2-one, (5E,13Z)-6,10,14,18-tetramethylnonadeca-5,13,17-trien-2-one, (5Z,13E)-6,10,14,18-tetramethylnonadeca-5,13,17-trien-2-one, (5Z,13Z)-6,10,14,18-tetramethylnonadeca-5,13,17-trien-2-one; (5E,9E)-6,10,14,18-tetramethylnonadeca-5,9,17-trien-2-one, (5E,9Z)-6,10,14,18-tetramethylnonadeca-5,9,17-trien-2-one, (5Z,9E)-6,10,14,18-tetramethylnonadeca-5,9,17-trien-2-one, (5Z,9Z)-6,10,14,18-tetramethylnonadeca-5,9,17-trien-2-one; (5E,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5E,9E,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5E,9Z,13E)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5E,9Z,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (ZE,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5Z,9E,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5Z,9Z,13E)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5Z,9Z,13Z)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one, (5E,9E,13E)-6,10,14,18-tetramethylnonadeca-5,9,13-trien-2-one.
In case there are chiral centres in the group R 5 , particularly if R 5 has the formula (III-ARR), the corresponding compounds of formula (II-B) can be prepared by asymmetrically hydrogenating olefinic unsaturated precursors thereof using chiral iridium complexes as disclosed in WO 2006/066863 A1 and WO 2012/152779 A1 the entire content of which is hereby incorporated by reference.
In case the compounds just mentioned have chiral carbon centre(s) it is preferred that said chiral centre(s) has/have the configuration as indicated in formula (III-x).
Preferably the compound of formula (II-B) in this embodiment is (E)-6,10-dimethylundec-5,9-dien-2-one (geranyl acetone) or (Z)-6,10-dimethylundec-5,9-dien-2-one (neryl acetone) or (5E,9E)-6,10,14-trimethylpentadeca-5,9-dien-2-one (E,E-farnesyl acetone) or (5Z,9Z)-6,10,14-trimethylpentadeca-5,9-dien-2-one (Z,Z-farnesyl acetone) or (E)-6,10-dimethylundec-5-en-2-one or (Z)-6,10-dimethylundec-5-en-2-one or (E)-6,10,14-trimethylpentadec-5-en-2-one or (Z)-6,10,14-trimethylpentadec-5-en-2-one, preferably geranyl acetone or E,E-farnesyl acetone or (Z)-6,10-dimethylundec-5-en-2-one or (Z)-6,10,14-trimethylpentadec-5-en-2-one, more preferably geranyl acetone or E,E-farnesyl acetone.
More preferred the compound of formula (II-B) is 6,10-dimethylundecan-2-one or 6,10,14-trimethylpentadecan-2-one.
Most preferred the compound of formula (II-B) is either (6R),10-dimethylundecan-2-one or (6R,10R),14-trimethylpentadecan-2-one.
It is more preferred that the compound of formula (II-C) is selected from the group consisting of
The process of the present invention comprises the steps of reacting compound of formula (II-A) and compound of formula (II-B) in the presence of at least one chiral compound of formula (II-C) and of at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B).
For the sake of clarity, it is stressed that substituents having the same label in the same formula represent in the present application the same group, meaning that in formula (X-A) and (X-B) the two groups Z 1 are identical.
In those formulae Z 1 represents either H or a group CH 2 Z 4 or an aryl group and Z 2 represents either H or a group CH 2 Z 4 or an aryl group and Z 3 represents either H or a group CH 2 Z 4 or an aryl group, wherein Z 4 represents H or an C 1 -C 6 alkyl group, with the proviso that if Z 1 is different from H, that Z 2 represents H.
In other words, it is important to realize that except for the case of urea and thiourea (Z 1 =Z 2 =Z 3 =H), all suitable ureas or thioureas have necessarily the structural element of formula (XI-a1) or (XI-a2) or (XI-b1) or (XI-b2) in common.
Furthermore, in the structures of (XI-a1), (XI-a2), (X-I-b1) and (XI-b2) the carbon(s) (indicated by C) attached to the nitrogen atom is either a CH 2 carbon atom or an aromatic carbon atom.
The aryl group in Z 1 or Z 2 or Z 3 is preferably a group of formula (XII)
wherein Z 5 is a C 1 -C 6 alkyl group or a CF 3 group and n stands for 0 or 1 or 2 or 3.
Said group of formula (XII) has, hence, either no or 1 or 2 or 3 groups Z 5 attached to the phenyl ring.
In case of two groups Z 5 attached they are preferably attached in the meta positions in view of the binding site.
In case of three groups Z 5 attached they are preferably attached in the ortho positions and the para position in view of the binding site.
In a preferred embodiment the urea compound of formula (X-A) is a selected from the group consisting of urea, 1,3-dimethylurea, 1,3-diethylurea, 1,1,3-trimethylurea, 1,1,3-triethylurea, 1,3-diphenylurea and 1,3-bis(3,5-bis(tri-fluoromethyl)phenyl)urea.
In a preferred embodiment the thiourea compound of formula (X-B) is a selected from the group consisting of thiourea, 1,3-dimethylthiourea, 1,3-diethylthiourea, 1,1,3-trimethylthiourea, 1,1,3-triethylthiourea, 1,3-diphenylthiourea and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)thiourea.
More preferred urea compound of formula (X-A) or thiourea compound of formula (X-B) are either selected from the group consisting of urea, 1,3-dimethylurea, 1,1,3-trimethylurea and 1,3-diphenylurea or of the group consisting of thiourea, 1,3-diphenylthiourea and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)thiourea.
The compounds of formula (II-C) are chiral compounds. The compounds are either used directly as pure stereoisomers or separated by known techniques into the R- and the S-stereoisomer prior to the use for the present invention.
It has been found that the isomer shown in formula (II-C) yields preferentially the isomers of compound of formula (I), respectively of formula (V), showing the R-configuration at the chiral centre indicated by *.
Therefore, it has been found that the chirality of the compound of formula (II-C) has an important effect on the chirality of the compound being formed, i.e. on compound of formula (I) or of formula (V).
Hence, the isomer having the R-configuration at the chiral centre marked by * in formula (I) is preferentially formed in respect to the corresponding isomer having the S-configuration at said chiral centre by the above process.
On the other hand, it has been found that when using the stereoisomers shown in formula (II-C′) instead of compounds of formula (II-C) preferentially the isomers of compound of formula (I) resp. formula (V) showing the S-configuration at the chiral centre indicated by * are obtained.
Compound of formula (II-A) and compound of formula (II-B) are reacted in the presence of at least one chiral compound of formula (II-C) and of at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B).
It is preferred that this reaction occurs in an organic solvent. In one embodiment the reaction is undertaken in an organic solvent which is a hydrocarbon, preferably in an aromatic hydrocarbon, particularly in toluene, particularly at a temperature of preferably between 80° C. and 150° C., more preferably of between 90° C. and 140° C., most preferably at a temperature of between 100 and 110° C. at ambient pressure. It is preferred that the reaction temperature is about 5 to 10° C. below the boiling point of the solvent.
In another embodiment the reaction is undertaken in an organic polar solvent which is selected from the group consisting of alcohols, ethers, esters, carbonitriles, halogenated hydrocarbons and lactams. Particularly suitable polar solvents are acetonitrile, ethyl acetate, methanol, ethanol, dichloromethane, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), 1,2-dichloroethane, 2,2,2- and isopropanol.
Furthermore, it has been shown that the amount of organic solvent is preferably chosen so that at least a 4% by weight solution of compound of formula (II-A) is obtained. In a preferred embodiment the weight ratio between compound of formula (II-A) and organic solvent is between 2:98 and 80:20, particularly between 3:97 and 50:50, preferably between 4:96 and 30:70.
It has been found that the lower the temperature for the reaction of compound of formula (II-A) and compound of formula (II-B) is, the higher the chiral purity of the compound of formula (I) resp. (V) in view of chirality at the chiral centre indicated by * is. This chiral purity is expressed by the enantiomeric excess (ee) being determined by the absolute value of the difference of amounts of the R and S isomers divided by the sum of amounts of both isomers: and is normally expressed in %.
e
e
=
abs
(
[
R
]
-
[
S
]
[
R
]
+
[
S
]
)
We have been able to show that by using a reaction temperature of 0° C. the process has yielded in the formation of a product having an enantiomeric excess up to 40%, corresponding to a ratio of [R]/[S] of 2.3. However, the reaction rate was rather low.
In view of reaction rate, it is preferred to have the reaction taking place at higher temperatures higher than 0° C.
Furthermore, it might be helpful, particularly in the case where at low reaction temperatures are used, to use molecular sieves in the reaction medium.
The enantiomeric ratio can be increased further by optimizing the reaction conditions. The larger the enantiomeric ratio is the better. However, also at lower enantiomeric ratios the invention can be advantageous as the complete separation of the isomers, such as by chromatography, particularly by chromatography using chiral stationary phases, needs much less efforts as compared to a racemic mixture. Hence, the enantiomeric ratio should be at least 15%, preferably at least 20%, more preferably at least 25%.
In a further aspect, the invention relates to a process of manufacturing a compound of formula (V) comprising the steps
i) process of manufacturing of formula (I) as it has been described in detail above; ii) reducing of compound of formula (I)
The substituents R 1 , R 2 , R 3 , R 4 and R 5 are already discussed in detail above.
Most preferably the chiral isomers of formula (V) are the isomers selected from the group consisting of
α-Tocopherol (R 1 =R 3 =R 4 =CH 3 , R 5 =(II-A), particularly (II-ARR), R 2 =H), β-Tocopherol (R 1 =R 4 =CH 3 , R 3 =H, R 5 =(II-A), particularly (II-ARR), R 2 =H), γ-Tocopherol (R 1 =H, R 3 =R 4 =CH 3 , R 5 =(II-A), particularly (II-ARR), R 2 =H), δ-Tocopherol (R 1 =R 3 =H, R 4 =CH 3 , R 5 =(II-A), particularly (II-ARR), R 2 =H), α-Tocotrienol (R 1 =R 3 =R 4 =CH 3 , R 5 =(II-B), R 2 =H), β-Tocotrienol (R 1 =R 4 =CH 3 , R 3 =H, R 5 =(II-B), R 2 =H), γ-Tocotrienol (R 1 =H, R 3 =R 4 =CH 3 , R 5 =(II-B), R 2 =H), δ-Tocotrienol (R 1 =R 3 =H, R 4 =CH 3 , R 5 =(II-B), R 2 =H),
and the esters, particularly the acetates (R 2 =COCH 3 ), or phosphates thereof.
Particularly preferred compounds of formula (V) are esters of organic and inorganic acids. Examples of esters of organic acids are acetate and succinate esters, esters of inorganic esters are tocopheryl phosphates, ditocopheryl phosphates, particularly α-tocopheryl phosphate and α-ditocopheryl phosphate.
Most preferred compounds of formula (V) are tocopherols and tocopheryl acetates.
Most preferred compounds of formula (V) are tocopherols and tocopheryl acetates.
The reduction in step ii) can be made by different ways. Typically it is reduced by using a reduction means.
Preferably the reduction is made by metallic zinc in the presence of an acid or an acid mixture, for example as disclosed for in U.S. Pat. No. 6,096,907 or EP 0 989 126 the whole disclosure of which is incorporated herein by reference.
The reduction step ii) is typically done in stirred vessel under inert atmosphere. It is further preferred that the step ii) is done at a temperature in the range of 30 to 90° C., particularly between 40 and 65° C.
After completion of the reaction the compound of formula (V) is purified, particularly by means of extraction.
It has been observed that the reduction of compound of formula (I) to compound of formula (V) does not modify the chirality of the chiral centre indicated by * in the formulae (I) resp. (V).
It has been found that the isomer shown in formula (II-C) yields preferentially the isomers of compound of formula (I), respectively of formula (V), showing the R-configuration at the chiral centre indicated by *.
Hence, the isomer having the R-configuration at the chiral centre marked by * in formula (V) is preferentially formed in respect to the corresponding isomer having the S-configuration at said chiral centre.
On the other hand, it has been found that when using the stereoisomers shown in formula (II-C′) instead of compounds of formula (II-C) preferentially the isomers of compound of formula (I) resp. formula (V) showing the S-configuration at the chiral centre indicated by * are obtained.
In a further aspect, the invention relates to a composition comprising
a) at least one compound of formula (II-A) and b) at least one ketone of formula (II-B) and c) at least one chiral compound of formula (II-C) and d) at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B)
The substituents R 1 , R 2′ , R 3 , R 4 , R 5 , Y 1 , Z 1 , Z 2 and Z 3 have already been discussed in detail above.
Furthermore, details for the compound of formula (II-A), for compound of formula (II-B), for compound of formula (X-A), for compound of formula (X-B) and for chiral compound of formula (II-C) as well their preferred embodiments and their ratios have been discussed in detail already above.
As described above this composition is very suitable for the synthesis of compound of formula (I) which can be transformed to compound of formula (V).
Therefore, a chiral compound of formula (II-C) can be used for the preparation of tocopherols or tocotrienols as it also discussed in great detail above. This use particularly involves the use of a chiral compound of formula (II-C) for the preparation of compound of formula (I) followed by transformation to compound of formula (V). When this use is made in the presence of at least one urea compound of formula (X-A) or at least one thiourea compound of formula (X-B) the formation of the stereoisomer of formula (I) resp. (V) having the R configuration at the chiral carbon centre marked by * in formula (I) resp. (V) is obtained in an excess related to the corresponding stereoisomer having the S-configuration.
The details for chiral compound of formula (II-C), for compound of formula (I), for formula (V) and for the urea compound of formula (X-A) or thiourea compound of formula (X-B) as well their preferred embodiments and their ratios have been discussed in detail already above.
EXAMPLES
The present invention is further illustrated by the following experiments.
Use of Additives
0.5 mmol of 2-acetyl-3,5,6-trimethylhydroquinone and 0.795 mmol of the additive indicated in table 1 have been suspended in a 20 mL round bottom flask equipped with a magnetic stirring bar, heating device, water and argon supply at 23° C. in 2.5 mL (23.47 mmol) toluene. Then 0.514 mmol of E,E-farnesylacetone has been is added and finally 0.795 mmol (S)-2-(methoxymethyl)pyrrolidine has been added. The reaction mixture has been stirred at 23° C. for the time indicated in table 1. When heated to 120° C. water is distilled off and the reaction mixture was getting brown. After the indicated time at 120° C., the reaction mixture was cooled to 23° C. Then 1 mL of 2 N HCl has been added and the mixture has been transferred to a separation funnel and was well shaken. The toluene phase was separated and washed with portions of 10 mL water until a neutral water phase was obtained. The organic layers are dried over sodium sulfate, filtered and concentrated at 40° C. and 10 mbar.
The product formed and isolated by column chromatography on SiO 2 has been identified to be 6-hydroxy-2,5,7,8-tetramethyl-2-((3E,7E)-4,8,12-trimethyltrideca-3,7,11-trien-1-yl)chroman-4-one:
1 H NMR (CDCl 3 , 300 MHz) δ 1.30 (s, 3H); 1.51 (s, 6H); 1.52 (s, 3H); 1.54-1.58 (m, 1H); 1.61 (d, J=0.9 Hz, 3H); 1.67-1.78 (m, 1H); 1.67-2.10 (m, 10H); 2.08 (s, 3H); 2.16 (s, 3H); 2.48 (s, 3H); 2.51 (d, J=15.8 Hz, 1H); 2.68 (d, J=15.8 Hz, 1H), 4.45 (s br, 1H); 4.99-5.05 (m, 3H) ppm.
13 C NMR (CDCl 3 , 75.5 MHz) δ 12.1; 12.8; 13.3; 15.9; 16.0; 17.7; 22.2; 23.7; 25.1; 26.6; 26.8; 39.4; 39.7 (2C); 49.5; 79.4; 116.7; 120.4; 123.5; 124.0; 124.1; 124.4; 131.3; 132.0; 135.1; 135.7; 145.8; 152.8; 195.2 ppm.
Determination of enantiomeric ratio: HPLC, Chiralcel® OD-H, 250×4.6 mm, 10 mL EtOH, 990 mL n-hexane, 1.0 mL/min; detection at 220 nm.
TABLE 1 Different additives. t 23° C. t 120° C. Yield 1 ee Additive [h] [h] [%] [R]:[S] [%] Ref. 1 none 20 1.5 2.2 50:50 0 Ref. 2 1,1-dimethylurea 17 24 0 — 2 — 2 Ref. 3 1,1,3,3-tetramethylurea 17 48 0 — 2 — 2 Ref. 4 1,3-dicyclohexylurea 17 24 0 — 2 — 2 Ref. 5 1,1,3,3-tetramethylthiourea 17 48 0 — 2 — 2 Ref. 6 1,3-dicyclohexylthiourea 17 24 0 — 2 — 2 1 urea 16 24 16 63:37 26 2 1,3-dimethylurea 16 124 18 58:42 16 3 1,1,3-trimethylurea 16 124 9 61:39 22 4 1,3-diphenylurea 0 17 2.6 61:39 22 5 thiourea 0 5 13 60:40 20 6 1,3-diphenylthiourea 0 14 3 62:38 24 7 1,3-bis(3,5-bis(trifluoromethyl)- 0 14 2 70:30 40 phenyl)thiourea 1 yield relative to 2-acetyl-3,5,6-trimethylhydroquinone 2 as no reaction occurred (yield: 0%) no measurements were possible
Conversion of Chromanones to Chromans
6-hydroxy-2,5,7,8-tetramethyl-2-((3E,7E)-4,8,12-trimethyltrideca-3,7,11-trien-1-yl)chroman-4-one been transformed to α-tocotrienol by treatment with zinc dust and aqueous hydrochloric acid, as described in detail by Baldenius et al., EP 0 989 126 A1:
6-Hydroxy-2,5,7,8-tetramethyl-2-((3E,7E)-4,8,12-trimethyltrideca-3,7,11-trien-1-yl)chroman-4-one (5.0 mmol) (example 2) was dissolved under an argon atmosphere in 25 mL toluene, and 25% aqueous HCl (41.7 mL, 340 mmol) was added. To this mechanically stirred two-phasic mixture zinc dust (65 mmol) was added in small portions (ca. 0.5 g) during 4 h. Stirring was continued at 40° C. for 16 h and at 65° C. for 1 h. After completion of the reaction (TLC control), the mixture was cooled to room temperature and filtered through a pad of Dicalite. The filter residue was washed with 100 mL n-heptane, and the combined filtrates washed with 50 mL water. The organic layer was dried over sodium sulfate, filtered, concentrated at 40° C. and 10 mbar and dried for 2 h at 0.003 mbar at 23° C. The 2.22 g yellowish-brown oil was purified by column chromatography (100 g SiO 2 silica gel 60, n-hexane/EtOAc 9:1). After evaporation (40° C./20 mbar) and drying (0.021 mbar/23° C.) α-tocotrienol was obtained as a yellowish-brown oil (1.291 g, purity 93.9 wt %, yield 57%).
The compound obtained showed identical retention time in comparison to an authentic sample of natural (R,E,E)-α-tocotrienol, and the values obtained by measuring the 1 H NMR (CDCl 3 , 300 MHz) were identical with the values for α-tocotrienol, as for example reported by P. Schudel et al., Helv. Chim. Acta 1963, 46, 2517-2526.
Determination of enantiomeric ratio: HPLC, Chiralcel® OD-H, 250×4.6 mm, 0.5% EtOH in n-hexane, 1.0 mL/min; detection at 220 nm. | The present invention relates to a synthesis of chromanones or chromanes in a stereospecific matter in view of the 2-position in the chromanone or chromane ring. It has been found that this synthesis is particularly possible in the presence of a chiral compound of formula of a specific type and of at least one urea or thiourea. | 2 |
[0001] This application claims the benefit of prior U.S. provisional patent application No. 60/963,688 date Aug. 7, 2008, the contents of which is hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a pliable kitchen utensil dryer.
[0003] Hereinafter in specification and claims the term ‘kitchen utensils’ is used to denote any cutlery, crockery, cooking utensils and the like—it being obvious that the invention may be applied to other utensils which require drying.
BACKGROUND OF THE INVENTION
[0004] In order to dry kitchen utensils at a vicinity of a kitchen sink, it is common to place kitchen utensils over a regular kitchen towel for drying purposes. Such a kitchen towel typically comprises a single layer of a fabric material which is often a terry cloth or plain cotton. Such towels have a restricted liquid absorption capacity and are slow in drying. Even more so placing fine crockery utensils such as wine glasses over a single layered towel may result in breaking or chipping of the utensil. Placing wet dishes over the single layered fabric material often results in steam that accumulates in the utensils (in particular glasses and the like) placed over the material, as the steam and humidity do not evaporate. Such conditions may result in water stains on the utensils and may even cause development of mold and bacteria which may cause unpleasant smell and health hazard.
[0005] Various types of multilayered pliable articles are known in the art. Such articles are often directed to cleaning various surfaces, to wash surfaces and to retain various liquids.
[0006] U.S. Pat. No. 6,858,281 discloses a golf towel for retaining water over four hours. Such cloth comprises an outer layer of Terry cloth made of a composite texture of, including but not limited to, cotton, polyester and polyimide; an inner layer of porous hydrophilic polymer; and a grommet for a holding means. The layers are cut into a similar size and stitched together to prevent a separate moving.
[0007] EP0060076 describes a cleaning cloth which comprises a layer of foamed synthetic plastics material united with a piece of woven or knitted fabric. The foamed synthetic plastics material according to this patent can be sandwiched between two layers of fabric.
[0008] U.S. Pat. No. 3,162,964 relates to cleaning cloths employed for various household purposes and for similar uses and also to wash cloths for personal use.
SUMMARY OF THE INVENTION
[0009] The present invention is concerned with a multi layered kitchen utensil dryer comprising at least one layer of porous absorbent material enveloped by at least one sheet material, said sheet material being secured to the absorbent material.
[0010] The invention is further directed towards a multi layered kitchen utensils dryer comprising at least two layers of sheet material co-extensive in shape with an at least one layer of a porous absorbent material, wherein the at least one layer of the absorbent material is sandwiched between the at least two layers of sheet material and secured to one another at least around their common periphery to prevent separate moving.
[0011] Any one or more of the following features and characteristics may be implemented in a kitchen utensil dryer according to the present invention: the dryer may be capable of rapid large volume liquid absorption and vast evaporation; the sheet material may comprise a first layer corresponding with one face of the absorbent material, and a second layer corresponding with another face of the absorbent material, and wherein said first layer and said second layer may be made of same material or different material; at least one of the first layer and second layer of sheet material may be a fabric material; the fabric material may be Terry cloth; the fabric material may be microfiber; the fabric material may be mesh; the absorbent material may be enveloped by a single continuous layer of the sheet material; at least one of the sheet material and the absorbent material may be impregnated with at least one of an anti bacterial, anti microbial, anti fungi and anti mold agent; the absorbent material and the sheet material may be co-extensive; the layers may be secured at least around the edges thereof; and the layers may be secured together at least around their edges and in at least two intervaled longitudinal and traverse stitches on faces thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In order to understand the invention and to see how it may be carried out in practice, embodiments will now be described, by way of non-limiting examples only, with reference to the accompanying drawings, in which:
[0013] FIG. 1 is an isometric view of a kitchen utensil dryer according to an embodiment of the present invention;
[0014] FIG. 2A is a section along III-III in FIG. 1 ;
[0015] FIG. 2B is an enlargement of the portion marked B in FIG. 2A ;
[0016] FIG. 3 is an exploded isometric view of the kitchen utensil dryer seen in FIG. 1 ;
[0017] FIG. 4 is a diagram representing liquid evaporation rate over time, from a kitchen utensil dryer according to an embodiment of the present invention, and a typical kitchen towel;
[0018] FIG. 5 is an exploded isometric view of the kitchen utensil dryer according to an embodiment of the invention; and
[0019] FIGS. 6A-6B is a sectional view of a kitchen utensil dryer according to another embodiment of the present invention
DETAILED DESCRIPTION OF EMBODIMENTS
[0020] In the following description the present invention will be described with reference to a kitchen utensil dryer.
[0021] In FIG. 1 a multilayered kitchen utensil dryer generally designated 10 is shown. The multilayered kitchen utensil dryer 10 is capable of rapid large volume liquid absorption and rapid liquid evaporation. The dryer 10 comprises according to an exemplified in FIG. 1 embodiment two layers of sheet material (only layer 12 seen in FIG. 1 ; see also FIGS. 2A and 2B ) co-extensive in shape with at least one layer of porous absorbing material such as sponge 16 (not seen in FIG. 1 ).
[0022] The at least one layer of porous absorbent material 16 is sandwiched between the two layers of sheet material 12 and 14 and is secured to the same by stitches 20 , at least around their common periphery, such that a separate movement of the sponge away from the layers 12 and 14 enveloping it is prevented. In addition to the stitches 20 around the common periphery, the layers of the dryer 10 are also secured in a warp 22 and weft 24 pattern. The warp stitch 22 and weft stitch 24 secure all the layers of the dryer 10 together in a fixed relationship and in an eye pleasing fashion.
[0023] The porous absorbent material 16 is such that when soaking wet, washed and dried, e.g. in a washing machine and dried in a dryer machine, the separate layers of the dryer will not shrink and will prevent the fabric layers from deformation of the dryer as typically happens with kitchen towels used for similar purposes.
[0024] Noting that the dryer is used extensively and in wet vicinity, it is often soaked with liquid, typically water, giving rise to generation of fungi, bacteria, mold and the like. In order to prevent this from happening the dryer, in addition to it's rapid liquid evaporation property, may optionally be impregnated with at least an anti bacterial agent, anti microbial and/or anti fungi (including micro fungi such as mold) agents.
[0025] FIG. 2B is an enlargement of the portion marked B in FIG. 2A illustrating an edge of the dryer 10 and it shows the overlapping relation of the second layer 14 over the first layer 12 such that the stitch 20 secures the two layers 12 and 14 and the sponge 16 together in a fixed relation and in an eye-pleasing fashion. The pipe stitch includes all layers of the dryer and provides a reliable coupling arrangement which apart for being eye-pleasing also ensures that the dryer maintains its shape and that the different layers do not detach from one another, whilst not deteriorating the absorbing qualities of the dryer.
[0026] Referring now to FIG. 3 , an exploded view of an embodiment of a dryer 39 is shown, wherein the absorbent material 40 is enveloped by a single, continuous layer of sheet material 42 , having a first layer 44 corresponding with a face 46 of the absorbent material 40 , and a second layer 48 corresponding with a second face 50 of the absorbent material 40 . Other features are substantially similar to the embodiment of FIG. 1 .
[0027] The embodiment of FIG. 5 illustrates a dryer 52 wherein the absorbent material 54 is enveloped by two individual layers of sheet material, a first layer 56 corresponding with a face 58 of the absorbent material 54 , and a second layer 60 corresponding with a second face 62 of the absorbent material 54 .
[0028] According to any of the embodiments previously described, the porous absorbent material may be porous rubber, porous cellulose, a sponge and the like. The sheet layer enveloping the absorbent material may be a natural or synthetic fabric material such as Terry cloth, mesh, microfiber, regular cotton fabric and the like.
[0029] For example, one layer of a sheet material may be a terry cloth which assists in rapid absorption of liquid and the second layer of the sheet material may be a layer of flat cotton fabric or mesh material which is particularly useful for rapid evaporation of the liquid absorbed into the dryer.
[0030] Turning now to FIG. 6A , a sectional view of a dryer 70 according to still an embodiment of the present invention is illustrated. According to this embodiment the two faces of the absorbent material 72 are each covered by two separate layers of sheet material 74 (inside layer) and 76 (outside layer). This embodiment is useful, for example, to increase stability and rigidity of the structure. For example the inside layer may be reinforced mesh material, and the outside layer may be any textile material as discussed herein.
[0031] In the embodiment of FIG. 6B a section of a dryer 82 according to still an embodiment of the invention is illustrated. According to this embodiment the porous absorbent material 84 is composed of two co-planar layers 84 A and 84 B, each having different absorption capacity.
[0032] In order to illustrate the features of the dryer, an experiment was performed using the dryer of the present invention and regular cotton kitchen towel. The following were the results of the experiments:
[0033] 50 grams of water were instantaneously soaked into the dryer of the present invention and a typical cotton kitchen towel;
[0034] the diagram shown in FIG. 4 represents the rate and amount of the liquid evaporation over 10 hours at room temperature;
[0000] I It can be seen that the rate of evaporation rate of water from the cotton kitchen towel is substantially slower than the rate of evaporation from a kitchen dryer according to the present invention.
[0035] Specifically, after 10 hours almost all liquid (>45 gr.) was evaporated from the kitchen utensil dryer according to the present invention while the cotton towel was left with almost 18 gr. of water soaked into it during the same period of time.
[0036] Those skilled in the art to which this invention pertains will readily appreciate that numerous changes, variations, and modifications can be made without departing from the scope of the invention, mutatis mutandis. | A multi layered kitchen utensil dryer is provided comprising at least one layer of porous absorbent material enveloped by at least one sheet material, said sheet material being secured to the absorbent material. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on German Application No. 102006060256.0 filed on Dec. 14, 2006, of which the contents are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The invention relates to a method for controlling the operation of a washing machine, where a conductance sensor is placed in a washing liquid or powder container of the washing machine.
BACKGROUND OF THE INVENTION
[0003] For controlling the operation of a washing machine it is for example known from US 2006/0191496 A1 or EP 633 342 A1 to place a conductance sensor in the interior thereof, for example in the lower area of the washing liquid container. The measured values of the conductance sensor are determined and evaluated by the washing machine control unit. However the possibilities for further processing or using these measured values as described therein are limited.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] Embodiments of the invention are described hereinafter relative to the attached diagrammatic drawings, wherein:
[0005] FIG. 1 illustrates a diagrammatic inner view of one embodiment of an inventive washing machine; and
[0006] FIGS. 2 to 4 illustrate different graphs for representing relationships between surfactant concentration, surface tension and conductance.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0007] A problem addressed by the invention is to provide an aforementioned method with which the functionality of a washing process or operating process for the washing machine or the evaluation of an aforementioned conductance sensor can be improved.
[0008] One embodiment is a method having the features of claims 1 , 3 , 5 , 6 , 9 or 12 . Advantageous and preferred embodiments of the invention form the subject matter of the further claims and are explained in greater detail hereinafter. It is in particular also possible to combine several of the aspects according to the invention. By express reference the wording of the claims is made into part of the content of the description.
[0009] In a first basic embodiment of the invention, the conductance sensor detects the water level and, if said water level has dropped below the placing of the conductance sensor, an emptying of the washing liquid container is stopped, i.e., in particular, a pumping out with a pump is stopped. This makes it possible to prevent an idle running of the pump when the washing liquid container has been completely pumped empty, which on the one hand avoids unnecessary power consumption and on the other hand, in those phases where the drum does not rotate, prevents unpleasant, audible noises.
[0010] Particularly if an aforementioned pump is provided for emptying the washing liquid container, it is advantageous for the switching off of the pump to take place with a few seconds delay after the water level has dropped below the conductance sensor. Such a delay can in particular be matched to the fact that with a normal pumping capacity the water level is admittedly lowered somewhat further below the conductance sensor, but an idle running of the pump or an intake of air at the same is avoided. This ensures that the pump is operated close to an optimum range, i.e., for emptying of the washing liquid container or a lowering of the water level to just above the pump. However, this is not essential, because the pump can also be switched off if the water level is below it. What is important is to establish where the water level is relative to the pump in order to avoid any noise.
[0011] According to another basic embodiment of the invention, the conductance sensor is constructed to detect whether it is surrounded by foam during the washing process. This can not only be detected by the conductance sensor, but also in cooperation with the washing machine control unit or conductance sensor control unit. Fresh water is added as a countermeasure for the reduction or elimination of foam. Thus, the foam or liquid is at least diluted and as far as possible the foam removed. A detection of the foam on the conductance sensor is consequently possible with a high reliability level within the scope of the invention. Particularly in the case of capacitive conductance sensors, measured values for said foam state at the conductance sensor are between those for air and those for the case where said sensor is surrounded by water.
[0012] It is advantageously also possible as a countermeasure when foam is present, to add fresh water in such a quantity or for so long as to ensure that during the washing process or during the drum rotation, the conductance sensor is essentially or particularly advantageously constantly surrounded by water. This avoids the negative effects of excessive foam during washing.
[0013] According to another basic embodiment of the invention by means of the conductance sensor, it is possible to detect the surface tension of the washing liquid in the drum or in the liquid by determining the ionic concentration in the washing liquid. On the basis of this, it is possible to determine whether a specific surface tension is exceeded and a rinsing of the washing or laundry can be ended. In this way, it is possible to establish whether the detergent has been adequately rinsed out of the laundry. Thus, for example, as a function of the detected ionic concentration, the length or number of rinsing processes can be adapted accordingly. This is, in particular, continued until the ionic concentration or surface tension has exceeded a given, predetermined value and consequently the laundry is considered as being adequately rinsed.
[0014] According to another basic embodiment of the invention, it is possible during the spin drying process, particularly with the pump constantly running, to increase the spin drying speed only until the conductance sensor is largely uninterruptedly or even constantly surrounded by water. This means that initially slow spin drying speeds are used, because then with the laundry still very wet, sufficient water is ejected from the said laundry, so that the water level is above the conductance sensor. Since as a rule the pumping capacity is limited or the pump always runs at its maximum capacity, it serves little purpose to spin dry the laundry even faster and eject even more water if this cannot be conveyed away in good time and sufficiently rapidly by the pump. Moreover, the laundry in the drum is constantly rotated through the water at the bottom of the washing liquid container and becomes wet again, which is to be avoided.
[0015] It is advantageously additionally possible to only increase the spin drying speed when the conductance sensor after a long period of time, particularly a few minutes during which it was constantly or essentially surrounded by water, is no longer or is no longer essentially surrounded by said water. This means that then the pump can keep up with the water being removed from the laundry and can remove it and, as a result, the laundry can be spin dried with ever greater intensity and speed. With particular preference the spin drying speed can be slowly increased until the conductance sensor is again essentially or constantly surrounded by water. This can be repeated several times and the spin drying speed can be ever further increased. Due to this slow rise in the spin drying speed, an unnecessarily early or rapid spinning of the drum with the associated power consumption and bearing wear can be avoided.
[0016] Advantageously by means of the conductance sensor and its measured values, a control of the pump operation is possible. It is possible on reaching a maximum spin drying speed to switch off said pump again if the conductance sensor is no longer or essentially no longer surrounded by water. It is advantageously only switched on again when the conductance sensor is constantly or essentially surrounded by water. Thus, it is possible to ensure that the pump is not continuously running at a maximum spin drying speed. Admittedly, the above-described idle running of the pump with an intake of air is not critical with respect to the noise burden during spin drying, especially at high speeds, because it is much less noisy than the spin drying operation. However, an unnecessary power consumption and wear to the pump can be reduced.
[0017] It is particularly advantageously possible between a state change at the conductance sensor, i.e., a state when it is essentially surrounded by water and a state when it is essentially exposed and a switching on and off of the pump, to wait for a time interval of a few seconds, as described hereinbefore. This time interval can for example be in the range 5 to 30 seconds, particularly 10 to 20 seconds. As described hereinbefore, this brief time interval can also be provided to ensure that when the pump continues to run, further water is pumped out until just prior to pump idling. When the pump is stationary and the water rises there is a wait until the water level is just above the conductance sensor, but has not yet reached the laundry again. This reduces the pump operating frequency.
[0018] According to another basic development of the invention, as stated hereinbefore, it is possible to determine on the conductance sensor whether it is surrounded by water, foam or air. Thus, during a spin drying process, the drum speed can be reduced if foam is detected at the conductance sensor. The reduction of the drum speed is a countermeasure for reducing foam formation, because the foam is then impacted less or no longer by the drum passing through it. A speed reduction can for example be 10 to 30%. In particular, the speed can be reduced slowly or in stages until the conductance sensor is no longer surrounded by foam. In certain circumstances it is even possible to completely stop the drum if the conductance sensor is still surrounded by foam. It is particularly advantageously possible, after stopping the drum, to wait for a few minutes, for example up to 5 minutes. If the conductance sensor is still surrounded by foam or detects foam, it is possible to use the further countermeasure of introducing fresh water for rinsing the foam away. After introducing fresh water for a certain time, or in a certain quantity, a check is again made to establish whether the conductance sensor is surrounded by foam. If this is the case, further fresh water can be added until the foam is eliminated. As a further test measure, the pump can be started. If it then idles, which can be easily established by measuring the power consumption of the pump and this lasts for a few seconds to a few minutes, there is in fact still foam at the conductance sensor.
[0019] According to a further basic embodiment of the invention, it is possible in a method for operating an aforementioned conductance sensor, or during the measurement of the conductivity in the washing liquid container or liquid, to briefly interrupt the washing or rinsing process, particularly also a spin drying process, in order to carry out the conductance measurement. Particularly in the case of an interruption or for the conductance measurement, the drum can be stopped and then the conductance is measured with the drum stationary. This avoids the liquid being impacted by the drum movement in the washing liquid container so as to produce foam. It is also possible to calm the water in the washing liquid container, which also permits a better and more reliable conductance sensor evaluation.
[0020] It is also possible within the scope of the invention that one of two prescribed safety circuits for the heater can be avoided, because it is possible to determine with the conductance sensor within the framework of the aforementioned water level measurement whether the heater is in the water. This permits a simpler washing machine construction.
[0021] These and further features can be gathered from the claims, description and drawings and individual features, individually or in the form of subcombinations, can be implemented in an embodiment of the invention and in other fields and can represent advantageous, independently protectable constructions for which protection is claimed here. The subdivision of the application into individual sections and the subheadings in no way restrict the general validity of the statements made thereunder.
[0022] FIG. 1 shows a washing machine according to an embodiment of the invention and having a drum 13 containing washing or laundry 14 . Drum 13 is driven by motor 15 with a belt drive. A washing liquid or powder container is located below and surrounds the drum 13 and has an outflow 18 . Said outflow 18 leads to a pump 20 , which conveys water out of the washing liquid container 17 , via an outflow hose 21 from the washing machine 11 . Into the washing liquid container 17 projects a heater 23 in order to heat the water or liquor therein. FIG. 1 does not show an inflow for fresh water and for the detergent-mixed water. However, in the same way as the washing machine is described in this connection, the inflow can be constructed as is known in the prior art.
[0023] In the embodiment shown, a conductance sensor 24 projects into the washing liquid container 17 close to the heater 23 , as is for example known from US 2006/0191496 A1. The conductance sensor 24 effectively defines a broken line-represented level 25 marking the height up to which it can detect water or foam and further reference will be made thereto hereinafter. The conductance sensor 24 is also connected to a control unit 26 , which can also be connected to the pump 20 and/or heater 23 , particularly for the control thereof or for evaluating the operating state thereof. Motor 15 can also be connected to control unit 26 and both can be controlled by the latter and additionally or alternatively for the detection of its operating state, as described hereinbefore.
[0024] As stated hereinbefore, the conductance sensor 24 can, for example, establish whether water or foam is located above or below the level 25 or whether it is immersed in water. This can in particular be used in impacting the above-described pumping operation. It is also pointed out here that the conductance sensor 24 with level 25 is well below the lowermost point of drum 13 . Thus, a water level can rise well above the conductance sensor 24 or level 25 without reaching the drum 13 and the washing 14 therein and making the latter wet again. Appropriate consideration must be taken of this height difference in connection with the above-described, hysteresis curve-like possibility so that when the water rises above level 25 , the pump 20 is only switched on after a certain time, but always in sufficient time before the water reaches drum 13 . The same applies regarding the lowering of the water below level 25 before pump 20 runs dry during pumping away.
[0025] As the different possible methods have already been described, there is no need to go into detail in this connection here, but are made even clearer in conjunction with FIG. 1 .
[0026] FIG. 2 shows how it is possible to measure the surface tension of the liquid in which is located the content of drum 13 , particularly the laundry 14 , based on the surfactant concentration. There is a fixed relationship between the same and in particular control unit 26 can draw the indicated conclusions therefrom.
[0027] In a similar way the conductance and surfactant concentration are in a fixed mutual relationship, as shown in FIG. 3 .
[0028] Finally, in accordance with FIG. 4 , the conductance can be related to the surface tension in the liquor in drum 13 or washing liquid container 17 . Then for the different surfactants and different surfactant concentration ranges, virtually linear relationships are obtained, namely ranges 1 to 4 in FIG. 4 . If the surfactant concentration range is known to be, for example a very high surfactant concentration during the washing process, conclusions regarding the surfactant concentrations can be drawn from the liquid conductivity on the basis of the conductance. However, if the surfactant concentration is low, for example when rinsing laundry 14 in drum 13 , the conductance can also be established from the fixed relationship. As the control unit 26 advantageously forms the complete control for the washing machine 11 , it is aware of the given program sequence and therefore also knows whether a washing process or a rinsing process is taking place. The precise nature of the surfactant used need not necessarily be known, because on the basis of a starting value and with a random surfactant the concentration change can be detected. This is adequate for the aforementioned optimization of the washing and rinsing processes. In particular, different curves according to FIG. 4 can be stored in control unit 26 and used for detection purposes. | A washing machine is constructed with a special control unit and a conductance sensor in a washing liquid container for detecting a water level including whether there the water is above or below a given water level, and the presence of foam during a washing cycle. The control unit controls the operation of a pump, as well as the addition of fresh water, for eliminating excessive foam in the washing liquid container and in the drum. It is also possible to stop the pump from discharging this disturbing foam. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates to a surgical device for creating precise, small skin incisions for the introduction of a percutaneous conduit. In particular, the invention relates to such a device, which is designed for creating a small skin incision of controlled geometry about a puncture created by a guidewire or needle for the purpose of introducing a catheter or other percutaneous conduit.
BACKGROUND OF THE INVENTION
[0002] Many medical procedures require the deployment of a percutaneous device or conduit which penetrates the skin and allows connection of a cavity or organ inside the body with equipment that are externally located. For example, in the facilitation of fluid transport, percutaneous conduits or catheters, are used to access blood vessels for dialysis, pressure monitoring, laboratory diagnosis, drug delivery, nutritional solution delivery, or to drain excess fluid from a wound.
[0003] In the placement of catheters, it is often desirable to enlarge the puncture hole created initially by a needle. The enlarged hole allows the introduction of a larger diameter catheter. Generally, an introducer device such as a needle attached to a syringe, is used to insert a catheter in a blood vessel. One common approach is the Seldinger technique. A needle is attached to a syringe and inserted under the patient's skin, the vessel is identified by aspiration using the suction from the syringe. When blood enters the syringe, indicating that the vessel has been found, the syringe body is removed and a guidewire is introduced through the needle lumen and into the interior of the vessel. The needle is then removed, leaving a portion of the guidewire within the vessel and the remainder projecting outwardly beyond the surface of the patient's skin. A catheter or other introducing device may then be inserted over the guidewire using one of several techniques well known to one skilled in the art. In order to introduce a catheter or other devices (e.g. sheath, dilator, introducer), which has a larger diameter, over the guidewire and into the patient's body, an incision often must be made around the guidewire at the point of entry into the patient's body. Typically, the incisions are made with a No. 11 scalpel blade or an equivalent device by cutting outwardly from the wire. Finally, a catheter is inserted along the guidewire through the skin into the deeper tissues.
[0004] The skin incision step is particularly problematic since it is difficult to make a cut of the desired width and depth necessary for introduction of the catheter without forming a cut either greater or smaller than desired. Since the guidewire is inserted inside a vessel within soft tissues, the guidewire and the tissue may move easily relative to each other. In addition, the medical practitioner also needs to hold on to the guidewire to maintain the proper position of the guidewire. With the other hand holding on to the scalpel, and having no appropriate anchor point for the knife or the hand, it is generally difficult to make a precise incision with the appropriate length and depth. Furthermore, care must be taken not to sever the guidewire when making the skin incision, since the resulting internal piece of wire might then travel within the vascular system, resulting in various complications.
[0005] Because the purpose of the guidewire is to facilitate insertion of catheters or other percutaneous device into the vessel, it is preferable that the guidewire enters the tissue at an appropriate angle. Poor positioning of the guidewire may result in damage to the vessel, puncture of the vessel and/or coagulation inside the vessel. Thus, maintaining the appropriate insertion angle and making an incision with the appropriate depth around the site of guidewire insertion may be critical to successful placement of the catheter.
[0006] It is also known that a significant number of nurses and clinicians are uncomfortable with operating a surgical scalpel. The risk of cutting oneself will increase proportionately with the time spend handling sharp cutting devices. Under high stress environments such as an emergency room or at the seen of a car accident, the risk of accidental contact with the blade is further amplified.
[0007] The associated risks of accidental cutting after the completion of medical procedures have became a public health problem due to increasing number of patient's carrying blood borne pathogens, such as HIV virus or hepatitis. After the completion of the cutting procedure, the exposed blade (usually containing blood and/or bodily fluids) poses a significant danger to health care professionals. The danger occurs during the use of the scalpel, in cleaning up the operating room or patient's room, or in subsequent disposal of the used scalpel.
[0008] While no specific data is available with regard to accidental injury due to scalpels, the risk is at least comparable to the problems associated with needle sticks. The Centers for Disease Control and Prevention (CDC) has reported that about 384,000 needle-stick or similar injuries occur among U.S. hospital health-care workers every year. In addition, in one study, out of 3,978 needle sticks from patients known to be HIV positive, 13 health care workers became infected, roughly 1 out of 300.
[0009] Various mechanisms have been devised for cutting and introducing tubing into the human body. Examples of such devices are disclosed in U.S. Pat. No. 2,753,105, issued Jul. 3, 1956 to Werner et al.; U.S. Pat. No. 3,863,339, issued Feb. 4, 1975 to Reaney et al.; U.S. Pat. No. 3,895,411, issued Jul. 22, 1975 to Horak; U.S. Pat. No. 3,906,626, issued Sep. 23, 1975 to Riuli; U.S. Pat. No. 4,414,974, issued Nov. 15, 1983 to Dotson et al.; U.S. Pat. No. 4,438,770, issued Mar. 27, 1984 to Ungey et al.; U.S. Pat. No. 4,601,710, issued Jul. 22, 1986 to Moll; U.S. Pat. No. 4,617,738, issued Oct. 21, 1986 to Kopacz; U.S. Pat. No. 4,633,860, issued Jan. 6, 1987 to Korth et al.; U.S. Pat. No. 4,643,189, issued Feb. 17, 1987 to Mintz; U.S. Pat. No. 4,902,280, issued Feb. 20, 1990 to Lander; U.S. Pat. No. 4,760,848, issued Aug. 2, 1988 to Hasson; U.S. Pat. No. 4,955,887, issued Sep. 11, 1990 to Zirm; U.S. Pat. No. 4,955,890, issued Jun. 18, 1996 to Yamamoto et al.; U.S. Pat. No. 5,066,288, issued Nov. 19, 1991 to Deniga et al.; U.S. Pat. No. 5,139,507, issued Aug. 18, 192 to Dolgin et al.; U.S. Pat. No. 5,186,168, issued Feb. 16, 1993 to Spofford et al.; U.S. Pat. No. 5,208,983, issued May 11, 1993 to Masse; U.S. Pat. No. 5,211,652, issued May 18, 1993 to Derbyshire; U.S. Pat. No. 5,370,654, issued Dec. 6, 1994 to Abidin et al.; U.S. Pat. No. 5,527,333, issued Jun. 18, 1996 to Nikkels et al.; U.S. Pat. No. 5,529,581, issued Jun. 25, 1996 to Cusack; U.S. Pat. No. 5,545,175, issued Aug. 13, 1996 to Abidin et al.; U.S. Pat. No. 5,749,886, issued May 12, 1998 to Abidin et al.; U.S. Pat. No. 5,843,108, issued Dec. 1, 1998 to Sammuels; U.S. Pat. No. 6,221,047, issued Apr. 24, 2001 to Greene et al.; U.S. Pat. No. 6,238,369 B1, issued May 29, 2001 to Burbank et al.; U.S. Pat. No. 6,277,100 B1, issued Aug. 21, 2001 to Raulerson et al.; U.S. Pat. No. 6,402,770 B1, issued Jun. 11, 2002 to Jessen; each of which is incorporated in its entirety by reference herein. Although the above references suggests various cutting mechanisms, they do not teach nor suggest a device with safety features and a channel for providing guidance for appropriate angle of deployment of the device.
[0010] Therefore, a device equipped with a retraceable surgical blade, adapted for placement over a guidewire, which may be used as guidance to locate the insertion site, and capable of making a skin nick with predetermined incision angle at the insertion point of the guidewire or introducer needle is desirable. Such a device may significantly improve both the quality and safety of procedures for deployment of a percutaneous device or conduit in patients.
SUMMARY OF THE INVENTION
[0011] Accordingly, one of the objectives of the present invention is to provide a cutting device equipped with a surgical blade for microintroduction. It is another objective of the present invention to provide a cutting device for placement over a guidewire, which may be used as guidance to locate the insertion site. It is yet another objective of the present invention to provide a cutting device that is able to make a skin nick at the insertion point of the introducer needle to enlarge the hole for accommodating various french sizes (e.g., 3.5 to 7.0 fr.) of splittable sheath/dilators. It is a further objective to provide a cutting device with safety features (e.g. retractable blade, blade-locking mechanisms). It is also a further objective to provide a cutting device- that may be easily operated with one-hand. Various other objectives and advantages of the present invention will become apparent to those skilled in the art as more detailed description is set forth below.
[0012] One aspect of the present invention provides a cutting device with a retractable blade for making incisions around a guidewire, which is partially inserted into a mammalian body, to enlarge the point of entry. The cutting device may comprise of a housing with a channel so that the housing may be slidably placed over a guidewire. The guidewire may be used as guidance to locate the insertion site by sliding the cutting device on the guidewire towards the insertion location. The cutting device may further comprise a retractable blade adapted for making an incision at the guidewire entry location once the housing is positioned at the cite of insertion. Various retractable blade mechanisms well known to one skilled in the art may be adapted for this cutting device.
[0013] The cutting device may have a bottom surface such that when the cutting device is positioned over the guidewire and at the point of insertion, the bottom surface comes into contact with the subjects skin surface. The bottom surface may have a large enough surface area to provide stability for the cutting device when actuating the cutting device. Preferably, the bottom surface has a surface area between about 0.5 square centimeters to about 10 square centimeters. More preferably, the bottom surface has a surface area of about 1 square centimeters to about 7 square centimeters. Even more preferably, the bottom surface has a surface area of about 2 square centimeters to about 6 square centimeters. The bottom surface may be a smooth flat surface or alternatively it may have groves and/or notches. The bottom surface may comprise of a planner area or a virtual plan formed of multiple support points extended from the housing, such that the planner area is parallel to the skin surface when the housing is placed on the skin of the subject. In one variation, the bottom of the housing has an arc, such that when the housing sits on a planner surface, the two end points of the arc come into contact with the planner surface. In this case, the two end points of the arc form the bottom surface of the housing. In another variation, the bottom surface is comprised of plurality of arcs.
[0014] In another aspect of the invention, a channel is provided such that when a guidewire is passed through the housing, the guidewire exits the housing at a predefined angle (i.e., the incision angle) from the bottom surface of the housing. The predefined angle may be selected based on the particular application for which the cutting device is designed and should generally be in the range of approximately 10 degrees to 60 degrees. As shown and described herein with respect to using in an application for making incisions around a guidewire, the incision angle should be in the range of approximately 25 degrees to 35 degrees.
[0015] In another variation, the predefined angle may be adjustable on the cutting device. The cutting device may have a pivot allowing the position of the channel be adjusted relative to the bottom surface. The cutting device may further have a locking mechanism for securing the bottom surface once the desired angle is selected. For example, the cutting device with a variable angle adjustment mechanism may be preset at 30 degrees. The medical professional using the device may reset the angle to 45 degrees before applying the cutting device, if such angle is desirable.
[0016] In one variation of the invention the guidewire channel may be enclosed within the chamber except that the distal end and proximal end of the channel are exposed at opposite sides of the housing. The channel may be straight and allow the guidewire to pass through without bending. Alternatively, the channel may partially bend, such that the guidewire enters the housing at an angle (relative to the bottom surface) that is greater than the angle (between the guidewire and the bottom surface) from which the guidewire exists the housing. In another variation, the channel may have a curvature.
[0017] In another aspect of the invention, the channel may be partially open along the channel on at least one side of the channel. In one variation, the housing has a relatively flat and elongated profile. The channel runs from the distal end of the housing to the proximal end of the housing. Along the length of the channel, the channel may be exposed on one side such that a guidewire may be placed inside the channel laterally without the need to slide the housing on to the guidewire through either the distal end or proximal end of the channel.
[0018] The housing may further include a locking mechanism such that once the guidewire is laterally slid into the channel the locking mechanism may be activated to prevent the guidewire from sliding out of the channel laterally. This may allow the housing to slide along the guidewire securely without the risk of detachment form the guidwire through the lateral opening. When the user completes the cutting procedure, he may unlock the locking mechanism and remove the housing firm the lateral opening in the guidewire. Alternatively, a flap or other flexible materials may be placed along the chamber on the exposed side of the channel, such that to place the housing over the guidewire laterally, or to remove the housing from the guidewire laterally, would require the user to overcome a resistive force.
[0019] In one variation, the retractable blade is a surgical grade stainless steel blade. In an alternative variation, the surgical blade is a No. 11 surgical blade. The surgical blade may be coupled to a elastic member such as a spring. The spring may keep the blade in the chamber when the cutting device is not actuated. The spring may comprise a resilient plastic, an elastic metal, an elastic alloy, an elastic polymer, natural rubber, synthetic rubber, or a combination thereof. Alternatively, the spring may comprise of materials or mechanisms that are well known to one skilled in the art to have an elastic property that may regain its shape/position after it is stretched or compressed.
[0020] When the cutting device is actuated the spring may either be compressed or stretched depending on the particular design of the cutting device. In one variation, one end of the spring is connected to the inside of the housing and the other end couple to the blade. When the cutting device is activated, the spring is stretched and allows the blade to protrude from the housing. When the device is deactivated, the spring contracts and brings the blade back inside the chamber. In another variation, the spring is positioned in such a way that when the device is activated, the spring in compressed. Thus, in this variation when the device is deactivated, the spring expands into its original position pushing the blade back into the chamber.
[0021] The cutting device may further comprise an actuating member. The actuating member may be coupled to the spring and the blade. The acutating member may be a knob or piece of material, such as plastic slidably disposed in the chamber. The movement of the actuating member may compress or expand the spring and allow the blade to protrude from the housing. In one variation, the housing has an opening adapted for placement of the actuating member. An actuating member may be partially positioned within the housing and partially protrude from the housing, such that the user may use his finger to move the actuating member and force the blade to exit the housing.
[0022] In another variation, markers may be provide on the housing along the sliding path of the actuating member such that the operator may use the marker as guidance to determine the amount of blade extension and hence the amount of incision induced by the blade. In another variation, the spring is comprised of a spring arm. One end of the spring arm may be connected to the blade and the other end connected to a wall inside the housing. When the spring arm is compressed, whether through direct pressure from users finger or through an actuating member, the spring expends sideways and forces the blade to protrude from the housing. In an alternative design, the spring and/or the actuating member may be slidably disposed within a spring ramp. The spring ramp may allow the spring to expend and compress without interference from other mechanical parts. The spring ramp may be an independent channel separate from the guidewire channel. Alternatively, the spring may share the same channel as the guidewire.
[0023] The housing may be comprised of various metals, metal alloys, ceramics, rubber, plastic, polymers or combination thereof. Examples of polymers that may be utilized for the fabrication of the housing include, but not limited to, Polycarbonate, Polypropylene, Acrylonitrile Butadiene Styrene (ABS), Polyvinylchloride (PVC), and Polysulfone. The housing may also be constructed of various polymers or malleable plastic that one skilled in the art would consider suitable for constructing a surgical instrument. One may also design the housing structure and the select fabrication material to minimizes cost of production. For example, in one variation, all the components of the cutting device, except the blade and the spring, may be fabricated from molded plastic such as Acrylonitrile Butadiene Styrene (ABS). The housing may be easily molded of plastic material. In one example, the housing is comprised of two mating halves. In such a design, after the remaining components are assembled onto the front housing half, the rear housing half may be snapped into engagement with front housing half.
[0024] The economy of materials and assembly may permit marketing the device as a completely disposable device. Alternatively, the cutting device may be designed for repeated use, where after each use the device may be opened up and the blade may be replaced. The cutting device may be sterilized before the next use. The cutting device may have a low profile such that it may be dispose into a conventional biological waste disposal container. The low profile may make it easy for the medical practitioner to insert the used cutting device through the slot on the waste disposal container. The width of the cutting device is preferably less than 3 centimeters, more preferably less than 2 centimeters, and most preferably less than 1.5 centimeters.
[0025] In another aspect of the invention, the housing is comprised of transparent or translucent materials. The housing may also comprise of a combination of transparent and translucent materials. In one variation, the housing is comprised of clear plastic parts such that the operator of the device may see through the cutting device and observe the area around the guidewire entry point while the cutting device is positioned over the site of incision. In alternative variations, the cutting device may include other clear (optically transparent, partially transparent or translucent) materials, such as glass, polymers, plastic, crystal, laminates, or the like for the operator to see through the cutting device and observe actuation of the blade. Having a translucent and/or transparent device may limited obstruction of the view of the site of insertion and/or limit blockage of light at the cite of insertion.
[0026] In yet another aspect of the invention, the cutting device may include a locking mechanism for securing the blade. The locking mechanism may be adapted such that when the blade is actuated and extends outside the housing, it may be maintained at the extended position until the locking mechanism is released. Alternatively, the locking mechanism may be adapted such that once the cutting device is used, the operator may active the locking mechanism to prevent accidental actuation of the blade. Locking mechanisms that are well known to one skilled in the art that are suitable for securing a slidable blade may be implemented in this cutting device. In another variation, the locking mechanism may include a breakable plastic part or a irreversible locking mechanism such that once the locking mechanism is activated the blade can not be actuated again and thus must be disposed of.
[0027] Another aspect of the invention involves a method for utilizing the cutting device. Once a guidewire is inserted into the body of a patient, the cutting device may be utilized to enlarge the hole at incision site. The guidewire may be inserted into a patient's blood vessel with the Seldinger technique, which is well known to one skilled in the art. The cutting device may then be placed over the guidewire at the distal end of the guidewire and slid along the guidewire until the cutting device comes into contact with the patient's body at the site of incision. The cutting device is actuated to extend the blade out of the housing, thus allowing the blade to make a cut into the skin at the edge of the guidewire to increase the hole at the site of the incision. The actuating member may be released to allow the blade to retract back into the housing. The cutting device may then be removed and disposed of. A catheter may be inserted over the guidewire and into the patient's body through the enlarged hole at the point of incision. As discussed above, the cutting device may be placed onto the guidewire laterally, if the channel has a lateral opening. Furthermore, the blade in the cutting device may be extended before the cutting device is moved to the incision site. In this case, as the cutting device is slid onto the incision site the blade may penetrate the skin and make a cut on the skin tissue. It may also be possible to extend the blade before placement of the cutting device over the guidewire.
[0028] The present invention may provide various advantages over conventional methods for enlarging the entry hole around the guidewire. The cutting device disclosed in this application may provide improved precision and simplify the incision procedure such that nurses and clinicians are able to enlarge the hold at the incision site with less time and effort. In addition, since the blade may be retraced automatically after the release of the actuating member at the end of the procedure, accidental injuries caused by exposed blades may be minimized. Furthermore, the present cutting device may be designed in such a way that it may be implemented with one hand, and the low profile design may allow easy disposal of the device in a sharp container.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] In the accompanying drawings, reference characters refer to the same parts through out the different views. The drawings are intended for illustrating some of the principles of the cutting device and are not intended to limit the description in any way. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the depicted principles in a clear manner.
[0030] [0030]FIG. 1 is a cross-sectional view of one variation of a cutting device, shown with the blade in the retracted position.
[0031] [0031]FIG. 2 is a cross-sectional view of the same device illustrated in FIG. 1 with its blade actuated and partially extended outside the housing.
[0032] [0032]FIG. 3 illustrates another variation of the cutting device where the spring is compressed when the blade is actuated. For illustration purposes, the front housing half and the rear housing half are shown in a partially detached position with a small gap between the two halves.
[0033] [0033]FIG. 4 illustrates the same device in FIG. 3 with the front housing half and the rear housing have completely detached. The front housing half is shown on the right and the rear housing half is shown on the left.
[0034] [0034]FIG. 5 illustrates a variation of the cutting device with indentation pattern on the right lateral side of the housing.
[0035] [0035]FIG. 6 illustrates another variation of the cutting device with a lateral opening along the length of the channel for placement of a guidewire through the rear housing half of the cutting device.
[0036] [0036]FIG. 7 illustrates yet another variation of the cutting device with a build-in mechanism for adjusting the guidewire insertion angle.
[0037] [0037]FIG. 8 shows a schematic block diagram of one variation of method for utilizing the cutting device.
DETAILED DESCRIPTION OF THE INVENTION
[0038] The following detailed description should be read with reference to the drawings, in which like elements in different drawings are identically numbered. The drawings, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of the invention.
[0039] Those skilled in the art will recognize that many of the examples of preferred embodiments provided have suitable alternatives which may be utilized. Thus, it is to be understood that unless otherwise indicated this invention is not limited to specific blade, spring, polymer, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects of the invention only, and is not intended to be limiting.
[0040] A catheter and a guidewire are used herein as an example application to illustrate the functionality of the different aspects of the invention disclosed herein. It will be understood that embodiments of the present invention may be applied in a variety of processes and are not limited to introducing a catheter into a mammalian vessel. Variations of the present invention may be adapted for introducing other percutaneous devices or conduits into a mammalian body. It will also be understood that embodiments of the present invention may be applied over other introducer devices, and it is not limited to applications with a guidewire.
[0041] It must also be noted that, as used in this specification and the appended claims, the singular forms “a,”“an” and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, the term “a spring” is intended to mean a single spring or a combination of springs, “a blade” is intended to mean one or more blades, and the like.
[0042] Referring now to FIG. 1, a cutting device having a retractable blade 2 and a channel 4 for positioning of the device around a guidewire is illustrated. In this embodiment of the cutting device, the housing 6 is wedge-shaped and provides the guidewire channel 4 such that the insertion of a guidewire (not shown) through the guidewire channel 4 will result in the guidewire exiting the channel at a predefined incision angle α. In this example, α=30 degrees. The guidewire channel 4 in this variation is enclosed within the housing 6 and runs from the distal opening 8 on the distal end 10 of the cutting device to the proximal opening 12 on the proximal end 14 of the cutting device. The cutting device may be placed over the guidewire by inserting the guidewire into one of the openings 8 , 12 of the guidewire channel 4 and sliding the device over the guidewire.
[0043] In a blade channel 16 , which may be partially connected to the guidewire channel 4 , sits a surgical blade 2 . The surgical blade 2 may be a No. 11 scalpel blade. No. 11 scalpel blades are commonly used by most nurses and clinicians so that it may be easier for them determine the amount of incisions needed to accommodate various sizes of splittable sheath/dilators. A spring 18 may be placed in the blade channel 16 with one end of the spring 18 connected to an inner surface 21 of the housing and the other end coupled to the blade 2 . The spring 18 may be directly connected to the blade 2 , or alternatively, the spring 18 may be connected to a secondary member that is connected to the blade 2 .
[0044] In one embodiment of the invention, the blade is connected to an actuating member which is connected to the spring 18 . The actuating member transfers pressure delivered by the user to the blade 2 in order to force the blade 2 out of the housing. The actuating member 20 may be a plastic part that is connected to the blade 2 and partially protrude from the housing 6 , thus allowing the user's figure to come into contact with actuating member 20 . The actuating member may comprise one or more parts. The housing may have a slot allowing the actuating member to move within it in a predefined path. Although a wedge-shaped housing is shown here, it is understood that the housing may assume various shapes and geometries (e.g, cube-shape, pentagon-shape). The surface of the housing may also have curvatures.
[0045] When pressure is applied to the blade 2 , the spring 18 may expand and the blade 2 may be displaced and protrude from the housing 6 , as seen in FIG. 2. Once the pressure is released the spring 18 may contract and the blade 2 may be pulled back into the housing 6 of the cutting device. In an alternative design the blade channel 16 may be independent of the guidewire channel 4 and exit the cutting device at its own independent channel opening. A spring ramp may be provided for supporting the spring as it expands and compresses within the housing.
[0046] In another embodiment, the cutting device is comprised of two plastic parts that form a small channel for over the wire placement, as shown in FIG. 3. In this particular example, the moving parts (e.g., blade 2 , actuating member 20 , spring 18 ) may be assembled into the front housing unit 22 initially. As shown in FIG. 4, the rear housing unit 24 may then be snapped onto the front housing unit by aligning the locking members 26 on the front housing unit 22 with its corresponding receiving holes (not shown) on the rear housing unit 24 . The spring 18 may be positioned within a blade channel 16 within the housing. The actuating member 20 may extend within the chamber such that the distal end 28 of the actuating member 20 is positioned behind the spring 18 . A blade 2 that is slidably positioned within the blade channel 16 may be connected directly to the actuating member 20 .
[0047] Alternatively, the blade 2 may be coupled to the actuating member 20 through one or more connecting members such that movement of the actuating member 20 may induce the movement of the blade 2 . When pressure is applied on the contact surface 30 of the actuating member 20 , and the actuating member 20 is slid forward toward the distal end 10 of the cutting device, the distal end 28 of the actuating member 20 forces the spring 18 to compress and the blade 2 to extend outward through the opening 32 on the distal end 10 of the cutting device. In one variation, the spring l 8 is not directly attached to the housing 6 or the actuating member 20 , as seen in FIG. 4. When the cutting device is not actuated, the spring 18 sits in a slot within the housing in an relaxed and unbiased condition. When the device is actuated, the actuating member 20 maintains contact with the proximal end 34 of the spring and applies pressure to the spring 18 . The distal end 36 of the spring maintains contact with at least one surface in the housing and forces the spring to compress. When the actuating pressure is released, the spring 18 expands and forces the actuating member 20 to move towards the proximal end 14 of the housing, and as a result brings the blade 2 back into the housing 6 .
[0048] In an alternative embodiment, the spring 18 may be physically connected to the housing 6 and/or connected to the actuating member 20 . In one variation of this embodiment, markers 40 are provided on the surface of the housing, such that from the position of the actuating member 20 relative to the markers 40 , the operator may determine the size of incision made by the blade 2 . In yet another variation, the lateral surface 42 on the rear housing (i.e., the right side surface of the device) may have groves or patterns 44 assisting the operator of the device to position his or her finger on the device, as seen in FIG. 5.
[0049] In another aspect of the invention, a lateral opening 46 is provided such that access is allow along the length of the channel 4 , as illustrated in FIG. 6. The lateral opening 46 allows the guidewire to be placed into the channel 4 without the need to thread the guidewire through the opening 8 of the channel at the distal end 10 of the housing. Once the cutting device with the lateral opening 46 is positioned on the device, the operator may slide the cutting device along the length of the guidewire toward the location of the incision.
[0050] A flexible flap or flaps (e.g. rubber flap or silicon flap) may be positioned at the lateral openings 46 on the cutting device such that placement of the cutting device over the guidewire through the lateral opening 46 requires the user to overcome the resistance caused by the flap. The rubber flap may prevent the guidewire from prematurely slipping out of the channel 4 while operating the device. The flap or other force resistive material may also be place inside the channel 4 . Although in FIG. 6 the lateral opening is shown on the right side surface 42 of the device, it is within the contemplation of this invention that the lateral opening 46 may be located on the left side surface 48 , the bottom surface 50 , or the top surface 52 of the housing 6 depending on the particular design criteria. The position of the mechanical parts may be adjusted in the design to accommodate the location of the channel 4 and/or the lateral opening 46 , as one skilled in the art will appreciate.
[0051] Referring to FIG. 7; another aspect of the cutting device with an adjustable base 60 is illustrated. A pivot 62 may be provided such that the housing 6 of the cutting device may pivot along a base 60 that is connected to the housing through the pivot 62 . This may allow the guidewire channel angle be adjusted relative to the base 60 of the cutting unit. A locking mechanism 64 may be provided to secure the position of the insertion angle.
[0052] This invention also includes various methods for utilizing the disclosed cutting device, one of which is illustrated in the schematic block diagram of FIG. 8. The initial step 70 comprises inserting a needle into a patient to make a puncture (at this point the distal end of the needle may be positioned inside a targeted vessel). In a next step 72 , a guidewire is inserted into the patients body through the lumen of the needle and a portion of the guidewire length may be advanced into the vessel. In step 74 , the needle is removed, leaving the guidewire in place. Step 76 comprises providing a cutting device with a channel for positioning the guidewire at a predetermined angle relative to the base of the cutting device. In step 78 , the cutting device is placed over the guidewire, which may include inserting the guidewire into the distal end of the guidewire channel and sliding the cutting device toward the puncture location where the guidewire enters the body.
[0053] In step 80 , the cutting device is positioned at the location of the puncture, including potentially sliding the cutting device along the guidewire until the Cutting device comes into contact with the patient's body. In step 82 , the cutting device is actuated, which may include the step of applying pressure on an actuating member and extending the blade out of the housing of the-cutting device. In step 84 an access cut is made on the patient at the puncture location and in step 86 , the blade is released and allowed to retract into the housing. In step 88 , the cutting device is removed from the guidewire and in step 90 , a catheter is inserted over the guidewire through the now enlarged opening and into the patient's body. Finally, in step 92 the guidewire is removed from the patient's body.
[0054] All publications and patent applications cited in this specification are herein incorporated by reference in their entirety as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. This invention has been described and specific examples of the invention have been portrayed. The use of those specifics is not intended to limit the invention in anyway. Additionally, to the extent there are variations of the invention, which are within the spirit of the disclosure or equivalent to the inventions found in the claims, it is our intent that this patent will cover those variations as well. | A surgical cutting device for producing a skin incision of controlled length and depth at a guidewire skin puncture location. The cutting device is particularly useful for making incisions for the insertion of catheters. In one variation, the cutting device comprises a retractable blade and a channel for positioning the cutting device around a guidewire. The channel may be adapted such that when a guidewire is placed inside the cutting device, the guidewire may exit the channel at a 30 degree angle relative to the base of the cutting device. Methods for using the cutting device are also described. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a National Phase filing under 35 C.F.R. §371 of and claims priority to PCT Patent Application No.: PCT/IL2014/050952, filed on Nov. 3, 2014, which claims the priority benefit under 35 U.S.C. §119 of U.S. Provisional Application No. 61/926,651, filed on Jan. 13, 2014, the contents of which are hereby incorporated in their entireties by reference.
TECHNOLOGICAL FIELD
The present invention concerns a wheel for use in bicycles and other land vehicles.
BACKGROUND
PCT Application WO 2011/067742 discloses a human-powered land vehicle, such as a bicycle, which is structured from palpable recyclable material, having wheels that may be made of cardboard. Cardboard-based wheels have also been disclosed in Publication U.S. Pat. No. 3,492,016.
GENERAL DESCRIPTION
The present invention provides a wheel that is made substantially out of cardboard, has sufficient rigidity to support a load and can, thus, be used in a land vehicle, such as a bicycle.
The term “made substantially out of cardboard” means to denote that cardboard is the main structural component of the wheel that functions to support the load exerted on the portion of the wheel that bears on the ground or on another driving/riding surface. For example, a wheel that is made substantially out of cardboard may have a hub that incorporates the wheel's axle that will be made of a material other than cardboard, it may comprise coating layers that line portions of the wheel's external surfaces (at times the entire surface) for environmental protection, e.g. a polymeric film layer, lacquer, etc.
Typically, but not exclusively, the wheel of the invention is fitted with a tire or an elastomeric, ground-bearing material on its rim. In the following, the term “tire” will be used to refer, collectively, to an elastomeric, ground-bearing element that is fitted around the wheel's rim. The tire may, for example, be a solid mass of an elastomeric material, may be inflatable, may be an elastomeric strip fitted on the rim, etc. As is well known in the tire industry, tires may at times comprise also reinforcing metal or non-metallic fibers or mash, may have a treading pattern, etc.
In accordance with the invention, it has been realized that a multi-layered cardboard structure having at least one high density cardboard (hereinafter, at times, “HDC”) layer and at least two layers of low density cardboard (hereinafter, at times, “LDC”) sandwiching the HDC layer, forms a robust and relatively light structure that has significant compression resistance as well as torsional and flexural resistance. Such a structure having a rounded circumference, arranged around the central hub, allows it to be used as a wheel in a bicycle or other land vehicle with sufficient rigidity which, in the case of a bicycle, is sufficient to bear the weight load of a rider.
There is, of course, a correlation between the load-bearing capacity and the service lifetime of such a wheel, on the one hand, and the type of HDC and LDC used for forming such layers. It would be a relatively routine undertaking that would not require undue experimentation, to find out the optimal combination (in terms of weight and rigidity) of HDC and LDC for a specific use. For example, a wheel intended for a children's bicycle may be constructed of thinner HDC layers, or a less dense LDC layer than for a bicycle intended for adults.
The term “resistance” should be understood in the context of use of the wheel and is intended to denote that, during regular use and stress, encountered during riding/driving, the wheel maintains its integrity as well as its generally planar and rounded structure.
The term “high density cardboard” or “HDC” is intended to denote a cardboard sheet in which the cardboard is packed without visible voids or gas-containing pockets. A high density cardboard sheet typically has an areal density in the range of 400 to 600 g/m 2 . A particular example is heavy duty cardboard having a density in the range of 500 to 600 g/m 2 . The HDC used in accordance with the invention may have a thickness in the range of 0.5 to 3 mm, typically 1 to 1.5 mm.
The term “low density cardboard” or “LDC” refers to cardboard sheets having internal structure defining a plurality of cells or voids, e.g., formed by corrugated, fluted or otherwise loosely packed paper sheets or strips that define a plurality of voids therebetween, and comprising one or more liner cardboard sheets lined at one side or both sides of the low-density layers (namely sandwiching the low-density layer between them). Examples of such cardboard panels are such known as “corrugated cardboard”, which consists of a fluted or corrugated paper panel(s) or strip and one or two flat linerboards at one or both (i.e. sandwiching) sides of the fluted or corrugated paper; and may also be such referred to as “honeycomb cardboard”. The corrugated or honeycomb cardboard sheets may be single-walled or multi-walled cardboard sheets. These terms are also meant to encompass cardboard of various strengths, ranging from a simple arrangement of a single thick panel of paper to complex configurations featuring multiple corrugated, honeycomb and other layers.
The LDC is typically a honeycomb or corrugated cardboard having a thickness in the range of 8 to 20 mm, typically 8 to 15 mm and even 8 to 12 mm.
The invention, thus, provides a wheel that comprises a generally planar, multi-layered cardboard body defined between two side faces, and having circular circumference and a hub that defines its central axis. The layers are arranged parallel to the two side faces. The layers comprise at least one layer of HDC and at least two layers of LDC sandwiching the HDC layer. The at least two LDC layers and the at least one HDC layer are fixedly attached to one another. The fixed attachment is typically by gluing.
By one embodiment, the wheel includes a single HDC at the wheel's mid-line with two LDC layers sandwiching this single high density cardboard layer. Typically, a wheel with such embodiment would have axial symmetry about the HDC layer. However, other embodiments may also be envisaged, in accordance with the general teachings of the invention. By way of example, there may be alternating layers of high and low density cardboard, e.g. the following layer arrangement: one with a plurality of alternating LDC-HDC layers, for example: LDC-HDC-LDC-HDC-LDC; or HDC-LDC-HDC-LDC-HDC; or the same layer structure with additional, respective, HDC or LDC layers at each side of these structures; etc. By other examples, the HDC layer at the mid-line may consist of two or more HDC sheets fixedly attached to one another, forming a thicker HDC mid-line layer; or one or more LDC layers may be formed by two or more LDC sheets.
By one embodiment, the wheel comprises one or more pliable strips that are fitted around the circumference of said body, in fact defining the perimeters of the cardboard body. Such a strip may typically be made of cardboard or paper but other materials, such as plastic, rubber or other polymeric material, may also be used.
Such a strip, particularly where it is made of cardboard, typically comprises lateral flaps that are folded and attached to the wheel's side faces thereby securing the strip in position and providing further reinforcement to the structure.
By one embodiment the body of the wheel is a continuous mass extending from the hub to the circumference. By another embodiment said body is patterned by cutouts defining arms with side and inner faces extending radially between the hub and a circumferential wheel portion. Such inner faces may be overlaid with a pliable sheet, e.g. cardboard or paper. Such a patterned wheel configuration, define also inner faces of the circumferential wheel portion, which by one embodiment are also overlaid with a pliable sheet, e.g. cardboard or paper.
The wheel, as noted above, is typically fitted with a tire.
For environmental, in particular water-resistance, the wheel's external faces may be impregnated, e.g. by a water repelling material or coated by such a material. Examples are resins such as lacquer or epoxy, a polymeric sheet, a combination of these, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:
FIG. 1 shows a perspective view of a wheel in accordance with an embodiment of the invention.
FIG. 2 shows the wheel of FIG. 1 fitted with a tire.
FIG. 3 is an exploded perspective view of the wheel of FIG. 2 showing its constituting elements.
FIG. 4A is a cross-section along lines IV-IV in FIG. 2 .
FIG. 4B shows a layered structure according to another embodiment of the invention.
FIG. 5 shows a side view of a wheel according to another embodiment, patterned through cut-outs.
FIG. 6 is a cross-section along lines VI-VI in FIG. 5 .
DETAILED DESCRIPTION OF EMBODIMENTS
Referring first to FIG. 1 , shown is a wheel which has a generally planar configuration and has a cardboard body 102 with two side faces 104 and 106 . As inherent in a wheel structure, it has a circular circumference and a hub 108 that defines the wheel's central axis. The cardboard body, as can be seen in FIG. 4 and as will be elaborated upon further below, has layered structures, the layers being arranged in parallel to the two side faces.
The wheel of FIG. 1 is made substantially out of cardboard, although the hub may be made of other materials, such as plastic, wood, metal, may comprise ball bearings, etc. The hub may be incorporated into the wheel by forming a circular cut-out in body 102 and fitting the hub element 108 into it, tightly attaching it to the body, e.g. through gluing.
As can be seen in FIG. 2 , the wheel is typically fitted with a tire 110 made of rubber or another elastomer. In the embodiment seen in FIG. 2 , the tire is a solid elastomeric mass, but according to other embodiments the tire may be a foamed mass, may be inflatable, may be of reinforced rubber, or may have a variety of other structures.
As can further be seen in FIG. 1 , the circumference of body 102 is fitted with a pliable strip 112 , typically made of cardboard, paper or a polymeric film, having flaps 114 that are folded onto side faces 104 and 106 to secure the strip in position. This strip, among others, seals the otherwise exposed perimeter of the layered structure.
Typically, the wheel will be covered by an environmentally protected layer, e.g. polymeric resin, polymeric layer, epoxy, lacquer, paint, etc.
The exploded view of the wheel of FIG. 2 can be seen in FIG. 3 , showing the four basic constituting elements which are the hub 108 , body 102 , strip 112 and tire 110 .
FIG. 4A shows a cross-section through the wheel of FIG. 2 . As can be seen, the layers include an inner HDC layer 116 defining a mid-line 118 . The HDC layer 116 is sandwiched by two LDC layers 120 and 122 , arranged symmetrically about it. The HDC typically is made of high density or heavy duty cardboard having a thickness in the range of 0.5-3 mm, typically of about 1-1.5 mm; while the LDC layers are typically corrugated or honeycombed cardboard having a thickness in the range of 8-20 mm, typically of about 12 mm.
As can further be seen in FIG. 4A , the pliable strip 112 that surrounds the wheel's circumference is overlaid with a tire 110 .
Another embodiment of a cardboard body for use in a wheel can be seen in FIG. 4B . In this embodiment, two additional HDC layers 124 and 126 sandwich the two LDC layers. It should, however, be noted that the two embodiments illustrated in FIGS. 4A and 4B are mere examples and other different embodiments, e.g. those noted above in the summary, may be used in accordance with the invention.
The wheel according to another embodiment is illustrated in FIG. 5 . The wheel of FIG. 5 is based on that of FIG. 1 and is patterned through cut-outs 130 that together define an enlarged hub portion 132 linked to a peripheral portion 134 through radial arms 136 . Inner faces 138 of arms 136 , inner faces 140 of peripheral portion 134 , as well as inner face 142 of hub portion 132 , are typically lined with a liner layer which may be identical in constitution to that of strip 112 .
As can be seen in FIG. 6 , arm 136 is enveloped by a layer 144 . However, in other embodiments, rather than enveloping the entire arm, a strip of such pliable material may be fitted only on the inner faces, e.g. in a similar manner as in the case of strip 112 , by deploying, for example, flaps to fix the strips in position. | Some embodiments are directed to a generally planar wheel, including a multi-layer cardboard body having at least one layer of a high-density cardboard sheet sandwiched between at least two layers of low-density cardboard sheet. | 8 |
BACKGROUND OF THE INVENTION
There are known piperazine compounds of the formula ##STR2## where R 2 is hydrogen or a chlorine atom in the 2-position and R 1 is a lower alkyl group, a phenyl radical, a benzyl radical or a chlorophenyl radical when Y is a single bond between the piperazine ring and the phenyl group, or where R 1 is a lower alkyl group, a phenyl radical a benzyl radical a chlorophenyl radical or a methoxyphenyl radical when Y is methylene, dimethylene, trimethylene, or the group --CH 2 --CH═CH. Several of these compounds, especially those where Y is the group --CH 2 --CH═CH-- have proven to be analgetically active (J. Med. Chem. Volume 11, page 803 (1968)).
Furthermore, there are known piperazine compounds of the following formula ##STR3## In this formula A, for example, stands for the group --CH 2 --CH 2 --CO-- and R is a 2-chlorophenyl radical a 2-methylphenyl radical or a pyridyl-(2) radical These compounds were examined as to whether they had a suppressing action on the central nervous system (sedative and atactive actions; tranquillizing action). Several of the compounds showed activity (J. Med. Chem. Volume 12, page 867 (1969)).
Finally, there are described in German OS No. 2623772 piperazine derivatives of the general formula ##STR4## in which R is a low molecular weight straight or branched chain alkyl group having 1 to 6 carbon atoms, a low molecular weight, straight or branched chain alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a low molecular weight, straight or branched chain alkyl group having 1 to 6 carbon atoms which is joined to a low molecular weight, straight or branched chain alkoxy group having 1 to 6 carbon atoms or a hydroxy group, a low molecular weight, straight or branched chain alkenyl group having 2 to 5 carbon atoms which is joined to a low molecular weight, straight or branched chain alkoxy group having 1 to 6 carbon atoms, or a tetrahydrofuryl group; R 1 and R 2 , which can be the same or different are hydrogen or low molecular weight, straight or branched chain alkyl groups having 1 to 4 carbon atoms (with the proviso that both groups R 1 and R 2 cannot be a hydrogen atom); and R 3 is a hydrogen atom, a halogen atom, a low molecular weight, straight or branched chain alkyl group having 1 to 4 carbon atoms, a low moleclar weight, straight or branched chain alkoxy group having 1 to 4 carbon atoms or a hydroxy group.
These compounds are stated to have an analgetic action, in which case however, it is a matter of peripherally active materials. In contrast the compounds of the invention are centrally active analgetics.
SUMMARY OF THE INVENTION
The invention is directed to compounds of the formula ##STR5## where R 1 a phenyl group, pyridyl group, pyrimidyl group or pyrazinyl group or a phenyl group, pyridyl group, pyrimidyl group, or pyrazinyl group substituted by the radicals R 3 and R 4 which are the same or different and are hydrogen, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, C 1 -C 6 alkyl group, C 1 -C 6 -alkoxy groups, C 3 -C 6 -alkenyloxy group, C 3 -C 6 -cycloalkyloxy groups, phenyl-C 1 -C 4 -alkoxy groups, C 1 -C 6 -alkylmercapto groups, the nitro group, the amino group, C 1 -C 6 -alkylamino groups, C 1 -C 6 -dialkylamino groups, C 2 -C 6 -alkanoyl groups, C 2 -C 6 -alkanoylamine groups or C 2 -C 6 -alkanoyloxy groups and R 2 is the adamantyl group, the 3,3-dimethylbicyclo [2,2.1]hept-2-yl group, a saturated C 3 -C 16 -cycloalkyl group or a single unsaturated C 3 -C 16 -cycloalkenyl group and alk is a straight or branched C 1 -C 6 -alkylene chain and their physiologically (or pharmaceutically) acceptable salts.
The invention also includes the preparation of compounds of formula I(a) by reacting a compound of the formula ##STR6## where Z is the group R 1 or --CO--alk--R 2 with a compound of the formula
Z'X III
where X is a halogen atom, e.g. chlorine, bromine, or iodine, when Z' is the group R 1 and Z the group --CO--alk--R 2 or where X is a halogen atom or is the group --OR, when Z' is the group --CO--alk--R 2 and Z is the group R 1 and R is hydrogen, a C 1 -C 6 -alkyl group, a benzyl group or a phenyl group or a phenyl group substituted by chlorine, bromine, the nitro group, or C 1 -C 4 alkyl group, or (b) by reacting a compound of the formula
R.sub.2 --alk--CO--N(CH.sub.2 --CH.sub.2 Hal).sub.2 IV
where Hal is a halogen atom with a compound of the formula
R.sub.1 NH.sub.2 V
and optionally reducing a nitro group in the compound obtained to the amino group and/or optionally acylating, and/or alkylating or alkenylating the compound obtained and/or converting it into the acid addition salt.
The invention furthermore is directed to medicines containing compounds of formula I together with conventional carriers and/or diluents or adjuvants.
Also the invention includes a process for the production of a medicine comprising processing a compound of formula I with customary pharmaceutical carriers or diluents to form pharmaceutical perparations.
Additionally, the invention includes the use of the compounds of formula I for the production of medicines.
The compounds of the invention are active pharmacologically or pharmacotherapeutically. For example, they are analgetically active. They possess a wide therapeutic breadth and furthermore are characterized by the lack of central nervous system side effects such as for example, sedation and ataxia. The compound of the invention are centrally active analgetics. Tolerance experiments show that the compounds of the invention are not habit forming. The analgetic action is not like opiates, that is the compounds of the invention do not show affinity for the opiate receptor (for example no antagonism of the analegesic when there is subsequently dispensed Naloxon). Furthermore, the compounds of the invention arrest the secretion of gastric juice and are antiulcerative and antiphlogistically active.
Thus the invention is directed to making available compounds having favorable pharmacological properties which are useful as medicines.
The alkyl radicals occuring in the compounds of formula I (for example as the alkyl group or in the form of the alkoxy group, the alkylmercapto group, the alkylamino group, the dialkyamino group of the phenalkoxy group) and alkenyloxy radical as well as the alkylene chain can be straight or branched. In the event that the radicals R 3 and/or R 4 are alkyl groups or contain alkyl radicals, these consist of especially 1 to 4 carbon atoms (methyl, ethyl, propyl, isopropyl, or butyl groups). Illustrative of specific groups are methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, amyl, or hexyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, amyloxy, hexoxy, methylamino, ethylamino, propylamino, butylamino, sec.butylamino, hexylamino, dimethylamono, diethylamino, methyl ethyl amono, diisopropylamino, dipropylamino, dibutylamino, diamylamino, dihexylamino, methylmercapto, ethylmercapto, propylmercapto, butylmercapto, hexylmercapto, allyloxy, methallyloxy, crotyloxy, benzyloxy, phenethoxy, phenpropoxy, phenbutoxy.
The chain alk indicates an alkylene group such as for example, the methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene group or also for example, the group ##STR7## particularly the chain alk consists of 1,2 or 3 C-atoms. In case the radical R 3 or R 4 is a C 3 -C 6 -alkenyloxy group, the alkenyl portion especially consists of 3 or 4 carbon atoms. In the event that the radical R 2 represents a C 3 -C 16 cycloalkyl radical, it is for example, cyclopropyl, cyclobutyl,, cyclopentyl, cyclohexyl, cycloheptyl cyclooctyl, cyclononyl, or cyclodecyl, or cyclododecyl or cyclohexadecyl. In case the radicals R 3 and R 4 are C 3 -C 6 -cycloalkoxy groups, they are cyclopropoxy, cyclobutoxy, cyclopentoxy, or cyclohexoxy groups.
In the event the radicals R 3 and R 4 are alkanoyloxy groups, alkanoylamino groups or alkanoyl group, the alkanoyl radical especially consists of 2 to 4 carbon atoms (for example, the acetyl radical, propionyl radical, butyryl radical, valeroyl or hexanoyl). Illustrative groups are acetoxy, propionoxy, butyroxy, valeroxy, hexanoyloxy, acetamibno, propionamino, butyramino, valeramino, or hexanoylamino.
The pyridyl group (R 1 ) is preferably joined via the 2-position with the piperazine group. The same is true in regard to the pyrimidyl and pyrazinyl groups. The radicals R 3 and R 4 can be on the 2, 3 and/or 4 position of the phenyl group R 1 . In the event this phenyl group contains a substituent, this is preferably in the 2-position, in the case where there are two substituents R 3 and R 4 , are preferably in the 2,6-positions of the phenyl group. Especially favorably activities are shown by compounds of formula I where one or both substituents R 3 and/or R 4 are C 1 -C 6 -alkoxy groups, especially C 1 -C 4 alkoxy group, C 2 -C 6 -alkanoylamino groups, especially C 2 -C 4 -alkanoylamino groups, or fluorine or chlorine, alk contains 2 or 3 C-atoms and R 2 is a cyclohexyl radical. At the same time R 3 and R 4 contain the same or different substituents of the types mentioned. In case R 1 is pyridyl group or a pyrazinyl group and these groups contain a substituent R 3 , it is located preferably in the 6-position of the pyridyl or pyrazinyl group. With 2 substituents the pyridyl group is preferably substituted in the 3 and 6 position and the pyrazinyl group is preferably substituted in the 5 and 6 positions by the substituents R 3 and R 4 .
The products of the process can optionally be alkylated or alkenylated. Hereby, for example, there is introduced a C 1 -C 6 -alkyl group, a C 3 -C 6 cycloalkyl group, a phenyl-C 1 -C 4 -alkyl group or a C 3 -C 6 -alkenyl group in compounds where R 3 and/or R 4 is an amino or monoalkylamino group or a hydroxy group.
This alkylation is carried out in known manner. As alkylating agents there can be employed for example, esters of the formula R'Hal, ArSO 2 OR' and SO 2 (OR') 2 , whereby Hal is a halogen atom (especially chlorine, bromine, or iodine) and Ar is an aromatic radical such as for example, a phenyl or naphthyl residue which optionally is substituted by one or more lower alkyl groups (e.g., methyl, ethyl, propyl, butyl, or hexyl) and R' is a C 1 -C 6 -alkyl group, a C 3 -C 6 -alkenyl group, a C 3 -C 6 -cycloalkyl group or a phenyl C 1 -C 4 -alkyl group. Examples are p-toluenesulfonic acid-C 1 -C 6 -alkyl esters (e.g., methyl p-toluene sulfonate, hexyl p-toluene sulfonate, p-toluenesulfonic acid-C 3 -C 6 -alkenyl esters (e.g., alkyl p-toluenesulfonate, methallyl p-toluenesulfoate), C 1 -C 6 -dialkyl sulfates (e.g., dimethyl sulfate, diethyl sulfate), C 1 -C 6 -alkyl halides (e.g., methyl chloride, methyl bromide, methyl iodine, ethyl bromide, ethyl chloride, ethyl iodide), C 3 -C 6 -alkenyl halides, e.g. allyl chloride, C 3 -C 6 -cycloalkyl halides (e.g., cyclopropyl chloride, cyclopropyl bromide, cyclohexyl chloride), cyclohexyl chloride), phenyl-C 1 -C 4 -alkyl halides (e.g., benzyl chloride, benzyl bromide) and the like. The alkylation reaction is optionally carried out with the addition of customary acid binding agents such as alkali carbonates (K 2 CO 3 ), alkali hydroxides (NaOH, KOH), pyridine or other customary tertiary amines at temperatures between 0° and 200° C., preferably 20° to 150° C., in an inert solvent such as lower alcohols (methanol, ethanol, isopropanol), lower ketones (acetone methyl ethyl ketone), lower haloalkanes (chloroform, methylene chloride, dichloroethane), dioxane, dimethyl formamide, dimethyl sulfoxide, aromatic hydrocarbons (benzene, toluene, xylene) or pyridine.
This alkylation can also be carried out by first producing an alkali compound of the compound of formula I to be alkylated wherein for example, R 3 and/or R 4 is an amino, monoalkylamino, or hydroxy group, by reacting it in an inert solvent such as dioxane, tetrahydrofurane, dimethyl formamide, benzene, toluene, or xylene or in liquid ammonia with alkali metal, alkali hydride, or alkali amide (especially sodium or sodium compounds) at temperatures between -70° and 120° C. and then adding the alkylating agent (for example C 1 -C 6 -alkyl iodide or C 1 -C 6 -alkyl bromide) at a temperature between -70° and +50° C.
The alkylation can also be carried out in the presence of tetraalkyl ammonium salts (especially the halides) in combination with alkali hydroxides at temperatures between 0°-100° C., preferably 20°-80° C. in an aprotic solvent or also in chloroform or methylene chloride. As aprotic solvent there can be used for example: tertiary amides (dimethyl formamide, N-methyl pyrrolidone, hexamethyl phosphoric acid triamide), dimethyl sulfoxide, acetonitrile, dimethoxyethane, acetone, or tetrahydrofurane.
In those products of formula I wherein R 3 and/or R 4 is an amino group or a hydroxy group by acylation, there can be introduced a C 2 -C 6 -alkanoyl group into the amino or hydroxy group. This acylation for example is carried out in known manner for this type of process using C 2 -C 6 -alkanoyl halides or C 2 -C 6 alkanoyl anhydrides. For example, this acylation is carried out in a solvent or suspension agent (aliphatic halohydrocarbons such as chloroform or dichloromethane, lower aliphatic ketones, dioxane, dimethyl formamide, benzene, toluene) in the presence of an acid binding material (pyridine, trialkylamine, alkali carbonate, alkali bicarbonate, alkaline earth carbonate, alkali acetate) at temperatures between 0°-180° C., preferably 0°-100° C. Optionally the acylation can be carried out in such manner that there is first produced an alkali compound of the compound to be acylated by reacting it in an inert solvent such as dioxane, dimethyl formamide, benzene, or toluene with an alkali metal, alkali hydride, or alkali amide (especially sodium or sodium compounds) at temperatures between 0° and 150° C. and then the acylating agent (for example the alkanoyl halide) is added.
In place of the acylating agents mentioned there can also be used other chemically equivalent agents used in chemistry (see for example, also L. F. and Mary Fieser "Reagents for Organic Synthesis", John Wiley and Sons, Inc., New York 1967, Volume 1, pages 1303-1304 and Volume 2, page 471). It is understood that acyl groups in the compounds obtained can also be split off again, for example, with aqueous alkali or alcoholic alkali liquor (for example, methanolic KOH) or also optionally by means of mineral acids such as hydrochlorine acid or sulfonic acid in alcoholic or aqueous-alcoholic solution at temperatures between 20° and 100° C.
In the case of those products where the radicals R 3 and/or R 4 signify nitro grouops, these can be reduced to the corresponding amino groups.
Catalytic hydrogenation is especially considered for this reduction. As catalysts there can be used: Raney nickel, noble metals such as palladium and platinum, as well as compounds thereof with or without carriers such as for example barium sulfate, calcium sulfate, etc. It is recommended to carry out the hydrogenation of the nitro group at temperatures between 20° and 80° C. and a pressure of approximately 5-50 atmospheres absolute in a solvent for example, alcohols, dioxane, tetrahydrofurane, etc. It can be advantageous in many cases for the subsequent isolation of the reduced compounds if there are added to the mixture being hydrogenated, drying agents such as sodium or magnesium sulfate. However, the reduction can also be carried out with nascent hydrogen, for example, zinc/hydrochloric acid, tin/hydrochloric acid, iron/hydrochloric acid or with salts of hydrogen sulfide in alcohol/water at about 70 to about 120° C. or with activated aluminum in aqueous ether at 20° to 40° C. or with tin (II) chloride hydrochloric acid.
In regard to process (a):
This process is generally carried out in an inert solvent or suspension agent at temperatures between 0°-250° C., especially 5°-180° C., preferably 20°-150° C. As solvents there can be employed for example: saturated alicyclic and cyclic ethers (dioxane, tetrahydrofurane, lower dialkyl ethers such as diethyl ether, diisopropyl ether), lower alkanols such as ethanol, isopropanol, butanol, lower aliphatic ketones (acetone, methyl ethyl ketone), lower aliphatic hydrocarbons or halohydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane) aromatic hydrocarbons (benzene, toluene, xylene), lower dialkyl amides of lower saturated aliphatic carboxylic acids (dimethyl formamide, dimethyl acetamide), tetramethyl urea, N-methyl pyrrolidone, dimethyl sulfoxide, or mixtures of these agents.
In case X is a halogen atom it is especially a matter of chlorine, bromine, or iodine, preferably chlorine or bromine.
Generally the reactants are reacted in molar amounts. However, optionally it can be suitable to employ one reactant in slight excess. This is especially true in case the compound of formula III represents a carboxylic acid ester R 2 --alk--CO--OR, whereby R is a lower alkyl group. (In this case it is recommended, optionally to continuously remove the lower alcohol formed in the reaction.) Optionally the reaction can also be carried out in the presence of basic or acid binding agents such as alkali carbonates (potash, soda) alkali hydrogen carbonates, alkali acetates, alkali hydroxides, or tertiary amines (for example, triethylamine). The latter is especially true if compounds of formula III are employed wherein X is a halogen atom.
In a given case, it is also favorable to add condensation agents such as dicyclohexyl carbodiimide, tetraethyl pyraphosphite, 5-(3'-sulfonephenyl)-ethyl-isooxazole, sulfurous acid-bisalkyl amides (for example SO[N(CH 3 ) 2 ] 2 ) or N,N'carbonyl-diimidazole (in case for example X is OH). In case R represents a substituted phenyl radical, this preferably contains one or two of the stated substituents, whereby these preferably are located in the 3 and/or 4-position of the phenyl radical. Unknown starting materials of formula III wherein X is a halogen atom (preferably chlorine or bromine) and Z' is the group --CO--alk--R 2 , can be obtained in known manner for example, from the corresponding acids by reaction with thionyl chloride or thionyl bromide. For example, there is given the production of 3-cyclohexyl propionyl chloride:
Within 45 minutes there is dropped into 135.6 grams (1.14 moles) of thionyl chloride 60 grams (0.38 mole) of 3-cyclohexyl propionic acid. After the ending of the dropping in, the mixture was stirred for a further 2 hours at 50° C. Subsequently the excess thionyl chloride was concentrated in a vacuum and the residue remaining reacted without purification.
Those starting materials of formula III wherein X is the group OR and Z' the group --CO--alk--R 2 can be produced in the customary manner from the just mentioned acid chlorides or acid halides by reaction with compounds HOR or their metal salts (alkali salts) (see in regard to this Organikum, Organisch Chemisches Grundpraktikum, VEB; Deutscher Verlag der Wissenschaften Berlin, 9th edition 1976, pages 400 et seq.). Unknown starting materials of formula II wherein Z is the group --CO--alk--R 2 can be produced for example, by reaction of benzyl pyperazine with the corresponding acid chlorides R 2 --alk--COCl and subsequent debenzylation. The reaction of the benzyl piperazine with the acid chloride for example is carried out at 0° C. in acetone as solvent. After removing the solvent the thus obtained crude product is taken up in methanol, treated with Pd/C and debenzylated at 5 bar and 40° C. After filtering off the catalyst the solvent is distilled off in a vacuum. The product produced in this manner can be further processed without additional working up.
In regard to Process (b):
This process is preferably carried out in a polar solvent at temperatures between 40°-200° C. Preferably it is performed in the presence of an acceptor for the hydrohalide formed in the course of the reaction. As acid acceptors there can be used for example: alkali carbonates (K 2 CO 3 , Na 2 CO 3 , NaHCO 3 ), tertiary amines such as triethylamine, pyridine, alkali acetate, alkali hydroxide. Hal in the starting compound for this process preferably means chlorine or bromine.
As solvents there can be used for example: lower alkanols (ethanol, isopropanol, butanol, isoamyl alcohol), lower alicyclic or cyclic ethers (diethyl ether, dioxane, tetrahydrofurane), diethylene glycol, di-C 1 -C 4 -alkyl ethers (dimethyl ether of diethylene glycol), lower dialkyl amides of lower saturated aliphatic carboxylic acids (dimethyl formamide, dimethyl acetamide), tetramethyl urea, N-methyl pyrrolidone, dimethyl sulfoxide as well as mixtures of these agents.
Starting materials of formula IV can be obtained for example, from acid chlorides of the formula R 2 --alk--COCl and an amine of the formula HN(CH 2 --CH 2 --Hal) 2 , in the customary manner. Hal is preferably chlorine, bromine, or iodine. For this purpose for example, there are reacted equimolar amounts of the corresponding acid chloride, N-(bis-2-haloethyl)-amine acid and triethylamine at 0° C. in acetone as a solvent. Then the mixture is stirred for a further 8 hours at room temperature. Then the triethylamine hydrochloride formed is filtered off and the filtrate concentrated in a vacuum. The residue formed, without further purification is reacted with the corresponding anilines to the compounds of the invention as described in Example 39. For example, the N-(bis)-2-chloroethyl)-3-cyclohexyl-propionamide is produced as follows: 10 ml of acetone were slowly dropped into a mixture of 0.01 mole (1.8 gram) of N-(bis-chloroethyl)-amine-hydrochloride, 0.02 mole (1 gram) of triethylamine and 0.01 mole (1.7 gram) of 3-cyclohexyl-propionyl chloride in 50 ml of acetone cooled to 0° C. After the end of the dropping in, stirring was continued for a further 8 hours at room temperature. Then the triethylamine hydrochloride formed was filtered off and the filtrate concentratd in a vacuum. The product thus obtained, without further purification, was reacted with 0.03 mole (1.2 grams) of 3-methoxyaniline, as described in Example 39.
Depending on the process conditions and the starting material, there are obtained the final product of formula I either in the free form or in the form of their salts. The salts of the final products can be again converted into the bases in known manner, for example with alkali or ion exchangers. From the bases there can be obtained salts by reaction with organic or inorganic acids, especially those which are suitable for formation of therapeutically useful salts. As such acids, there can be mentioned: hydrohalic acids, e.g. hydrochloric acid, hydrobromic acid, acids of sulfur, sulfuric acid, sulfurous acid, acids of phosphorus, phosphoric acid, phosphorous acid, nitric acid, perchloric acid, organic mono-, di-, or tricarboxylic acids of the aliphatic, alicyclic, aromatic, or heterocyclic series as well as sulfonic acids. Examples of these are: formic acid, acetic acid, propionic acid, succinic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, maleic acid, fumaric acid, hydroxymaleic acid, pyruvic acid, phenyl acetic acid, benzoic acid, p-aminobenzoic acid, anthranilic acid, p-hydroxybenzoic acid, salicylic acid, or p-aminosalicylic acid, embonic acid, methanesulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid, ethylenesulfonic acid, halobenzenesulfonic acid, e.g. p-chlorobenzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, or sulfanilic acid or even 8-chlorotheophylline.
Those compounds which contain asymmetric carbon atoms and are usually produced as racemates may be split into the optically active isomers in a known manner, for example, by means of an optically active acid. However, it is also possible to use an optically active or also diastereomeric starting material from the beginning, in which case a corresponding pure optically active or diastereomeric configuration is obtained as the end product.
Diastereomeric racemates can also occur, in case there are present two or more asymmetrical carbon atoms in the compounds produced. Separation is possible in customary manner, for example by recrystallization.
The compounds according to this invention are suitable for the preparation of the pharmaceutical compositions or preparations. The pharmaceutical compositions or medicaments contain an active principle one or more of the compounds according to the invention, optionally in admixture with other pharmacologically or pharmaceutically active substances. The medicaments are prepared in known manner with the usual pharmaceutical additives and other conventional excipients and diluents.
Examples of excipients and additives of this kind are the substances recommended and specified in the following literature references as additives for pharmacy, cosmetics and related fields: Ullmanns Encyklopadie der technischen Chemie, Volume 4 (1953), pages 1-39; Journal of Pharmaceutical Sciences, Volume 52 (1963), pages 918 et seq.; H. V. Czetsch-Lindenwald, Hilfsstoffe fur Pharmazie und angrenzende Gebiete; Pharm. Ind., No. 2, 1961, pages 72 et. seq.; Dr. H. P. Fiedler, Lexikon der Hilfsstoffe fur Pharmazie, Kosmetic und angrenzende Gebiete Cantor KG. Aulendorf (Wurtt.)
Examples of such materials include gelatin, natural sugars such as sucrose or lactose, lecithin, pectin, starch (for example cornstarch), alginic acid, tylose, talc, lycopodium, silica (for example collodial silica), glucose, cellulose, cellulose derivatives, for example cellulose ethers in which the cellulose hydroxyl groups ar partially etherified with lower aliphatic alcohols and/or lower saturated oxyalcohols (for example, methyl hydroxypropyl cellulose, methyl cellulose, hydroxyethyl cellyulose), stearates, e.g. methyl stearate and glyceryl stearate, magnesium and calcium salts of fatty acids with 12 to 22 carbon atoms, especially saturated acids (for example, calcium stearate, calcium laurate, magnesium oleate, calcium palmitate, calcium behenate, and magnesium stearate), emulsifiers, oils and fats, especially of plant origin (for example, peanut oil, castor oil, olive oil, sesame oil, cottonseed oil, corn oil, wheat germ oil, sunflower seed oil, cod-liver oil), mono, di, and triglycerides of saturated fatty acids (C 12 H 24 O 2 to C 18 H 36 O 2 and their mixtures), e.g., glyceryl monostearate, glyceryl distearate, glyceryl tristearate, glyceryl trilaurate, pharmaceutically compatible mono- or polyhydric alcohols such as glycerine, mannitol, sorbitol, pentaerythritol, ethyl alcohol, diethylene glycol, triethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol 400, and other polyethylene glycols as well as derivatives of such alcohols and polyglycols, esters of saturated and unsaturated fatty acids (2 to 22 carbon atoms, especially 10 to 18 carbon atoms), with monohydric aliphatic alcohols (1 to 20 carbon atom alkanols), mannitol, ethyl alcohol, butyl alcohol, octadecycl alcohol, etc., e.g., glyceryl stearate, glyceryl palmitate, glycol distearate, glycol dilaurate, glycol diacetate, monoacetin, triacetin, glyceryl oleate, ethylene glycol stearate; such esters of polyvalent alcohols can in a given case, also be etherified, benzyl benzoate, dioxolane, glycerine formal, tetrahydrofurfuryl alcohol, polyglycol ethers with 1 to 12 carbon atom alcohols, dimethyl acetamide, lactamide, lactates, e.g., ethyl lactate, ethyl carbonate, silicones (especially medium viscosity dimethyl polysiloxane), magnesium carbonate and the like.
As further adjuvants there can be used materials which cause decomposition (so-called explosive agents) such as: cross-linked polyvinyl pyrrolidine, sodium carboxymethyl starch, or microcrystalline cellulose. Likewise there can be used encasing agents such as for example: polyacrylic ester, cellulose ether and the like.
For the production of solutions, there can be used water or physiologically compatible organic solvents, as for example, ethanol, 1,2-propylene glycol, polyglycols, e.g., diethylene glycol, triethylene glycol and dipropylene glycol and their derivatives, dimethyl sulfoxide, fatty alcohols, e.g., stearyl alcohol, cetyl alcohol, lauryl alcohol and oleyl alcohol, triglycerides, e.g., glyceryl oleate, glyceryl stearate, glyceryl palmitate, and glyceryl acetate, partial esters of glycerine, e.g., glyceryl monostearate, glyceryl distearate, glyceryl monopalmitate, paraffins, and the like.
In the production of the composition, there can be used known and customary solution aids or emulsifiers. As solution aids and emulsifiers, there can be used, for example, polyvinyl pyrrolidone, sorbitan fatty acid esters such as sorbitan trioleate, lecithin, gum acacia, gum tragacanth, polyoxyethylated sorbitan monooleate, polyoxyethylated fats, polyoxyethylated oleotriglycerides, linolized oleotriglycerides, polyethylene oxide-condensation products of fatty alcohols, alkylphenols or fatty acids or also 1-methyl-3-(2-hydroxyethyl)-imidazolidone-2. As used herein, polyoxyethylated means that the materials in question contain polyoxyethylene chains whose degree of polymerization generally is between 2 and 40, particularly between 10 and 20.
Such polyoxyethylated materials, for example, can be obtained by reaction of hydroxyl group containing compounds (for example, mono- or diglycerides) or unsaturated compounds such as, for example, those containing the oleic acid radical with ethylene oxide (for example, 40 moles of ethylene oxide per mole of glyceride).
Examples of oleotriglycerides are olive oil, peanut oil, castor oil, sesame oil, cottonseed oil, corn oil (see also Dr. H. P. Fiedler, supra, pages 191-195.
Furthermore, there can be added preservatives, stabilizers, buffers, for example, calcium hydrogen phosphate, collodial aluminum hydroxide, taste correctives, antioxidants and complex formers (for example, ethylene diamine tetraacetic acid) and the like. In a given case for stabilization of the active molecule, the pH is adjusted to about 3 to 7 with physiologically compatible acids or buffers. Generally, there is preferred a neutral to weak acid (to pH 5) pH value.
As antioxidants, there can be used, for example, sodium meta bisulfite, ascorbic acid, gallic acid, alkyl gallates, e.g., methyl gallate and ethyl gallate, butyl hydroxyanisole, nordihydroguaiaretic acid, tocopherols as well as tocopherol and synergists (materials which bind heavy metals by complex formation, for example, lecithin, ascorbic acid, phosphoric acid). The addition of synergists increases considerably the antioxidant activity of tocopherol. As preservatives, there can be used, for example, sorbic acid, p-hydroxybenzoic acid esters (for example, lower alkyl esters such as the methyl ester and the ethyl ester), benzoic acid, sodium benzoate, trichloroisobutyl alcohol, phenol, cresol, benzethonium chloride, and formalin derivatives.
The pharmacological and galenical treatment of the compounds of the invention is carried out according to the usual standard methods. For example, the active material or materials and assistants or carriers are well mixed by stirring or homogenization (for example, by means of customary mixing apparatus, e.g., a colloid mill or ball mill), wherein the operation is generally carried out at temperatures between 20° and 80° C., preferably 20° to 50° C., especially at room temperature. Besides, reference is made to the following standard textbook: Sucker, Fuchs, Speiser, Pharmazeutische Technologie, Thieme-Verlag, Stuttgart, 1978.
The active principles of medicaments may be applied to the skin or mucosa or into the interior of the body, for example orally, enterally, pulmonarily, rectally, nasally, vaginally, lingually, intravenously, intra-arterially, intracardially, intramuscularly, intraperitoneally, intracutaneously, or subcutaneously.
The compounds of the invention show a good analgetic action in the electro pain test, mouse (B. Blake et al, Med, exp., Volume 9, page 146, (1963) or Haffner test, mouse (F. Haffner, Dtsch. Med. Wschr., Volume 55, page 731 (1929).
For example, in the above-mentioned test procedures there is obtained the analgetic action at a dosage of 20 mg/body weight kg mouse per os.
This analgetic action is comparable with the action of the known medicines Pethidin and Pentazocine.
The lowest clearly effective dosage (activity as stated above) in the above-mentioned animal experiments is for example:
5 mg/kg orally
0.5 mg/kg intravenously
As a general dosage range for the above-mentioned activities (animal experiments as above) there can be used:
5-100 mg/kg orally, especially 10-40 mg/kg
0.5-10 mg/kg intravenously, especially 0.1-4 mg/kg.
The compounds of the invention are indicated for pains due to various causes such as postoperative pains, wounds, and toothaches.
The pharmaceutical preparation generally contain between 0.5 and 150 mg, preferably 10 to 100 mg of the active components of the invention.
The preparations may be administered, for example, in the form of tablets, capsules, pills, dragees, suppositories, ointments, jellies, creams, powders, dusting powders, aerosols, or in liquid form. Examples of liquid formulations are oily or alcoholic or aqueous solutions, suspensions and emulsions. Preferred formulations are tablets containing from 10 to 50 mg or active substance, or solutions containing from 1 to 10% of active substance.
The active components according to the present invention may be used in individual doeses of, for example:
(a) from 5 to 100 mg, preferably from 10 to 50 mg in the case of oral formulations,
(b) from 0.5 to 10 mg, preferably from 1 to 5 mg in the case of parenteral formulations (for example intravenously, intramuscularly),
(c) from 0.5 to 300 mg, preferably from 10 to 100 mg in the case of formulations for rectal or vaginal application. (the doses are based on the free base in each case).
For example, 1 to 3 tablets containing from 10 to 50 mg of active substance may be prescribed three times daily or, for example, in the case of intravenous injection, a 1 to 10 ampoule containing from 1 to 5 mg of active substance may be prescribed one to five times daily. In the case of oral administration, the minimum daily dose is, for example, 30 mg, while the maximum daily dose should not exceed 1 gram.
For the treatment of dogs and cats the individual dosage orally is generally between about 1 and 100 mg/kg body weight. The parental dosage is between about 0.1 and 10 mg/kg body weight.
For the treatment of horses and cattle the individual dosage orally is generally between about 1 and 100 mg/kg; the parenteral individual dosage is between about 0.1 and 10 mg/kg body weight.
The acute toxicity of the compounds of the invention on the mouse (expressed by the LD 50 mg/kg; method according to Miller and Tainter: Proc. Soc. Exper. Biol. a. Med., Volume 57 (1944), page 261 for example, with oral application is between 100 and 2500 mg/kg (or above 2500 mg/kg).
The medicaments may be used in human medicine, veterinary medicine, or in agriculture, either individually or in admixture with other pharmacologically active substances.
Unless otherwise indicated, all parts and percentages are by weight.
The compositions can comprise, consist essentially of, or consist of the stated materials set forth.
The methods can comprise, consist essentially of, or consist of the steps set forth with the materials shown.
DETAILED DESCRIPTION
Example 1 (Process a)
1-(3-methoxy-phenyl)-4-(3-cyclohexyl-propionyl)-piperazine ##STR8##
There was dropped into a mixture of 0.06 mole (11.5 grams) of N-(3-methoxyphenyl)-piperazine and 0.06 mole (6.1 grams) of triethylamine in 100 ml of absolute toluene with stirring at room temperature 0.06 mole (10.5 grams) of 3-cyclohexylpropionyl chloride. After the end of the dropping in, stirring was continued at room temperature for a further 3 hours. The triethylammonium hydrochloride formed was filtered off and the filtrate concentrated in a vacuum. The residue was dissolved in 60 ml of acetone and treated dropwise with 11 ml of 6N isopropanolic hydrochloric acid. The hydrochloride precipitated out and was recrystallized from methyl ethyl ketone.
Yield: 9.9 grams.
M.P. of the hydrochloride: 175°-176° C.
In another embodiment the procedure can be as follows:
II
A mixture of 0.05 mole (7.8 grams) of 3-cyclohexylpropionic acid, 0.05 mole (9.6 grams) of N-(3-methoxy-phenyl)-piperazine and 0.05 mole (10.3 grams) of N,N-dicyclohexyl-carbodiimide dissolved in 150 ml of water-free methylene chloride was stirred for 7 days at room temperature. After the end of the reaction the dicyclohexylurea formed was filtered off, the filtrate concentrated in a vacuum and the crude product converted into the hydrochloride as described above.
Yield: 3.7 grams.
M.P. of the hydrochloride: 175°-176° C.
III
A mixture of 0.05 mole (8.5 grams) of 3-cyclohexylpropionic acid methyl ester and 0.06 mole (11.5 grams) of N-(3-methoxyphenyl)-piperazine dissolved in 100 ml of toluene was heated under reflux for 8 hours, whereby the alcohol (CH 3 OH) formed in the reaction was distilled off. After the end of the reaction the solvent was drawn off in a vacuum. The crude product was converted into the hydrochloride in the manner described through addition of 6N isopropanolic HCl and the hydrochloride was recrystallized from methyl ketone for further purification.
Yield: 4.6 grams.
M.P. of the hydrochloride: 175°-176° C.
In the manner analogous to Example 1 (according to Process a) the following compounds of formula I set forth in Table 1 were obtained:
__________________________________________________________________________Product YieldExampleR.sub.1 R.sub.2 alk in g M.P. (0° C.) Starting Materials__________________________________________________________________________ ##STR9## Cyclohexyl (CH.sub.2).sub.2 12,3 144-145 (HCl-Salt) 11.5 g N(o-Methoxy-phenyl)-pipe ra- zine 10,5 g 3-cyclohexyl-propionyl chloride3 ##STR10## Cyclohexyl CH.sub.2 10,9 150-153 (HCl-Salt) 7,8 g 2-Cyclohexyl-acetic acid and 9,6 g N(2-Methoxy-phenyl)-p ipera- zine4 ##STR11## ##STR12## (CH.sub.2).sub.2 9,0 198-199 (HCl-Salt) 11,5 g (2-Methoxy-phenyl)-piper azine and 12,9 g 3-(3,3-Dimethyl-bicyclo- [2.2.1]-hept-2-yl)-propionyl chloride5 ##STR13## As in Example 4 (CH.sub.2).sub.2 5,3 175 (HCl-Salt) 12,4 g N(2-Ethoxy-phenyl)-piper azine and 12,9 g 3-(3,3-Dimethyl-bicyclo- [2.2.1]-hept-2-yl)-propionyl chloride6 ##STR14## As in Example 4 CH.sub.2 11,8 183-187 (HCl-Salt) 11,5 g N(2-Methoxy-phenyl)-pipe razine and 11 g (3,3-Dimethyl-bicyclo- [2.2.1]-hept-2-yl)-acetyl chloride7 ##STR15## As in Example 4 CH.sub.2 10,1 107 (Base) 12,4 g N(2-Ethoxy-phenyl)-piper azine and 11 g (3,3-Dimethyl)-bicyclo- [2.2.1]-hept-2-yl)-acetyl chloride8 ##STR16## ##STR17## (CH.sub.2).sub.2 4,9 155-156 (HCl-Salt) 9,6 g N(2-Methoxy-phenyl)-piper azine and 7,1 g 3-Cyclopentyl-propionic acid9 ##STR18## ##STR19## (CH.sub.2).sub.2 4,8 134-136 (HCl-Salt) 10,3 g N(2-Ethoxy-phenyl)-piper azine and 7,1 g 3-Cyclopentyl-propionic acid10 ##STR20## Cyclohexyl (CH.sub.2).sub.2 12,6 147-148 (HCl-Salt) 12,4 g N(2-Ethoxy-phenyl)-piper azine and 10,5 g 3-Cyclohexyl-propionyl chloride11 ##STR21## Cyclohexyl (CH.sub.2).sub.2 9,2 146 (HCl-Salt) 13,2 g N(2-n-Propyloxy-phenyl)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride12 ##STR22## Cyclohexyl (CH.sub.2).sub.2 5,2 59-63 (Base) 13,2 g N(2-Isopropyloxyphenyl)- piperazine and 10,5 g 3-cyclohexyl- propionyl chloride13 ##STR23## Cyclohexyl (CH.sub.2).sub.2 8,3 37-39 (Base) 13 g N(2-Allyloxy-phenyl)-piper azine and 10,5 g 3-Cyclohexyl-propionyl chloride14 ##STR24## Cyclohexyl (CH.sub.2).sub.2 5,0 70-72 (Base) 15,6 g N(2-Cyclohexyloxy-phenyl )- piperazine and 10,5 g 3-Cyclo- hexyl-propionyl chloride15 ##STR25## Cyclohexyl (CH.sub.2).sub.2 11,5 86-87 (Base) 16,8 g N(2-Benzyloxy-phenyl)- piperazine and 10,5 g 3-Cyclo- exyl-propionyl chloride16 ##STR26## Cyclohexyl (CH.sub.2).sub.2 5,8 61 (Base) 13,1 g N(2-Acetoxy-phenyl)- piperazine and 10,5 g 3-Cyclo- exyl-propionyl chloride17 ##STR27## Cyclohexyl (CH.sub.2).sub.2 8,5 111-113 (HCl-Salt) 10,5 g N(2-Mercapto-phenyl)- piperazine and 12,5 g 3-Cyclo- exyl-propionyl chloride18 ##STR28## Cyclohexyl (CH.sub.2).sub.2 6,1 128-130 (Base) 10,7 g N(2-Hydroxy-phenyl)-pipe razine and 10,5 g 3-Cyclohexyl-propionyl chloride19 ##STR29## Cyclohexyl (CH.sub.2).sub.2 15,0 173-175 (HCl-Salt) 7,8 g 3-Cyclohexyl-propionyl and 9,6 g N(4-Methoxy-phenyl)- iperazine20 ##STR30## Cyclohexyl (CH.sub.2).sub.2 6,9 73-74 (Base) 11,4 g N(2,6-Dimethyl-phenyl)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride21 ##STR31## Cyclohexyl (CH.sub.2).sub.2 8,6 158 (HCl-Salt) 10,5 g N(2-Methyl-phenyl)-piper azine and 10,5 g 3-Cyclohexyl-propionyl chloride22 ##STR32## Cyclohexyl (CH.sub.2).sub.2 6,5 114-117 (HCl-Salt) 11,8 g N-(2-Chloro-phenyl)-pipe razine and 10,5 g 3-Cyclohexyl-propionyl chloride23 ##STR33## Cyclohexyl (CH.sub.2).sub.2 11,9 134-136 (HCl-Salt) 10,8 g N(2-Fluoro-phenyl)-piper azine and 10,5 g 3-Cyclohexyl-propionyl chloride24 ##STR34## Cyclohexyl (CH.sub.2).sub.2 7,0 52-54 (Base) 14,5 g N(2-Bromo-phenyl)-pipera zine and 10,5 g 3-Cyclohexyl-propionyl chloride25 ##STR35## Cyclohexyl (CH.sub.2).sub.2 7,0 160-162 (HCl-Salt) 13,8 g N(3-Trifluoromethyl-phen yl)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride26 ##STR36## Cyclohexyl (CH.sub.2).sub. 2 15,3 61-62 (Base) 12,4 g N(2-Nitro-phenyl)-pipera zine and 10,5 g 3-Cyclohexyl-propionyl chloride27 ##STR37## Cyclohexyl (CH.sub.2).sub.2 4,5 202-203 (HCl-Salt) 8,8 g N(2-Amino-phenyl)-piperaz ine and 7,8 g 3-Cyclohexyl-propionic acid28 ##STR38## Cyclohexyl (CH.sub.2).sub.2 6,5 89-91 (Base) 11,5 g N(2-Methylamino-phenyl)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride29 ##STR39## Cyclohexyl (CH.sub.2).sub.2 4,3 Oil Rf-Value 0,72* 12,2 g N(2-Dimethylamino-phenyl )- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride30 ##STR40## Cyclohexyl (CH.sub.2).sub.2 8,5 77 (Base) 13,9 g N(2-Diethylamino-phenyl) - piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride31 ##STR41## Cyclohexyl (CH.sub.2).sub.2 6,2 107-108 (Base) 13,1 g N(2-Acetamino-phenyl)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride32 ##STR42## Cyclohexyl (CH.sub.2).sub.2 6,0 93-94 (Base) 13,1 g N(2-Propionylamino-pheny l)- piperazine and 10,5 g 3-Cyclohexyl- propionyl chloride33 ##STR43## Cyclohexyl (CH.sub.2).sub.2 9,5 175-177 (HCl-Salt) 9,7 g Phenylpiperazine and 10,5 g 3-Cyclohexyl-propionyl chloride34 ##STR44## Cyclohexyl (CH.sub.2).sub.2 9,2 89-90 (Base) 9,8 g NPyridyl-(2)-piperazine and 10,5 g 3-Cyclohexyl-propion yl chloride35 ##STR45## Cyclohexyl (CH.sub.2).sub.2 7,1 104-105 (Base) 9,8 g NPyrimidyl-(2)-piperazine and 10,5 g 3-Cyclohexyl-propio nyl chloride36 ##STR46## Cyclohexyl (CH.sub.2).sub.2 10,7 95-96 (Base) 19,8 g N2-Chlor-pyrazinyl-(6)- iperazine and 10,5 g 3-Cyclohexyl- propionyl chloride__________________________________________________________________________ *The RFValue (from the English retention factor) was determined on a silicagel-thin layer chromatography plate (Si60.sub.F254 Fa. Merck, Darmstadt), Running agent: Chloroform/Methanol/NH.sub.3 at a ratio of 95:4:1.
Example 37
1-(2-Methylamino-phenyl)-4-(3-cyclohexylpropionyl)-piperazine
(The same compound as obtained in Example 28)
There was dropped into a mixture of 0.03 mole (10.4 grams) of 1-(2-aminophenyl)-4-(3-cyclohexyl-propionyl)-piperazine and 0.12 mole (10.1 grams) of NaHCO 3 in 50 ml of water at 10° C. 0.11 mole (13.9 grams) of dimethyl sulfate. After the end of the dropping in, the mixture was allowed to slowly warm to room temperature. Then it was stirred for a further 24 hours at room temperature. Subsequently it was heated to 50° C. for 4 hours. After cooling to room temperature the mixture was treated with 10% NaOH until alkaline reaction. It was shaken three times, each time with 100 ml of diethyl ether, the organic phase separated off, the combined organic phases dried over Na 2 SO 4 and concentrated in a vacuum. The concentrated residue was chromatographed over silica gel. As running agent there was employed CHCl 3 /ethyl acetate in the ratio 95:5.
Yield: 2.1 grams.
M.P. 89°-91° C.
The alkylation can also be carried out with methyl iodide.
At room temperature with stirring there was dropped into a mixtured of 0.02 mole (2.8 grams) of K 2 CO 3 and 0.018 mole (5.5 grams) of 1-(2-aminophenyl)-4-(3-cyclohexyl-propionyl)-piperazine dissolved in 75 ml of absolute tetrahydrofurane, 0.02 mole (2.84 grams) of methyl iodide dissolved in 20 ml of tetrahydrofurane. The mixture was heated at reflux for 7 days. The the solids formed were removed by suction filtering, the filtrate was washed with water, concentrated in a vacuum, and the concentrated residue chromatographed on silica gel. As running agent there was employed a mixture of diethyl ether/benzine in the ratio 1:1.
Yield: 1.6 grams.
M.P. 90°-91° C.
Example 38
1-(2-Propyloxy-phenyl)-4-(3-cyclohexylpropionyl)-piperazine
(The same compound was obtained as in Example 11.)
0.03 mole (0.7 gram) of sodium was dissolved in 50 ml of absolute ethanol. There was added with stirring at room temperature 0.025 mole (7.9 grmas) of 1-(2-hydroxy-phenyl)-4-(3-cyclohexylpropionyl)-piperazine and the mixture heated at reflux for 1 hour with stirring. The solvent was then drawn off in a vacuum and the residue dissolved in 70 ml of absolute dimethyl formamide. There was dropped into this solution 0.025 mole (3.1 grams) of n-propyl bromide in 10 ml of dimethyl formamide at room temperature. Then the mixture was heated for 8 hours at 40°-50° C. The mixture was then concentrated in a vacuum, a residue treated with water, treated with ammonia until alkaline reaction, shaken 3 times, each time with 50 ml of CHCl 3 , the organic phase dried over Na 2 SO 4 and concentrated in a vacuum. The crude product was chromatographed on silica gel. As running agent there was used a mixture of ethyl acetate/CHCl 3 (5:95).
Yield: 2.6 grams.
M.P. of the hydrochloride: 146° C.
If there is used in place of n-propyl bromide 0.025 mole of another alkylated compound, there is obtained a different alkylated product.
Thus there are obtained according to the above-mentioned procedure using 0.025 mole (3.15 grams) of benzyl chloride 5.1 grams of the compound made in Example 15.
M.P. of the base: 86°-87° C.
Using 0.025 mole (3.02 grams) of allyl bromide there are obtained 5.0 grams of the compound made in Example 13.
M.P.: 37°-39° C.
Using 0.025 mole (4.07 grams) of cyclohexyl bromide there are obtained 1.8 grams of the compound made in Example 14.
M.P.: 70°-72° C.
Example 39
1-(3-Methoxy-phenyl)-4-(3-cyclo hexyl-propionyl)-piperazine ##STR47##
0.01 mole (2.8 grams) of N-(bis-(2-chloroethyl))-3-cyclohexyl-propionamide and 0.03 mole (1.2 grams) of 3-methoxy-aniline were heated in 50 ml of diethylene glycol dimethyl ether for 14 hours at 150° C. The mixture obtained was treated with water and subsequently extracted 3 times with dichloromethane. The combined methylene chloride extracts were dried over Na 2 SO 4 ; after filtering off the solids, the filtrate was concentrated in a vacuum. The residue was taken up in 10 ml of acetone and treated dropwise with 3 ml of 6N isopropanolic hydrochloric acid. The hydrochloride precipitated and was recrystallized from methyl ethyl ketone.
Yield: 1.1 grams.
M.P. of the hydrochloride: 175°-176° C.
EXAMPLES OF PHARMACEUTICAL PREPARATIONS
Example, Capsules
10 kg of the compound made in Example 2 (hydrochloride) were granulated in known manner in a fluidized bed-spray granulation apparatus with a solution of 0.25 kg of gelatin in 2.25 kg of water. After mixing in 0.80 kg of cornstarch, 0.1 kg of magnesium stearate and 0.05 kg of highly dispersed silica, the mixture was filled into size 1 hard gelatin capsules in an amount in each sae of 224 mg.
Each capsule contains 200 mg of active material.
Example, Ampoule
100 grams of the compound made in Example 2 (hydrochloride) were dissolved in a mixture of 900 grams of propanediol-1,2 and 150 grams of ethanol. For injection purposes the solution was filled up to 2 liters with water, sterile filtered via a membrane filter of suitable pore size and filled into 2 ml sterilized ampoules under aseptic conditions.
One ampoule contains 100 mg of active material in 2 ml of solution. | There are prepared new pharmacologically active compounds of the formula: ##STR1## In formula I R 1 is a phenyl radical, pyridyl radical, a pyrimidyl group, or pyrazinyl radical, or a phenyl radical, pyridiyl radical, pyrimidyl radical, or pyrazinyl radical substituted by the radicals R 3 and R 4 which are the same or different and are hydrogen, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, C 1 -C 6 -alkyl groups C 1 -C 6 -alkoxy groups, C 3 -C 6 -alkenyloxy groups, C 3 -C 6 -cycloalkyloxy groups, phenyl-C 1 -C 4 -alkoxy groups, C 1 -C 6 -alkylmercapto groups, the nitro group, the amino group, C 1 -C 6 -dialkylamino groups, C 2 -C 6 -alkanoyl groups, C 2 -C 6 -alkanoylamino groups, or C 2 -C 6 -alkanoyloxy groups and R 2 is the adamantyl group, the 3,3-dimethyl-bicyclo[2.2.1]hept-2-yl radical, a saturated C 3 -C 16 -cycloalkenyl radical and alk is a straight or branched C 1 -C 6 alkyl chain. | 2 |
BACKGROUND OF THE INVENTION
The present invention regards an acoustic concentrator system and method for capturing particulates entrained in gaseous (e.g., aerosol) or liquid fluids, and delivering a concentrated sample or stream of the particulate. In some embodiments the system and method can further provide a continuous flow of concentrated particulate. By concentrating the particulate entrained in gaseous or liquid fluids, the system of the present invention can be used to more effectively and accurately sample fluids for particulates.
Prior art related to aerosol concentration relies on inertial methods of particle separation and concentration within, typically, an air stream. Specifically, when an air stream containing particulate undergoes acceleration, the relatively high inertia of the particulate (as compared to the surrounding air) causes relative motion between the air and particulate, allowing the particulate to be separated from the air. For example, a virtual slit impactor is a well-known aerosol concentrator that concentrates particulate by extracting a minor flow that contains more particulate through a narrow aperture or slit, while the major flow containing less particulate is drawn through a 90-degree turn in the housing (the inertia of the particulate makes it difficult to continue through the turn). However, high humidity (>90%) air can cause condensation and accumulation of particulate on internal surfaces (e.g., precisely machined knife edges for diverting major and minor air flows), which negatively impacts the concentration of particulate delivered by the system. Furthermore, the inertia methods are less effective as the size of the particulate decreases (e.g., below 3 microns).
In contrast to the prior art, the present invention uses a fundamentally different approach to particulate concentration, exploiting the physical interaction between a sound field and a particulate. In the system and method of the present invention, the sound field is used to force particulates entrained in a fluid towards storage locations near or within nodal and anti-nodal positions within an acoustic resonator. When the sound field is activated at a sufficiently high sound pressure level, the acoustic force overcomes other forces experienced by particulate, e.g., air flow and viscous drag. Particulates are thereby trapped in storage locations of the resonator. When the sound field is deactivated, the particulate is released from the storage locations and is delivered by the system of the present invention as a concentrated stream of particulate.
The present invention is thereby a novel improvement over prior art systems. As hereinafter discussed, the invention expands the application methods to include particulate concentration in fluids, improves concentration of particulates below 3 micron, provides a more compact system, allowing for adjustability of the level of concentration, functions over a wide range of humidity and temperature (as the system does not provide machined knife edges that may accumulate particulates in high humidity), and consumes less overall power than the prior art systems.
Useful applications of the system and method of the present invention include integration into the inlet of an aerosol detection system, whereby the present invention increases the sensitivity of the detection system by concentrating particulates within the sampled air, leading to earlier detection of aerosol agents. Other applications include improving the sensitivity of other biological, chemical, radionuclide, and explosives sensors, by delivering a more effective sample of particulates entrained in a fluid. Similarly, the system and methods of the present invention may be used to process powdered materials, such as in the manufacturing of pharmaceutical powders.
SUMMARY OF THE INVENTION
Device.
The acoustic concentrator system of the present invention includes one or more structure-filled acoustic resonators and means for applying a sound field within the resonators. The sound pressure level and the frequency of the applied sound field are selected to trap a desired particulate or aerosol within the resonator—specifically, the sound field tends to move the particle into an acoustic node/anti-node where it temporarily held in place as a result of the applied sound field. By removing or altering the sound field, trapped particulate can be released from near the structured material and expelled from the resonator. Further, the system includes means for drawing into the resonator an air or liquid sample from the environment, means for expelling excess air or liquid from the resonator, and means for periodically or continuously releasing from the resonator a concentrated stream of the particulate.
Method.
The acoustic concentrator method of the present invention removes and concentrates particulates entrained in a fluid using one or more structure-filled acoustic resonators, such as the system herein described. In one embodiment, the resonator is filled with a fiber material. In other embodiments, the resonator may be filled with other materials such as a mesh grid, granular material, or honeycomb structure. The method includes the steps of drawing into the resonator an air sample having particulate entrained therein and applying an acoustic field within the resonator to cause the particulate to be temporarily trapped within the structured network of the resonator. The acoustic field of the method of the present invention has sound pressure level and/or frequency selected to dislodge the particulate from the fluid and trap the particulate near the structures. The method of the present invention further includes the steps of expelling excess air from the resonator, and periodically or continuously releasing from the resonator a concentrated stream of the particulate in a fluid. In some embodiments this process is cycled in a sequence among a series of resonators, wherein at least one resonator is providing a concentrated release of particulate, to achieve a continuous-flow of concentrated particulate.
The method of the present invention may further comprise sensing or sampling the concentrated particulate within or released from the resonator. Devices suitable for use to accomplish such sensing/sampling include fluorescent aerosol detection systems and other biological, chemical, radionuclide, and explosives sensors. Specifically, one may position these sensors near the outlet of the acoustic concentrator device, or the sensor may be positioned to sense the contents within the acoustic resonator. A transparent acoustic resonator may also be constructed to permit optical detection of aerosols within the resonator itself.
FIGURES
The patent or application file contains at least one drawing executed in color (see FIG. 1 ). Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
FIG. 1 is a numerical simulation of the number of acoustic storage locations within a fibrous resonator chamber.
FIG. 1A is a depiction of various fibers suitable for use in the acoustic resonator of the present invention.
FIG. 2 is a depiction of a single-resonator embodiment of the system of the present invention.
FIG. 3 shows transient concentration measurements acquired with the ultrasonic resonator of the embodiment shown in FIG. 2 , as further described in Example 1.
FIG. 4 shows concentration output from three aerosol surges (concentrated air streams from an acoustic resonator of the system of the present invention), overlaid to demonstrate how a continuous-flow output can be achieved using three resonators.
FIG. 5 is a center-cut view of a 30-resonator embodiment of the present invention, further described in Example 2.
FIG. 6 shows results from testing of the embodiment of the present invention shown in FIG. 5 , demonstrating a 40:1 concentration in the 1 to 2 micron size range.
FIG. 7 shows results from testing of the embodiment of the present invention shown in FIG. 5 , demonstrating adjustment of the concentration ratio based upon sound decibels.
FIG. 8 shows results from testing of the embodiment of the present invention shown in FIG. 5 , demonstrating an increase in particle concentration by increasing the amount of time that the sound field is activated before releasing a surge of concentrated particulate.
FIG. 9A shows a theoretical increase in aerosol concentration at the acoustic node by means of the system of the parent invention, based upon frequency of the sound applied to the acoustic resonator, and the size of the particles.
FIG. 9B shows adjustment to the concentration ratios based upon mean particle diameters.
FIG. 9C shows concentration ratios changing with the rate of extraction flow.
FIG. 10 depicts another embodiment of the system of the present invention.
FIG. 11 depicts another embodiment of the system of the present invention, including multiple resonators.
FIG. 12 depicts another embodiment of the resonator of the system of the present invention.
FIG. 13 shows the inner brass tube of the valving system for the embodiment of the present invention as shown in FIG. 11 .
DETAILED DESCRIPTION
The present invention relates to novel methods and systems for capturing aerosols or particulates entrained in gaseous or liquid fluids using a high-amplitude sound field in a structure-filled resonator, to achieve particulate (including aerosol) concentration and deliver a concentrated sample or stream of the particulate.
System—
As shown in FIGS. 2, 5, 11 and 12 , the acoustic concentrator system of the present invention includes one or more structure-filled acoustic resonators 1 and means 2 for applying and removing a sound field within the resonators. The sound pressure level and the frequency of the applied sound field are selected to trap a desired particulate or aerosol within the resonator; by removing or altering the sound field, trapped particulate can be released from the structure and expelled from the resonator. Further, the system includes means 3 for drawing into the resonator an air or liquid sample from the environment, means 4 for expelling air or liquid from the resonator. In some embodiments, the expulsion means 4 includes at least two additional output ports, one 14 A for expelling excess fluid from the resonator, and a second 14 B for periodically or continuously releasing or gathering from the resonator a concentrated stream of the particulate. In these embodiments the expulsion means 4 may further include a single fan or similar conveyance mechanism, or a plurality of conveyance mechanisms, one associated with each expulsion port.
As shown in FIG. 12 , the acoustic resonator 1 of the system of the present invention may have a housing 11 to define a chamber or cavity 12 generally cylindrical in shape, or have any other three-dimensional shape, such as parallelepiped to form the body of an acoustic resonator. In some embodiments the cylindrical cavity 12 may have a diameter of from about 1/10″ up to about 24″; more typically ¼″ up to 2″, in some embodiments the cavity has a diameter of from about ¼″ to about 1″; in some embodiments the diameter is ⅝″. The resonator cavity may have a length of from about ¼″ to about 24″; in some embodiments this length may be between ¼″ and 2″; in other embodiments this length may be between 2″ and 12″. The length of the housing 11 may be adjusted so that the cavity resonance matches the natural frequency of the sound source, thereby achieving maximum efficiency and a resulting high sound pressure level. For example, in a simple one-dimensional resonator, resonance occurs at chamber lengths given by Length=½×N×(frequency of applied sound)/(speed of sound) where N=1, 2, 3, . . . . The resonator housing 11 may be constructed or molded out of any material, organic or inorganic, including metal, plastic, stone, and wood.
As shown in FIGS. 11 and 12 , the acoustic resonator housing 11 includes an inlet port 13 and an outlet port 14 A for air to pass through the device. Preferably the inlet port 13 and the outlet port 14 A are positioned on or near opposing ends of the housing 11 , so that the air passes from the inlet port through a large percentage of the structure-filled resonator before exiting the resonator at the outlet port. In some embodiments (as shown in FIGS. 2 and 12 ) the inlet port 13 is an aperture at, or tube extending from, the top of the housing 11 , and the outlet port 14 or 14 A is an aperture at, or tube extending from, the bottom of the housing. Fluid is drawn through the inlet port 13 and the outlet port 14 by a fan 4 A or other conveyance means.
As shown in FIGS. 2, 5, 11 and 12 , the acoustic concentrator system of the present invention includes one or more structure-filled acoustic resonators 1 and means 2 for applying and removing a sound field within the resonators. The sound pressure level and the frequency of the applied sound field are selected to trap a desired particulate or aerosol within the resonator; by removing or altering the sound field, trapped particulate can be released from the structure and expelled from the resonator. Further, the system includes means 4 A or 5 for drawing into the resonator an air or liquid sample from the environment and for expelling air or liquid from the resonator. In some embodiments, the expulsion means 4 A or 5 includes at least two additional output ports, one 14 A for expelling excess fluid from the resonator, and a second 14 B for periodically or continuously releasing or gathering from the resonator a concentrated stream of the particulate. In these embodiments the expulsion means 4 A or 5 may further include a single fan or similar conveyance mechanism, or a plurality of conveyance mechanisms, one associated with each expulsion port.
The inlet 13 and outlet port apertures or tubes 14 , 14 A or 14 B may be about ⅛″ diameter for the case of a ⅝″ resonator, but they may vary in diameter depending on the size of the resonator cylinder. The diameter of the outlet should be small in order to effectively contain the sound field and maintain efficient resonance.
By introducing a structured material 15 inside of the acoustic resonator 1 , the density of acoustic storage locations (nodes and anti-nodes) for particulate matter is greatly increased near the surface of the structure due to the creation of a complex sound field that is rich in nodal structure. This effect is numerically simulated in FIG. 1 , a cut view of a representative resonator cavity, with a standing wave field established through the application of sound from a sound source at one end, wherein the addition of a structured material serves to superimpose additional velocity nodes onto the bulk sound field. Notably, in this figure nodes appear along the length of the cylinder—at the top and about one-third up from the bottom, and smaller-sized nodes are near the surface of every structure. With this increased density of storage locations, the resonator of the present invention dramatically increases the quantity of particles that may be temporarily stored in the structure network while the sound field is activated.
The particle storage and concentration capacity of the present invention can be observed whether the resonator chamber 12 is partially or entirely filled with structured material 15 . The structured material need only be porous in nature with interconnected pore spaces. Examples include, but are not limited to, fibers, metallic fibers (including but not limited to aluminum fiber), meshes, open cell foams, nylon fibers and granular media. FIG. 1A shows structured materials suitable for use in the present invention, wherein M1 and M2 are nylon fiber mesh as is commonly used in household dishpan scrub pads, M3 is a loose fiber material as is commonly used in cushions or pillows, M4-M7 are various foams commonly used for padding in packaging items for shipping, and M8 is an aluminum mesh. While the bulk porosity of the materials affects what particle diameters can efficiently flow through without significant impaction losses, materials with porosities ranging from 5% to 99% can be utilized for particle concentration in the systems and methods of the present invention, and your inventors have found that the effect is insensitive to structured material diameter. However, the material needs to be stiff enough to hold shape during application of the sound field.
The placement of structured material in the resonator chamber adds complexity to the sound field. For example, in the case of a cylindrical chamber, the simple linear series of nodes and antinodes along the cylindrical axis of the chamber is superimposed by a complex node structure in the shape of the structured material itself. Every part of the structure acts as an acoustic velocity node, and therefore, as a place where particles can be levitated and stored while the sound field is active. See FIG. 1 , wherein discrete structures are put into a velocity antinode region (green) and the result is the addition of many small velocity nodes (blue regions above and below the structures).
Air flow through the resonator 1 may be adjusted, depending on whether the resonator is capturing or releasing particulate. The flow may be more significant if the resonator is capturing the particulate (with sound field applied), and pass over the filter at a slower rate if the particulate is being released (without sound field). Thus, as shown in FIGS. 5 and 12 , the major air flow A may be drawn through the resonator 1 by a fan or pump 4 A, while the minor air flow B (of concentrated sample) may be pulled by an external device that is receiving the concentrated flow (and sampling the same, as herein described) at that device's own rate(s). Alternatively, a separate external fan may be used to draw the minor flow. In systems having multiple resonators, one fan may be used to draw the major flow A through all resonators. The major flow may be from about 0.001 liters per minute (LPM) to 100,000 LPM; in some embodiments the major flow is between 1 and 60 LPM; in certain embodiments it is 8 LPM. The minor flow B may range from 0.001% to 50% of the major flow; in some embodiments the minor flow of concentrated aerosol is 0.5 LPM. Because the major flow is not itself dislodging the particulate from the fluid, the present invention has reduced overall power consumption over the prior art.
As shown in FIGS. 2 and 12 , the top and/or bottom of the resonator housing 11 includes means to accommodate or affix one or more sound sources 2 for applying and removing a sound field within the structure-filled acoustic resonators 1 . Such accommodation means may include apertures and o-rings, sized and shaped to accommodate the sound source; alternatively the sound source may be removably or permanently affixed to the interior of the housing 11 . The sound pressure level and the frequency of the applied sound field are selected to trap a desired particulate or aerosol within the resonator; by removing or altering the sound field, trapped particulate can be released from the structured material and expelled from the resonator
Any commercial off-the-shelf (COTS) piezoelectric ultrasonic sound sources may be used as the sound source 2 of the present invention, including those commonly used in motor vehicle “back-up sensors”. Other sound sources may be used including, for example, electrodynamic sound sources such as loud speakers or compression drivers. In some embodiments, as shown in FIGS. 2 and 11 , the ultrasonic sound source 2 is inserted into the bottom of the resonator housing 1 , which is sized to receive the sound source either with or without an o-ring or similar sealing structure. The top of the ultrasonic sound source 2 may then act as the bottom of the resonator 1 . The peak sound pressure level inside the resonator is about 150 dB re 20 microPascals. However, the effect works over a range of about 120 dB up to 190 dB peak sound pressure level.
When the sound field within the structure-filled acoustic resonator 1 , produced by the sound source 2 , is activated and air is passed through the resonator, the resonator functions as a ‘virtual filter’, whereby particulate may be temporarily accumulated therein. When the sound field is deactivated, nearly all particulate is released from its acoustic confinement, and with the fluid that continues to pass through the resonator (typically at a lower LPM), exits the resonator at the outlet port 14 or 14 B as a concentrated surge of particulate. The sound field may be controlled by a switch 2 A or other electronic or mechanical means.
With a single resonator system, the system expels either particulate-free fluid or particulate-concentrated fluid, depending on whether the sound field is activated or deactivated. In some embodiments of the present invention the sound field and air flow through the resonator 1 are controlled mechanically by means of a rotating outlet 5 . As shown in FIG. 12 , the mechanical control may further direct the air flow when the sound field is activated to the environment through a first port 14 A, and direct the air-flow to the second outlet port 14 B when the sound field is deactivated.
As evidenced in FIG. 4 , in some embodiments of the present invention a continuous stream of concentrated particulate may be produced when multiple acoustic resonators 1 are operated in sequence by mechanical control mechanisms, such that the system cycles the functionality of its resonators (collecting or releasing particulate) in sequence to achieve a near-continuous concentrated particulate stream at the outlet. For example, the multiple resonators may be cycled similar to the functioning of a multi-cylinder internal combustion engine in which valves open and close sequentially as controlled by a cam shaft. In multiple-resonator embodiments, the resonators may be provided in parallel structure, or about a circumference as shown in FIG. 5 . As shown in FIG. 4 , three transient concentration surges may be produced sequentially to produce average (upper dotted line) and minimum (lower dashed line) concentration ratios of 8-to-1 and 5-to-1 respectively. An embodiment of a thirty resonator system is shown in FIG. 5 ; FIG. 11 shows an embodiment of a six resonator system.
The thirty-resonator embodiment shown in FIG. 5 provides a system wherein twenty-eight of the resonators are activated and air is pulled through those resonators by a common fan that expels air to the environment (flow path A); an extraction nozzle 4 C rotates about the central axis in order to extract the concentrated aerosol from the remaining pair of resonators, and deliver it to an outlet 14 B at the bottom-center to provide a near-continuous concentrated sample. In this embodiment, the rotating extraction arm 4 C also depresses a switch 2 A that deactivates the sound field in the remaining pair of resonators. Once the extraction arm has passed the resonators and proceeds on to the next two resonators in the sequence, the switch 2 A is no longer depressed and the sound field is once again activated in the first pair of resonators until the arm completes another rotation.
In a similar six-resonator embodiment shown in FIGS. 11 and 13 , a rotating valving mechanism 4D is provided to sequentially capture exhaust from each of the six resonators. In this embodiment, the valving mechanism may include a rotating arm 4 C (as depicted in FIG. 5 ) or may be designed and configured as a brass tube, as shown in FIG. 13 . As shown in FIGS. 5 and 11 , the valving mechanism passes in front of the resonator outlets sequentially; when the arm or tube is in front of an outlet, the individual resonator's sound field is deactivated and the concentrated aerosol is sucked out through the hollow arm or tube 14 B. The rotation of the valving mechanism 4D may be controlled by an electric motor 6 .
The concentration factor can be adjusted by process control parameters including inlet flow rate, outlet flow rate, sound pressure level, sound activation time, frequency of sound, particle size, and other parameters. For example, as shown in FIG. 9A , theoretical modeling calculations reveal that the use of a lower frequency (e.g., 4 kHz) tends to concentrate larger particles more readily, and the use of a higher frequency (e.g., 32 kHz) tends to successfully concentrate smaller particles. FIG. 9B shows experimental data revealing similar trends, with the data generated by testing at 24 kHz, with a smaller particle size (0.6 microns) at peak concentration than the theoretical modeling (estimated at about 1.5 microns at peak concentration), demonstrating in part that the system of the present invention is more effective than the prior art at trapping, and delivering in a concentrated stream, smaller sized particles. As shown in FIG. 9C , the concentration ratio decreases with increasing extraction flow rate (minor flow rate). The testing in FIG. 9C was conducted after 1.25 LPM major flow, with a 60-second major flow time period. Sound pressure of the system of the present invention can be modified by changing the drive voltage to the ultrasonic transducers or other sound sources, which lowers or raises the sound pressure level from the sound source in the resonator.
The concentrated particulate flow from systems and methods of the present invention may be used in many applications such as material processing, aerosol sensing and detection, and similar and other methods of testing or using concentrated particulate fluids. A particularly beneficial application is attaching the system of the present invention, at the output port 14 , to the inlet of aerosol detectors such as chemical-biological agent detectors, in order to increase the sensitivity of these devices and improve their ability to detect particulate of interest. For example, output port 14 of the acoustic concentrator of the present invention may be attached on the inlet port of a fluorescence aerosol detector 140 in order to increase the received fluorescence signal, as shown in FIG. 10 . Suitable fluorescence aerosol detectors include the Tactical Biological Detector (TACBIO), the Rapid Agent Aerosol Detector (RAAD), and the Bio-Agent Sensor and Trigger (BAST).
Furthermore, the system of the present invention may be used in liquid applications, to remove and concentrate particles entrained in the liquid. For example, the system may be used to detect minute amounts of contaminants in drinking water to assure purity or attempt to detect intentional or accidental contamination of a water supply. Likewise, the system may be used to remove and concentrate cells (e.g., cancer cells) or other particulates from blood. Notably, the fibrous material must be denser and stiffer than the liquid.
The method of the present invention to concentrate particulate within an air sample using an aerosol/particulate concentrator device such as the device hereinabove described, includes drawing in a fluid sample into a structure-filled acoustic resonator and applying a sound field within the structure-filled resonator. The sound pressure level and frequency of the applied sound field are selected to trap a desired particulate or aerosol, as hereinabove described for the system of the present invention. The method also includes expelling fluid from the resonator. When the sound field is deactivated from the resonator, the method continues with releasing the trapped sample of particulate/aerosol in a concentrated fluid stream; activation and deactivation of the sound field may be electronically or mechanically controlled.
The method of the present invention may further include the use of additional structure-filled acoustic resonators, wherein the process is cycled through each resonator in a sequence to achieve a near continuous-flow of concentrated aerosol or particulate. Furthermore, the fluid released may be sampled for the concentrated particulate by means of a sensor selected from the group consisting of: chemical, biological, radionuclide, and explosives sensors.
As hereinabove described, adjustments to the sound pressure level may achieve varying levels of concentration of particulate, and adjustment of the frequency of the sound filed may achieve preferential concentration of different sizes or types of particulate/aerosols. In some embodiments, the applied frequency of the sound field is above 16 kHz, and the peak sound pressure level of the sound field in the resonator is above 140 dB.
Applications of the inventions as hereinabove described are demonstrated in the following examples:
Example #1
A single-resonator ultrasonic concentrator was fabricated and tested. The device included a cylindrical resonator cavity with an ultrasonic transducer, and having inlet and outlet ports, as shown in FIG. 2 . Tests were conducted with a 3.1 micron test particle entrained in air, where air was drawn through the resonator for 90 seconds with the sound field activated, and then the sound field was deactivated and air continued to flow at 0.25 LPM. As shown in FIG. 3 , t 92 seconds, the stored aerosol was released in a surge producing a 34-to-1 aerosol concentration, and at about 95 seconds the output returned to the ambient 1-to-1 concentration (no concentration).
Example #2
Data from the 30-resonator concentrator hereinabove described, and depicted in FIG. 5 , is shown in FIG. 6 , showing a concentration of 1 to 2 micron aerosols (the blue line) at a ratio of about 40-to-1. Smaller and larger particles are concentrated slightly less as shown by the red and black lines, respectively. Alteration of the applied frequency of sound, resonator geometry, and structured materials can be made to achieve a preferential concentration of a desired particle size. As shown in FIG. 7 , the concentration ratio may be increased or decreased by adjusting the dive voltage applied to the ultrasonic transducer, and therefore the sound pressure level. As shown in FIG. 8 , the particulate storage time may be adjusted to increase or decrease the level of concentration. | A process is disclosed for using multiple acoustic resonators to sample fluids (gas or liquids), capture particulate (or aerosols) entrained in the fluid, and deliver a concentrated sample of particulate. The acoustic concentrator demonstrates many improvements over prior art that includes improved concentration of particulate below 3 micron, adjustability of the level of concentration, ability to function over a wide range of humidity and temperature, and reduced overall power consumption. For example, when installed on the inlet of an aerosol detection system, the acoustic concentrator has been shown to increase sensitivity that may lead to earlier detection of bioaerosol agents. | 6 |
This is a division of application Ser. No. 699,289, filed June 24, 1976, now U.S. Pat. No. 4,099,359.
BACKGROUND OF THE INVENTION
Large load-supporting structural surfaces, either vertical, horizontal or a combination of both, are in universal and widespread use. These structures must support their own weight and, normally, very large loads such as layers of ground and soil of as much as 30 to 40 or more feet high, heavy payloads such as bridge traffic and the like. Since these structures are necessarily large, that is since they have long, essentially unsupprted spans of as much as 50 to 100 feet in length and more they are subjected to very large forces and deflections which could in the past only be handled with elaborate fabricated support beams and trusses, with massive reinforced concrete walls and beams, or with a combination of both.
Fabricated steel structures, though not excessively heavy, are expensive because they use a relatively large amount of expensive material, e.g., high quality steel which must be tediously fabricated, assembled and installed from a multiplicity of different, individually fabricated members such as I-beams, angle irons, plates and the like welded, riveted or bolted together. Furthermore, to obtain the necessary strength such structures required a great depth, often of many feet, which might not be available, or which is only available at significant costs, e.g., by performing expensive excavation and the like.
As an alternative to such fabricated metal structures, reinforced concrete has found increasing acceptance. Frequently the concrete structures are aesthetically more appealing and they are often less expensive. Nevertheless, they require the erection of complicated forms and the installation of the necessary reinforcing steel bars all of which requires individual, on-the-site fabrication, assembly and installation by skilled and, therefore, costly craftsmen.
After the necessary large volume of concrete has been poured into the forms and the forms have been dismantled the concrete structures are again quite expensive. Moreover, they too have to be massive to support a given load.
To overcome some of these shortcomings and to reduce construction costs, it has in the past been suggested to employ prefabricated plate, normally steel plate elements. Since plate as such is weak, that is since it cannot withstand large forces acting perpendicular to the plate, it has also been suggested to employ corrugated plate structures. Examples of such constructions are disclosed, for example, in U.S. Pat. Nos. 2,126,091; 2,536,759; 3,508,406; and 3,638,434.
The referenced patents disclose tunnel-like, load-supporting structures made of corrugated plate, that is relatively short sections of corrugated plate normally having corrugations with a pitch of up to six inches, a corrugation depth up to two inches, and a wall thickness of up to 3/8 inch. For the contemplated large structures, which have a width (perpendicular to the tunnel defined by the structure) of up to 60 feet and more, it is necessary to include stiffening members which rigidify the structure both for load-bearing purposes and for maintaining the structure in the desired, e.g., normally arched shape during the backfilling and compacting process. Even then such structures exhibit relatively little load, e.g., ground supporting capacity unless the structure is reinforced with suitable stiffeners and the like. As a consequence, these structures, though relatively less expensive because they could be assembled from uniform, prefabricated modules, i.e. like, prefabricated and, where applicable, curved corrugated plate elements, their relatively low strength limited their application to relatively short span lengths and relatively small loads. For example, typical highway overpasses which have to accommodate a ground fill height of 10 to 30 and more feet as well as a large payload such as a standard California State Highway surcharge of H20 (for standard freeway traffic) must be built as before from fabricated steel and/or reinforced concrete both of which renders such structures relatively expensive.
In other instances in which relatively long, load-bearing spans are required, such as in large bulk material, e.g., gravel storage bins, bin type retaining walls were suspended between upright posts and constructed of multiple, prefabricated, U-shaped members made from steel plate of the appropriate thickness which was press-formed to the desired shape. By providing the resulting U-shaped channel members with the appropriate depth the required strength could be obtained. The inherent shortcoming of this approach is that the maximum span length is limited by the effective length of the longest available press. Moreover, such fabrication method is tedious, each channel member must be separately fabricated and thereafter the channel members must be assembled, usually bolted together in a side-by-side relationship to form a wall of the desired height. The resulting structure, though having adequate strength but not necessarily an adequate length, was relatively expensive.
Thus, the prior art applicable to structures here under consideration, that is structures having relatively large load-bearing surfaces that are unsupported between ends of the surfaces such as are found in bridge, tunnel or retaining wall constructions, can be summarized as relying on fabricated steel or reinforced concrete or a combination of both to attain the necessary strength and stiffness. Both of these approaches require a great deal of hand labor and material, and therefore, time to assemble and install, all of which renders them relatively expensive. It has been recognized that prefabricated, modular metal plates are relatively less expensive to produce, assemble and install, however, these plates exhibited severe strength limitations and could only be used for relatively small structures unless suitable stiffeners and supports were provided and unless the structure under consideration had the necessary shape to not only be self-supporting but to also support a payload. This latter aspect required that the structures be tubular and continuously arcuate as distinguished from U-shaped, or tubular with straight walls or the like even if the latter shape is more desirable for the structure under consideration.
SUMMARY OF THE INVENTION
The present invention seeks to overcome the above-discussed shortcomings of the prior art by providing as a structural building element a prefabricated, corrugated plate capable of supporting large loads without requiring stiffeners, support beams and the like as was necessary in the past.
Generally speaking, a corrugated, high strength structural steel plate constructed in accordance with the present invention comprises a plurality of parallel, longitudinally extending, generally sinusoidally shaped corrugations defined by alternating convex and concave peaks and troughs. The spacing between adjacent peaks and troughs in a direction perpendicular to the plate, or the depth of the corrugations, is at least about four inches. The spacing between adjacent peaks and adjacent troughs in a direction parallel to the plate, or the pitch of the plate, is at least about 12 inches. Furthermore, the peaks and troughs preferably have a curvature radius of at least about two inches.
This plate can be fabricated from flat metal stock supplied, depending on the thickness of the stock, either in coils or in relatively long, flat sections, normally of a length well in excess of about 12 feet, the longest prior art corrugated steel plate lengths that could be made by pressbraking sheet stock into a corrugated plate. Thus, the plate of the present invention can be fabricated in length of as much as 30 feet or more, depending on the ultimate use of the plate. Depending on the desired strength and rigidity of the corrugated plate the plate can be constructed from stock of any thickness. For applications such as for the construction of highway overpasses, bridges, tunnels and the like the plate can have a thickness of 3/8 to 1/2 inch and more.
In accordance with this invention, such plate is constructed by passing it through a plate corrugator such as is described and claimed, for example, in the inventor's U.S. Pat. No. 3,940,965 the disclosure of which is incorporated herein by reference. Since the plate is essentially continuously rolled in the corrugator described in the referenced patent the ultimate corrugated plate length can be chosen to suit a particular application and is not arbitrarily limited by the maximum length of available press-braking equipment.
Moreover, the rolling of the plate can be performed much more rapidly, all corrugations in a given plate being formed in a single pass of the sheet through the corrugator. In contrast thereto, heavy walled, e.g., up to 3/8 inch thick prior art corrugated plate having a corrugation pitch of up to six inches and corrugation depths of up to two inches required the individual forming of each corrugation in a press-brake. This process is time-consuming, costly and severely limits the size of the plate that can be fabricated in this manner. Consequently, corrugated plate, and particularly heavy walled corrugated plate having a corrugation pitch of 12 inches and more and a corrugation depth of four inches and more can be economically fabricated in accordance with the present invention by fabricating it in a corrugating mill of the type discussed in the above-referenced U.S. patent of the inventor.
In addition to the lower fabrication costs the fabrication of corrugated plate with the above set forth large corrugation pitch and depth enables the formation of relatively large peak and trough radii which allows one to coat and in particular to zinc coat the plate in its flat state and to corrugate it thereafter without cracking or otherwise damaging the zinc coating. This simplifies and economizes the coating process and therefore contributes to reducing the cost of the corrugated plate of the present invention.
The corrugated plate of the present invention not only simplifies the fabrication, assembly and installation of large load-bearing surfaces, it also has far superior strength and rigidity without requiring a correspondingly larger amount of material, e.g. sheet stock. For bending, the strength and rigidity of the plate is primarily determined by the corrugation depth. However, by simply increasing the corrugation depth substantially more material is required for a plate of a given size. Moreover, the manufacture of the plate becomes increasingly difficult, particularly for heavier wall thicknesses. The present invention increases the corrugation depth but also increases the pitch of the corrugation by a factor of about 2:1 or more over what was heretofore thought possible or advisable. As a result, the plate strength and rigidity is greatly increased over prior art plate, yet the plate of the present invention requires virtually no more material for a given plate size than prior art plate. In addition, the plate of the present invention can be given much larger curvature radii at its peaks and troughs which greatly facilitates its manufacture as discussed above.
Another aspect of the present invention comtemplates a variety of structures which employ the corrugated plate of the present invention. Such structures include vertical retaining walls or bridge abuttment walls; bridge decking, single or multiple box culverts; gravel or like storage bins; bin type retaining walls, excavation retaining walls; and the like.
The advantages of the present invention are best illustrated on hand of an example, a 12 foot by 12 foot box culvert constructed of the 12 by 4 inch corrugated plate of the present invention as contrasted with a like box culvert constructed of reinforced concrete.
Such a box culvert constructed of the corrugated plate of the present invention for supporting a two-foot backfill cover and a California State H20 highway surcharge weighs approximately 685 lbs. per linear foot and costs, installed, approximately $275.00 per foot. A prior art concrete box culvert of the same dimension and capable of supporting the same load requires approximately three cubic yards of concrete and costs approximately $597.00 per linear foot completely installed, forms removed and concrete finished. Thus, the concrete box culvert is more than twice as expensive than the same culvert constructed in accordance with the present invention. Similarly, a 12×12 box culvert capable of withstanding a 20 foot backfill cover and a California State H20 highway surcharge constructed with the corrugated plate of the present invention weighs approximately 1890 lbs. per linear foot and costs approximately $756.00 per linear foot. The same culvert constructed of reinforced concrete requires approximately 51/3 cubic yards of concrete per linear foot and costs approximately $1,066.00 per foot, or almost 50% more than the corrugated plate box culvert constructed in accordance with the invention. Similar cost savings can be achieved by employing the corrugated plate of the present invention for box culverts of different sizes as well as for other load-supporting structures as are more fully described hereinafter.
To illustrate the great strength and rigidity of the corrugated plate of the present invention, it is noteworthy that a 12 foot span (such as in a 12 foot box culvert) can carry a 40-foot backfill cover and a California State H20 highway surcharge. A reinforced concrete slab or a span of equivalent strength requires a vertical wall thickness for the abuttment of 12 inches and a (horizontal) slab thickness of about 18 inches.
The versatility of the present invention is not limited to the type of structure in which the corrugated plate can be used. The corrugated plate itself can be strengthened almost at will by securing aligned, respective peaks and troughs of the plate to each other with bolts, rivets and the like. The strength and rigidity can be further increased by providing spacers between the aligned peaks and troughs through which the securing means, e.g. the bolts extend. The interior spaces between the plates can further be filled with concrete with or without reinforcing bars so that the corrugated plates both form a structural member and a permanent exterior, load-bearing mold for concrete poured between the plates.
To illustrate the superior strength and rigidity of plate and plate structures made from the corrugated plate of the present invention, it is noteworthy that a reinforced concrete slab must have a thickness of nine inches and No. 7 reinforcing bars on six inch centers spaced seven inches from the top of the concrete bar to withstand the same bending moment as the plate of the present invention having a 1/2 inch wall thickness. Similarly, for two corrugated steel plates of the present invention bolted together peak-to-trough a concrete slab of equivalent bending strength requires a thickness of 15 inches, and No. 9 reinforcing bars on 51/2 inch centers spaced 13 inches from the top of the slab. The comparison is even more dramatic when considering two corrugated plates constructed in accordance with the invention in which aligned peaks and troughs of the respective plates are spaced-apart by six inch spacers. A concrete slab of equivalent bending strength requires a thickness of 23 inches and No. 11 reinforcing bars on 51/2 inch centers spaced 21 inches from the top surface of the slab.
Another notable advantage of the present invention relates to the installation of large diameter pipe for thoroughfares, tunnels or the like. In the past, such pipe was constructed of corrugated sheet having a corrugation depth and pitch of up to two by six inches and wall thicknesses of up to 3/8 inch. The weight and size of the pipe limited the maximum pipe diameter to about 26 feet beyond which assembly becomes unmanageable because of excessive plate flexibility and a resulting sagging and deformation of the pipe. To counteract such sagging and deformation the prior art suggested to employ pipe stiffeners as is set forth, for example, in U.S. Pat. No. 3,508,406. By constructing the pipe of the corrugated plate of the present invention, pipe diameters of as much as 75 feet can be assembled and installed without experiencing unmanageable pipe deflection and without requiring pipe supporting stiffeners. This is accomplished without any significant increase in the linear weight of the pipe because the linear weight of the corrugated plate of the present invention is substantially the same as the linear weight of prior art corrugated plate of the same wall thickness.
In sum and substance, therefore, the present invention provides as a new building element corrugated plate of the above stated configuration which exhibits superior strength characteristics as compared to any corrugated plate heretofore known or suggested. Moreover, this plate is more economically fabricated than prior art corrugated plate of much lesser strength by combining superior fabrication methods with a plate configuration which increases the plate strength without correspondingly increasing the material consumption, that is, the amount of material required for fabricating a plate of a given size.
Furthermore, the corrugated plate of the present invention enables the construction of a large variety of load-bearing, large surface area structures from relatively low cost, modular plate sections which are readily and relatively inexpensively assembled, e.g. bolted together and installed. Of equal importance, the present invention contemplates the assembly of two or more plates into structures of vastly increased strength and rigidity to satisfy virtually any application. Thus, the present invention is a most significant cost saving contribution to the construction industry.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary, cross-sectional view through a corrugated plate constructed in accordance with the present invention;
FIG. 2 is a perspective side elevational view of a large, load-bearing and buttressed support arch constructed in accordance with the present invention;
FIG. 3 is a perspective, elevational view of a head or retaining wall constructed with corrugated plate in accordance with the present invention;
FIGS. 3A and 3B are fragmentary, side elevational, perspective views showing in greater detail the anchoring of the head or retaining wall illustrated in FIG. 3;
FIG. 4 is an elevational, perspective view of a bridge abuttment constructed in accordance with the present invention;
FIG. 5 is a schematic, perspective front elevational view of a multiple box culvert constructed with corrugated plate in accordance with the present invention;
FIGS. 5A-5B are schematic details of the construction of the box culvert illustrated in FIG. 5;
FIG. 5C is a schematic, perspective front elevational view of a prior art concrete box culvert;
FIG. 6 is a front elevational, perspective view of decking constructed of corrugated plate in accordance with the present invention;
FIGS. 7 and 8 are fragmentary, cross-sectional views of double-plate walls or decks constructed in accordance with the present invention;
FIGS. 9 and 10 are perspective, side elevational, sectional views of spacers employed in the double-wall construction illustrated in FIG. 8;
FIG. 11 is a fragmentary, side elevational view of bin type retaining wall for bulk materials constructed with corrugated plate in accordance with the present invention;
FIG. 12 is a perspective, front elevational view of a corner connector constructed in accordance with the present invention and employed in the bin illustrated in FIG. 11;
FIG. 13 is a perspective, side elevational view of a retaining wall constructed with corrugated plate in accordance with the present invention;
FIG. 14 is a perspective front elevational view of a column constructed in accordance with the present invention for use in connection with the retaining wall illustrated in FIG. 13; and
FIG. 15 is a schematic plan view of a corrugator employed for the fabrication of corrugated plate in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIG. 1, a corrugated plate 2 constructed in accordance with the present invention has a plurality of generally sinusoidal, parallel, longitudinally extending corrugations 4 which defines alternating convex peaks 6 and concave troughs 8. The corrugations have a pitch, that is adjacent peaks and adjacent troughs have a spacing (parallel to the sheet) of at least about twelve inches and the corrugations have a depth, that is a peak and an adjacent trough have a spacing (transverse to the sheet) of at least about four inches. The concave and convex peaks and troughs have a curvature radius R of at least about two inches and preferably of about two and one-quarter inches. The thickness of the plate may vary according to the ultimate use to which the plate is put and the strength required for such use. For most applications a plate thickness of no more than one-half inch suffices.
Referring now briefly to FIG. 15, a corrugator 10 for forming a flat sheet metal stock 12 into a corrugated plate 2 comprises a sheet metal supply 14 and a plurality of serially arranged corrugating roller pairs 16 which consecutively form corrugations in the sheet from the center towards the lateral sides of the sheet. The rollers are mounted to a frame 18, which may be vertically adjustable, and they are driven by a suitable power drive (not shown in the drawings). The corrugating rollers have nesting annular corrugation rings 20 which deform the flat sheet stock into the corrugated plate illustrated in FIG. 1.
As briefly discussed above, the sheet stock may be supplied in discrete lengths or, normally for sheet stock of lesser thickness, in large coils which are continuously fed through the corrugator. Downstream of the corrugator the corrugated plate may be served into pieces of lesser length if desired.
When the plate is to be coated, and particularly when it is to be zinc coated or galvanized, for example, with a three ounce coating (1.5 oz. of zinc per square foot for each side of the plate) the coating can be performed at coating bath 22 before the plate is corrugated. This is possible because of the large curvature radius R of the convex peaks and convex troughs 6, 8 respectively, of the corrugated plate. This large curvature radius subjects the zinc coating to only minor stretching and compressing while the sheet is deformed in corrugator 10 and the coating can normally withstand it without cracking or peeling although it could not withstand the more severe stretching and compressing to which it would be subjected in the manufacture of conventional corrugated plate having a much smaller curvature radius of one inch or less. By galvanizing the plate in its flat state the handling of the plate is simplified and the galvanizing bath can be maintained smaller, both of which reduces the manufacturing costs and, therefore, the overall costs of the finished corrugated plate.
Turning now to a more detailed description of the manner in which the corrugated plate 2 of the present invention can be used, and referring first to FIGS. 7-10, to increase the strength and rididity of the plate, two plates 2 can be secured to each other to form a double plate 24 by aligning respective peaks and troughs 6, 8 and intermittently securing the aligned peaks and troughs to each other with bolts 26, rivets or welds (not shown). Interior spaces 28 can be filled with concrete 30 and for that purpose the upper corrugated plate may be provided with a plurality of spaced-apart concrete filling holes 32 through which the fresh concrete can be introduced into the interior spaces. The concrete may be reinforced with conventional reinforcing steel bars 34 and 36 which may be oriented parallel or transversely, respectively, to the corrugations of the plate. For transverse steel bars suitable apertures are formed in the corrugations of the plates which is traversed by the bar; in FIG. 7 the lower plate.
To further increase the strength and rigidity of a double plate two corrugated plates 2 may be combined into a double plate 38 by placing tubular spacers 40 between aligned peaks and troughs 6, 8, respectively of the two plates and bypassing connecting bolts 42 or rivets (not shown) through the spacers to thereby secure the two plates to each other in a spaced-apart relationship. The length of the spacers is chosen to suit the particular application. As before, the hollow interior spaces between the plates may be filled with concrete with or without reinforcing bars (not illustrated in FIG. 8).
The spacers may comprise simple metallic tubes 44 (FIG. 9) which, preferably, include contoured ends 46 to snugly engage the two corrugated plates between which the spacers are disposed. Alternatively, the spacer may comprise a tubular concrete member 48 (FIG. 10) which also has contoured ends 50. The concrete spacer may further be fitted with an insert 52 that has female threads for engaging and securing a pair of bolts threaded into the insert from opposing ends of the spacer to thereby secure the corrugated plates 2 to the spacer and to each other.
Referring now to FIG. 2 corrugated plates constructed in accordance with the invention may be assembled into a tubular or tunnel-like structure such as an arch 54 defined by upright sides 56 and a curved span 58 interconnecting upper ends of the sides. The sides and the span are constructed of one or more corrugated sheet sections which are conventionally connected end to end with bolts, rivets, by welding them together, or the like depending on the overall size and configuration of the arch. It should be noted that the arch as defined by the upright sides and the span extends over 180° and does not require the undercut configuration of many large prior art plate structures. The lower end of the sides may be directly anchored into the ground, it may be secured to suitable foundation slabs (not shown in FIG. 2) or they may be secured to a ground or anchoring plate 60. The anchoring plate may interconnect the lower ends of the sides, it may project past the sides and suitable reinforcing buttresses 62 may further be provided to steady the arch on and to securely tie it to the anchoring plate.
Referring now to FIG. 3 in another application the corrugated plate 2 of the present invention may be employed as a head or abuttment wall 64 having a general upright, e.g., vertical orientation. The lower end of the abuttment wall is attached to a footing 66 which may comprise a concrete slab 68 or corrugated anchoring plates 70 such as are illustrated in FIGS. 3A and 3B. Tie rods 72 may be provided to secure the abuttment wall to the footing and to strengthen the connection between the lower end of the wall and the footing.
Referring now specifically to FIGS. 3A and 3B, the lower end of the abuttment wall is secured to the corrugated anchoring plate 70 with an angle iron 74 that contacts protruding peaks of the wall and the anchoring plate, respectively, and that is secured thereto with bolts or rivets 76 or suitably applied welds. The tie rods illustrated in FIG. 3A may be replaced with perpendicular, corrugated plate webs 78 which are also secured to the abuttment wall 64 and the anchoring plate 70 with suitably oriented and attached angle irons 80, 82, respectively.
Referring now to FIGS. 3-4 and 6, the abuttment walls illustrated in FIG. 3 can be employed as a bridge abuttment 84 by positioning two abuttment walls opposite each other. The upper ends of the abuttment walls support a bridge decking 86 which may comprise flat corrugated plate decking 88 as illustrated in FIG. 6 which, depending on the distance between the abuttment walls, may be directly supported by the walls or by suitable steel girders 90 which in turn are carried by the upper ends of the abuttment walls. Placed on top of the corrugated plate decking are planks 92 or concrete which then form the flat roadway of the bridge.
Referring next to FIGS. 5-5C, FIG. 5C illustrates a multiple box culvert 94 cnstructed of reinforced concrete in accordance with the prior art and having vertical concrete walls 96 interconnected by a horizontally disposed reinforced concrete floor 98 and concrete top 100. FIG. 5 illustrates a multiple box culvert 102 constructed of corrugated plate 2 in accordance with the present invention. The box culvert is defined by upright sides 104 and a plurality of side interconnecting floor plates 106 and top plates 108, both of which are also constructed of the corrugated plate of the present invention.
FIGS. 5A and 5B illustrate alternate constructions of the box culvert 102. The box culvert illustrated in FIG. 5A has an arched top plate 110 secured to straight vertical side walls 112 directly (righthand side walls) or via a curved connecting plate 112 (lefthand side wall). The lower ends of vertical sides 104 are connected to the floor plate 106 via corner plates 114. A hollow space 116 formed by adjacent corner plates secured to interior sides 104 may be filled with concrete to add rigidity and mass to the box culvert.
FIG. 5B illustrates a box culvert section which has a flat top plate 118. In addition, the righthand portion of FIG. 5B illustrates a box culvert construction in which the vertical side 104 is secured to an upwardly opening channel anchored directly to the ground. In all other respects, the box culvert illustrated in FIG. 5B is identical to the one illustrated in FIG. 5A.
Referring to FIGS. 11 and 12, a storage bin 122 for bulk material such as a roadside gravel storage bin or bin type retaining wall comprises a plurality of rectangularly spaced-apart upright posts 124 carried by suitable anchoring or bearing plates 126 and mounting upright side walls 128 constructed of the corrugated plate of the present invention so that the plate corrugations 130 run horizontally between the upright posts. In this manner, the superior strength and rigidity as well as the large length and width of the corrugated plate of the present invention can be employed to greatly simplify the construction, assembly and installation of the bin type retaining wall as contrasted with prior art structures of this type constructed of U-shaped channels of a narrow width and assembled side by side to cover the full height of the bin type retaining wall.
The upright posts are preferably T-shaped members having a web 132 and a pair of legs 134 which protrude transversely from the web. At least the legs have an undulating configuration to define alternating peaks and troughs 136, 138 respectively, which have the same corrugation pitch and depth as the side walls 128 to form an improved post-to-side wall fit and to prevent relatively fluid bulk material (such as dry sand) from flowing from the bin through gaps that otherwise form between the corrugations of the side walls and the posts if the latter were constructed of flat T-shaped members. The webs may also be of an undulated construction, particularly for posts defining the outside corners of the bin.
Referring to FIGS. 13 and 14, a retaining wall 140 such as is commonly used in ground excavations to prevent bulk material like sand, ground, etc. from collapsing into the excavation comprises a plurality of uprights posts 142 and wall panels 144 spanning the distance between adjacent posts and having horizontally oriented corrugations 146, that is corrugations which are perpendicular to the posts. Depending on the type of material that is shored up by the retaining wall and the excavation depth, the panels may be flat (not shown in FIG. 13) such as the corrugated side walls illustrated in FIG. 11, or the wall panels may be arched with their concave sides 148 facing inwardly, that is facing towards the excavation 150. The posts may comprise conventional I-beams or, for applications in which the shored material is relatively fluid, fabricated, generally T-shaped members 152 having a web 154 and a pair of legs 156 which protrude transversely from the web. The angle of inclination of the legs from the web is the same as the angle of inclination of the ends of the wall panels 144. Furthermore, the legs are undulated to define alternating peaks and troughs 158, 160 which have a pitch and a depth that equals the pitch and the depth of the corrugated wall panels.
The posts are conventionally anchored, either by driving them to a sufficient depth into the ground or by providing suitably mounted anchor plates 162 and tie rods 164 connecting a portion of the post to the anchor plate. | Corrugated steel plate is formed from a flat plate stock and has a length of at least about 12 feet, a corrugation pitch of at least about 12 inches, and a corrugation depth of at least four inches. The plate has thicknesses of up to 1/2 inch and more. Also disclosed are structures such as tunnel-type, heavy load-supporting structures defined by upright and horizontal structure portions which extend over no more than about 180° while being capable of supporting up to 40 feet of ground fill and payload thereon. The corrugated plate can be used singly or as double, spaced-apart plate assemblies which are hollow or filled with concrete or a like material, including steel reinforcing bars for the concrete. The corrugated plate can also be formed into vertical, sectional retaining walls, bin type retaining walls, bridge abuttment walls, flat support surfaces such as bridge decking, open air structures, guard rails, sheet piling, etc. | 4 |
This application is a 371 of PCT/GB 99/03599 filed Oct. 29, 1999 now wo 00/26220.
The present invention relates to diphosphines, a process for their preparation, metal catalysts derived from them and the use of such catalysts.
There has been much interest in the asymmetric hydrogenation of alkenes in recent years using, in particular, rhodium catalysts derived from P-chiral diphosphines. There is a need to improve such processes so as to enhance the enantio-selectivity.
It is commonly believed that C 2 symmetric diphosphines along with diols and diamines are endowed with superior properties as ligands in catalysis and this is, of course, augmented by their ease of synthesis. According, to the present invention, we have surprisingly found that excellent results can be obtained by a novel class of unsymmetrical diphosphines.
Accordingly the present invention provides a non-symmetrical diphosphine of the formula
R 1 R 2 P—(Z)—PR 3 R 4
wherein Z represents a chain of 2 to 4 carbon atoms which may be substituted, which chain may be saturated or unsaturated, eg. ethylenically unsaturated, R 1 , R 2 , R 3 and R 4 , which may be the same or different, are aliphatic, aromatic or heteroaromatic groups attached to the phosphorus by carbon, nitrogen, oxygen or sulphur such that each phosphorus atom and its substituents independently form a single enantiomer. It will be appreciated that, in general, there is a single stereochemical configuration around each phosphorus atom. Thus one or both phosphorus atoms may form a chiral centre. Suitable substituents of Z are hydrogen or aliphatic, aromatic or heteroaromatic groups.
Preferably the diphosphines are 1,2-ethanes ie. the carbon chain is —(CH 2 ) 2 —. Other typical Z groups include those having the chain structure —C—C═C—C and —C—C═C—.
Generally, the substituents R 1 , R 2 , R 3 and R 4 will be connected to the phosphorus atoms by carbon atoms. In a preferred embodiment, R 1 and R 2 and/or R 3 and R 4 are linked together to form the substituted or unsubstituted 3,4,5,6 or 7 membered phosphorus heterocycle and preferably a phospholane ie. a five membered ring. This ring desirably has the formula
wherein R 5 and R 6 , which may be the same or different, are hydrogen, hydroxy or C 1 to C 4 alkoxy and R 9 and R 10 , which may be the same or different, are hydrogen or C 1 to C 4 alkyl.
It is also preferred that R 1 , R 2 , R 3 and/or R 4 are substituted or unsubstituted phenyl, the substituents preferably being hydroxy or C 1 to C 4 alkoxy groups.
The alkyl and alkoxy groups are typically methyl and methoxy, respectively.
It will be appreciated that although the diphosphines are non-symmetrical R 1 , R 2 , R 3 and R 4 may all be the same provided that the stereo orientation of R 1 and R 2 on the one hand, is different from that of R 3 and R 4 . The values of R 1 , R 2 , R 3 and R 4 must be such that each phosphorus atom and its substituents independently form a single enantiomer.
Preferred diphosphines of the present invention have the formula
wherein R 5 and R 6 , which may be the same or different, are hydrogen, hydroxy or C 1 to C 4 alkoxy.
In accordance with another aspect of the present invention these diphosphines can be obtained in optically pure form rather than as a mixture of isomers.
It is usually convenient if at least one of the phosphorus atoms is ligated to a borane. This enhances the storage stability of the phosphine. It will be appreciated that it is a simple matter to de-boronate when it is desired to generate the ligand. Catalysts can be obtained from the diphosphine with a, generally low valent, metal such as rhodium, iridium, ruthenium, palladium or platinum. The ligand can be reacted in known manner to generate the catalyst. For example a rhodium catalyst can be obtained by reaction of the ligand with (COD) 2 RhBF 4 . By “COD”, as used herein, is meant cyclooctadiene. The preparation of the catalysts from the ligand can be obtained in known manner as one of skill in the art will appreciate.
The catalysts of the present invention are generally neutral or cationic complexes. Typical counterions which can be present if they are cationic include halide, for example fluoride or chloride, tetrafluoroborate, hexafluorophosphonate, hexafluoroantimonate, or sulphonate of formula R 7 SO 3 where R 7 is an aliphatic or aromatic group, or boronate of the formula (R 8 ) 4 B wherein the R 8 groups which may be the same or different are aromatic groups. The aromatic groups are typically phenyl groups which are optionally substituted. When R 7 is aliphatic it is typically an alkyl group, for example of 1 to 4 carbon atoms such as methyl.
The non-symmetrical diphosphines of the present invention are generally prepared by a Michael-type addition reaction of a nucleophilic phosphorus-containing reactant with an unsaturated, preferably an ethylenically unsaturated, phosphorus-containing reactant or a cyclopropyl phosphorus-containing reactant.
The nucleophilic phosphorus-containing reactant may be any compound of the formula
R 11 R 12 PH
wherein R 11 and R 12 , which may be the same or different, are aliphatic, aromatic or heteroaromatic groups attached to the phosphorus bycarbon, nitrogen, oxygen or sulfur. The nucleophilic phosphorus-containing reactant may also be an organometallic derivative of the formula
R 11 R 12 PM
which may be ionic or covalent, and in which R 11 and R 12 are as defined above and M is a suitable metal.
Preferably the nucleophilic phosphorus-containing reactant is an enantiomerically pure phosphine and most preferably it is an enantiomerically pure phosphine borane such as ortho-anisylphenylphosphine borane.
A phosphorus atom with electron-withdrawing substituents, attached to a double bond results in the alkene being responsive to nucleophiles. The unsaturated phosphorus-containing reactants suitable for use in the present invention may be oxidised phosphorus-bonded alkenes, for example diethyl vinylphosphonate, which may later be reduced to provide a primary phosphine. The alkene is preferably ethene or 1,3-butadiene.
The diphosphines of the present invention are typically prepared via a diphosphine intermediate comprising a primary phosphine and tertiary phosphine.
The primary phosphine may be elaborated by reaction with a doubly electrophilic carbon moiety which can provide a source of chirality giving an enantiomerically pure product. It may be converted into a phosphorus heterocycle by reaction with a diol activated by conversion of the hydroxyl groups into leaving groups. The diol may be activated by, for example, conversion into a halogen derivative, sulphate, sulfonate or phosphate. Diols suitable for use in the present invention include C 2 to C 6 diols. The diols may be unsaturated or saturated and they may optionally be substituted by oxygen, nitrogen, sulfur, aliphatic, aromatic or heteroaromatic groups.
It will be appreciated that other substituents may be attached to the primary phosphine in an analogous manner.
In the process of the present invention it is advantageous to convert one or both of the phosphorus atoms into, for example, oxide or sulfide derivatives, preferably borane derivatives, which may later be converted back into the desired phosphine or diphosphine.
DESCRIPTION OF THE DRAWING
FIG. 1 shows an example of preparation of diphosphines according to the present invention.
DETAILED DESCRIPTION
An example of preparation of diphosphines according to the present invention is shown in Scheme 1 of FIG. 1 . In Scheme 1 the diphosphines produced combine the phosphorus moieties of DIPAMP (R, R-1,2,-bis[(2-methoxyphenyl)phenylphosphino]ethane) 1 and BPE (1,2-bis[2,5-dialkyl phospholano]ethane) 2 are combined.
The synthesis shown in Scheme 1 of FIG. 1 is based on the conjugate addition of the racemic phosphineborane 3 to diethyl vinylphosphonate. Alane reduction of the product 4 gives the primary phosphineborane 5 . Following deboronation, stepwise double nucleophilic displacement on the cyclic sulfate 6 via BuLi deprotonation gives the diphosphones 7 and 8 as a diastereomeric mixture. These compounds may be separated by MPLC (EtOAc/pentane). The analogous compounds 10 -OH and 11 -OH may be prepared from the mannitol derivative 9 as with a corresponding methyl ethers 10 -OMe and 11 -OMe.
The catalysts of the present invention may be used in the asymmetric catalytic conversion of a variety of compounds wherein a new C—B, C—Si, C—O, C—H, C—N or C—C bond is formed through the influence of the catalyst with control of the configuration at carbon. Such reactions include, for example, catalytic hydroboration, hydrosilylation, transfer hydrogenation, amination, cross-coupling, Heck olefination reactions, cyclopropanation, aziridination, allylic alkylation and cycloadditions. Preferably the catalysts are used in asymmetric hydrogenation. Preferred substrates for asymmetric hydrogenation include unsaturated esters such as esters of dehydroamino acids or methylenesuccinic acids. It has been found that using the catalysts of the present invention, a high enantiomer excess can be obtained from unsaturated esters under mild conditions. It is believed that a single site in the ligand directs reaction by H-bonding to the reactant and improves the enantio-selectivity.
The Examples which follow further illustrate the present invention.
EXAMPLES
The Synthesis of Enantiomerically Pure 1-(2-Methoxyphenylphenylphosphino)-2-(2,5-dimethyl-3,4-dimethoxyphospholanyl)ethane
The cyclic sulfate precursor was prepared from the known mannitol-derived diol. (M Sanière, Y le Merrer, H El Hafa, J-C Depezay, F Rocchiccioli, J. Labelled Cpd. Radiopharm ., 1991, 29. 305.) Each compound may be obtained on ca 5 g scales as a crystalline solid. The cyclic sulphate 9 is preferably subjected to short-column chromatography, to remove traces of an impurity suspected to be the monofunctionalised sulphate (itself isolated and characterised by nmr). Nonetheless, it can be purified by crystallisation from ether-pentane. No acid-induced cleavage of the isopropylidene protecting group appears to take place.
Racemic o-anisylphenylphosphine and its corresponding borane complex were prepared without difficulty by the method of Imamoto. (T Imamoto, T Oshiki, T Onozawa, T Katsumoto and K Sato, J. Am Chem. Soc ., 112, 5244, 1990.) No scale-up problems were encountered and the reaction was adapted to give 40 g of product without difficulty. Both PhArPH and PhArPH(BH 3 ) (Ar=phenyl, o-anisyl) smoothly underwent KOtBu-catalysed Michael addition to diethyl vinylphosphonate. Racemic 2-anisyl-phenylphosphinoethyl diethylphosphinoethyl phosphonate 4 and 2-diarylphosphinoethyl diethylphosphonate were obtained as their borane complexes on a 10 g scale in five minutes at room temperature. Alane reduction of this product gave the primary phosphine 5 .
The cyclisation to diphosphines 10 -OH and 11 -OH was carried out by a two-stage sequence with butyl lithium in THF. Direct hydrolysis of the crude phosphine (TMSCI-MeOH) gave the diastereomeric diols which, running much more slowly on silica in pure ether than the impurities, were easily separated by column chromatography. The faster-running diastereomer ( 11 -OH rf=0.25) can easily be obtained in enantiomeric excesses better than 99%.
Hydrogenation of Esters of Deliydroamino Acids or Methylenesuccinic Acid
2 ml of degassed dichloromethane was added to (0.105 mmol) of diphosphine borane under argon. 1.05 mmol of HBF 4 was added then the solution was stirred at 20-25° C. during 14 hours. Then 41 mg (0.1 mmol) of [Rh(COD)2]BF 4 was added. After being stirred for 10 minutes, the solvent was removed in vacuo and the yellow-orange residue was triturated three times with 5 ml of diethyl ether. The ether was removed via cannula filtration or syringe and the orange residue dried in vacuo. These complexes were stored in Schlenk tubes under argon. For the catalytic hydrogenation reactions the complexes were prepared just before use. 1 ml of a solution of Rhodium complex (2 mmol/l) in methanol was transferred under argon via cannula or syringe to a Schlenk tube under argon or hydrogen containing 0.2 mmol of olefin. The solution was placed under hydrogen and stirred at 20-50° C. during 2-5 hours. After evaporation of the solvent, the product was purified by chromatography on silica (methanol/dichloromethane). Enantiomeric excesses determined by NMR using Eu(hfc) 3 as chiral shift reagent or by gas chromatography using a column Chrompack WCOT Fused Silica, CP-Chirasil-DEX CB, 25 meters, inlet pressure 8 psi.
The hydrogenation of dehydroamino acids of different structures is shown in Table 1. From this it will be seen that the configuration of the phosphine and of the phospholane can be “matched” or “mismatched” according to their relative configurations. For the matched cases 11 -OH and 11 -OMe, enantiomer excesses of up to 92% can be obtained. It will also be seen that the extent to which the two centres influence the course of catalysis may differ greatly depending on the substrate.
TABLE 1
substrate
ligand
e.e.
10-OMe 11-OMe 10-OH 11-OH 7 8
19 S 85 S 43 S 92 S 60 R 38 S
10-OMe 11-OMe 10-OH 11-OH 7 8
58 S 67 S 82 S 88 S 5 R 36 R
11OMe 10-OH 11-OH
77 S 72 S 90 S*
Conditions: substrate:catalyst: 100:1, (COD) 2 Rh BF 4 as precursor, 1.3 bar, MeOH, 1-3 h.
*OSO 2 CF 3 − instead of BF 4 −
The results of hydrogenation of itaconate esters and half-esters are shown in Table 2. The mismatched diastereomers of ligand 10 gave poor e.e.s and are not included. For the 1-substuted monoester 15 , the hydroxy-ligand 11 -OH gives a superior e.e. to its methyl ether. The reverse is true for the 4-substituted monoester 16, where the methyl ether 11 -OMe provides the product of higher enantioselectivity.
TABLE 2
substrate
ligand
e.e.
11-OMe 8-OH
85 R 95 R
11-OMe 11-OH
93 R* 87 R
8-OMe 8-OH
85 R 80 R*
Conditions: substrate: catalyst: 100:1, (COD) 2 Rh BF 4 as precursor, 1.3 bar, MeOH, 1-3 h.
*: 94% e.e. with OSO 2 CF 3 − instead of BF 4 −
These preliminary results indicate that, contrary to expectation, the enantioselectivity may be sensitive to a remote substituent in the phospholane ring. Inspection of molecular models suggests that the MeO— or HO— groups are axial in the 5-membered ring of the phospholane, and in the vicinity of substituents on the coordinated alkene. Hence cooperative association between ligand and substrate may exist through hydrogen-bonding. | A non-symmetrical diphosphine of the formula R 1 R 2 P—(Z)—PR 3 R 4 wherein Z represents a chain of 2 to 4 carbon atoms which may be substituted, which chain may be saturated or unsaturated, and R 1 , R 2 , R 3 and R 4 , which may be the same or differ, are aliphatic, aromatic or heteroaromatic groups attached to the phosphorus by carbon, nitrogen, oxygen or sulphur such that each phosphorus atom and its substituents independently form a single enantiomer. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to implantable medical devices. More particularly, the present invention relates to electrical interconnection structures for implantable medical devices.
Electrical feedthroughs provide a conductive path extending between the interior of a hermetically sealed container and a point outside the container. Implantable medical devices may include a connector module for connecting leads to the device. The connector module is electrically connected to circuitry inside a sealed case of the implantable medical device through one or more feedthroughs. Typically, an electronic module assembly (EMA) block is connected also to a feedthrough inside the implantable medical device, opposite the connector module. Wires are then connected to bond pads on the EMA block using conductive solders or brazes to complete the electrical connection across the feedthrough.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a method and structures for making electrical interconnections for implantable medical devices. Arc percussion welding can be used according to the present invention to weld together conductor materials. A connection structure can be formed between a wire and a feedthrough pin having an enlarged head.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an implantable medical device having a connector module that is electrically connected to feedthroughs.
FIG. 2 is a schematic representation of an interconnection assembly between a feedthrough and bond pads.
FIG. 3 is an exploded cross-sectional view of a feedthrough assembly.
FIG. 4 is a flow chart of a manufacturing process for creating electrical interconnection structures.
FIG. 5 is a schematic representation of an alternative embodiment of an interconnection assembly.
FIG. 6 is a schematic representation of another alternative embodiment of an interconnection assembly.
FIG. 7 is a cross-sectional view of a feedthrough assembly with a washer.
DETAILED DESCRIPTION
FIG. 1 is a perspective view of an implantable medical device 20 having a connector module 22 (also called a header) that is electrically connected to feedthroughs 24 that pass through a housing or cannister 26 of the device 20 . The feedthroughs 24 can be unipolar or multipolar. The connector module 22 includes electrically conductive ribbons 28 that extend between the feedthroughs 24 and components of the connector module 22 , such as sleeves or sockets 30 for accepting connector pins of leads (not shown).
FIG. 2 is a schematic representation of an interconnection assembly between a feedthrough assembly 24 and bond pads 32 A and 32 B that are located inside the canister of a device. A feedthrough pin 34 extends through a ferrule 36 of the feedthrough assembly 24 . The pin 34 has a first end 38 A at an interior side of the ferrule 24 A, and a bonding surface 40 is located at an enlarged portion 42 A of the first end 38 A of the pin 34 . A second end 38 B of the pin 34 also has a bonding surface 40 B on an enlarged portion 42 B. The bonding surfaces 40 A and 40 B provide substantially flat surfaces for making electrical connections. Although FIG. 2 shows enlarged portions 42 A and 42 B at both ends 38 A and 38 B of the pin 34 , it should be recognized that in further embodiments the pin 34 could have only a single enlarged portion at only one end.
The enlarged portion 42 A shown in FIG. 2 can have numerous alternative configurations according to the present invention. For example, the enlarged portion 42 A can be formed by welding or otherwise connecting a disc to the first portion of the pin 34 . Alternatively, the enlarged portion can be formed by coining the first end 38 A of the pin 34 . In any configuration, the enlarged portion 42 A generally has a greater area than a cross-sectional area of the pin 34 between the enlarged portion 42 A and the ferrule 36 . The enlarged portion 42 A in the illustrated embodiment has a diameter or width of about 30-40 mils. The relatively large surface area provided by the bonding surface 40 A of the enlarged portion 42 A facilitates aligning and connecting wires and other electrical components to the pin 34 . The enlarged portion 42 B can be configured similar to enlarged portion 42 A.
The bond pads 32 A and 32 B can be hybrid bond pads of a conventional type known to those skilled in the art of implantable medical device design. The bond pads 32 A and 32 B can be electrically linked to therapy circuits (not shown) or other components of an implantable medical device, as desired. The particular location of the bond pads 32 A and 32 B can also vary as desired.
A wire 44 is electrically connected between the pin 34 and the bond pads 32 A and 32 B. In particular, the wire 44 is electrically connected to the bonding surface 40 and to bonding regions 46 of the bond pads 32 A and 32 B. The wire 44 can be any electrical conductor in nearly any shape, for example, a conventional ribbon conductor.
The pin 34 and the wire 44 can each be made of a high conductivity material, for example, copper, platinum, tantalum, niobium, palladium, titanium, and alloys thereof. Also, alloys such as MP35N® nickel-cobalt-chromium-molybdenum alloy, nickel- and cobalt-based alloys and stainless steels can be used. Moreover, the wire 44 can be a copper-clad nickel ribbon. It should be recognized that in further embodiments, multiple wires can be connected to the pin 34 as desired.
FIG. 3 is an exploded cross-sectional view of one embodiment of a feedthrough assembly 50 that includes a ferrule 36 , a pin 34 extending through the ferrule 36 and a conventional hermetic seal 52 (e.g., a seal made of glass or other non-conductive seal material) between the pin 34 and the ferrule 24 A. A disc 42 A is positioned at the first end 38 A of the pin 34 , and for clarity is shown in an exploded cross-sectional manner in FIG. 3 . The disc 42 A provides a substantially flat bonding surface 40 A. The disc 42 A can be round, rectangular, or have other shapes, though any shape of the disc 42 A generally provides a substantially flat bonding surface 40 A.
In the illustrated embodiment, the disc 42 A has a recess 54 located opposite the bonding surface 40 A. The recess 54 in the disc 42 A is configured to mate with the first end 38 A of the pin 34 , where a welded connection can be made. In further embodiments, the recess 54 can be omitted (see FIG. 7 ).
FIG. 4 is a flow chart of a manufacturing process for creating electrical interconnection structures according to the present invention. Welded connections between components, such as between a wire and a bonding surface or between a disc and an end of a feedthrough pin, can be made using conventional arc percussion welding equipment.
With arc percussion welding, the components to be welded are first positioned at a selected distance from each other, such that an air gap is formed (step 60 ). Next, a burst of radio frequency (RF) energy ionizes the air in the air gap (step 62 ). A suitable cover gas is provided. Then an arc is created between the components to be welded to heat them to weldable temperatures, creating two molten masses (step 64 ). The arc can be created by discharging capacitor banks of the arc percussion welding equipment. The weldable temperature, and therefore the amount of electrical energy discharged by the capacitor banks, will vary depending on the particular characteristics of components to be welded. Once the components to be welded have reached a weldable temperature, they are accelerated together (step 66 ). The molten masses combine, metal to metal, are forged together. As the weld cools, a complete alloy bond is formed. One or more electromagnetic actuators can be used to accelerate the components to be welded together.
The arc percussion welding process can be performed to make an electrical connection at a feedthrough, and to form structures as shown and described with respect to FIGS. 1-3 . In such situations, the arc percussion welding process can be performed either before or after the feedthrough has been hermetically sealed (alternative steps 68 A and 68 B). An advantage of the method of forming electrical interconnection structures according to the present invention is that the electrical connections can easily be made after hermetically sealing the feedthrough.
It should be recognized that the method described above can be used in conjunction with conventional techniques for making electrical connections in implantable medical devices. For example, gas tungsten arc welding, electron beam welding, resistance welding, ultrasonic welding, laser welding, friction welding, coining and conductive adhesives can also be used. With respect to the structures shown in FIG. 2 , for instance, the electrical connection between the wire 44 and the bonding surface 40 can be formed by one technique and the electrical connection between the wire 44 and the bond pad 32 A by another technique.
The structures and method of the present invention can be applied in numerous ways. The following are some examples of alternative embodiments of the present invention. FIG. 5 is a schematic representation of an alternative interconnection assembly that includes a feedthrough assembly 124 and a pair of hybrid bond pads 132 A and 132 B. A feedthrough pin 134 , which extends through ferrule 136 , is electrically connected to the hybrid bond pads 132 A and 132 B directly. In other words, the pin 134 is directly connected to the bond pads 132 A and 132 B without the need for a separate wire therebetween. The pin 134 can be specially shaped or deflected to properly align it with respect to the bond pad 132 A to make the electrical connection therebetween. Moreover, the pin 134 can optionally include an enlarged portion in further embodiments. The connection between the pin 134 and the bond pad 132 A can be made using arc percussion welding.
FIG. 6 is a schematic representation of another alternative embodiment of an interconnection assembly that includes a feedthrough assembly 224 and a pair of hybrid bond pads 232 A and 232 B. A first wire 224 is connected to the bond pads 232 A and 232 B. A second wire 246 extends from the feedthrough 224 (e.g., from an enlarged end of a pin 234 that extends through a ferrule 236 of the feedthrough 224 ), and is connected to the first wire 244 at a joint location 248 . The first and second wires 244 and 246 , respectively, are connected together in an end-to-end configuration. In this embodiment, the connection between the first and second wires 244 and 246 enables the bond pads 232 A and 232 B and the feedthrough to be assembled and connected to separate wires ( 244 and 146 ) independently and later joined together at the joint location 248 . The joint can be formed using arc percussion welding.
FIG. 7 is a schematic representation of a feedthrough assembly 324 that includes a ferrule 36 and a pin 34 with an enlarged portion 42 . The feedthrough assembly 324 is generally similar to those described above. However, the feedthrough assembly shown in FIG. 7 further includes a non-conductive washer 326 that is positioned around the pin 34 , between the ferrule 36 and the enlarged portion 42 of the pin 34 . The washer 326 reduces the risk of welding splatter when the enlarged portion 42 is formed on the pin 34 , and can be placed around the pin 34 permanently or temporarily (and removed after the enlarged portion 42 is formed on the pin 34 ). The particular size and shape of the washer 326 can vary as desired.
The present invention provides for the use of arc percussion welding to weld together conductor materials used in implantable medical devices, and for connection structures to be formed between a wire and a feedthrough pin having an enlarged, nailhead-like head portion. Reliable electrical connections can be easily and simply made between a feedthrough and other components without the need for an electronic module assembly (EMA) block. By omitting the EMA block, manufacturing costs can be reduced and space inside an implantable medical device can be conserved.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. For example, the interconnection structures of the present invention can be used with nearly any type of implantable medical device. | An electrical interconnect structure for an implantable medical device includes a feedthrough that has a pin extending therefrom. The pin defines a first end and a middle portion. A bonding surface is formed at the first end of the pin, and the bonding surface has a surface area greater than a cross-sectional area of the pin at its middle portion. | 0 |
REFERENCE TO RELATED APPLICATION
[0001] This application is a nonprovisional of, and claims priority to, U.S. Provisional Application No. 61/305,135, filed Feb. 16, 2010, with title “High Efficiency Conversion of Solar Radiation into Thermal Energy,” pending. The entire disclosure in that application is incorporated herein by reference as if fully set forth.
FIELD
[0002] This disclosure generally relates to the use of solar heat. More particularly, the disclosure relates to solar heat collectors having working fluid conveyed through the collector and having means to exchange heat between plural fluids.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] FIG. 1 is a schematic view of a solar radiation conversion system according to one embodiment.
[0004] FIG. 2 is a top section view of a header and array of solar collection tubes for use in the embodiment of FIG. 1 .
[0005] FIG. 3 is a magnified section view of a header and part of an array of collection tubes used in the embodiment of FIG. 1 .
DESCRIPTION
[0006] For the purpose of promoting an understanding of the principles of the invention, reference will now be made to certain embodiments illustrated in the disclosure, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated device, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.
[0007] Generally, with reference to FIG. 1 , system 100 includes a solar collection subsystem 110 , a closed-loop circulation system 115 , and tank 130 . Solar collection subsystem 110 receives incident solar radiation E and moves the heat energy into the fluid flowing through circulation system 115 . That fluid circulates through tank 130 , where heat is drawn out, and back to solar collection subsystem 110 .
[0008] In particular, solar collection subsystem 110 includes collection tubes 112 (described further herein), header assembly 116 , support members 114 , and one or more legs 118 that support the other components of solar collection subsystem 110 at a desired angle and in a desired position. Each collection tube 112 includes a double-wall outer tube (a substantially transparent outer cylinder and an inner cylinder adapted to pass light and hold heat, fused together at the ends with evacuated space in between) that contains two or more inner “heat pipes,” which carry the heat energy up to the highest point in the tube. There the heat is transferred to recirculating fluid 128 (see FIG. 2 ) in header assembly 116 . Pump 120 moves recirculating fluid 128 through closed-loop circulation subsystem 115 , which includes pipe 122 , header 217 (see FIGS. 2-3 ) in header assembly 116 , pipe 124 , tank 130 , and pipe 126 . Within tank 130 , heat exchanger 132 pulls heat out of recirculating fluid 128 and into the water in tank 130 . The heated water in the storage tank 130 is then available for many uses, as will occur to those skilled in the art, including without limitation domestic hot water, heated water for radiant floor heating, recovery water for boiler systems, commercial hot water systems, and other applications.
[0009] In other embodiments, tank 130 holds fluid other than water, which is likewise used as will occur to those skilled in the art. In still other embodiments, recirculating fluid 128 transports heat energy to any other load for using heat energy that will occur to those skilled in the art. In these various systems, recirculating fluid 128 may be a mixture of 70 % propylene glycol and 30% water, or it may be any other fluid suitable for heat transport as will occur to those skilled in the art.
[0010] FIG. 2 illustrates an array 210 of collection tubes 212 that cooperate to capture solar energy for the system. As discussed elsewhere herein, each collection tube 212 connects with manifold 217 (within manifold assembly 214 ), where recirculating fluid 128 captures the heat. Recirculating fluid 128 enters manifold 217 through inlet 216 and exits through outlet 218 , flowing through the rest of circulation subsystem 115 as discussed above. End caps 221 protect the ends of collection tubes 212 and hold collection tubes 212 in position. They may be made from plastic, metal, or other material as will occur to those skilled in the art.
[0011] FIG. 3 illustrates more detail about collection tubes 212 and their interface with manifold 217 . In this embodiment, each collection tube 212 is a double-wall glass tube made of a transparent outer cylinder and an inner cylinder coated with a selective coating (such as AIN/AI) that features excellent solar radiation absorption and minimal reflection properties. The ends 213 of the cylinders are fused together as the space between them is evacuated at high temperature in order to create and maintain a vacuum gap between the cylinders.
[0012] The transparency of the outer cylinder allows light rays to pass through with minimal reflection. The inner cylinder absorbs radiation and reflects only minimal amounts thereof. The evacuated space between the inner and outer cylinders helps the efficiency of the collection subsystem in several ways, including but not limited to reducing the amount of radiant energy that is absorbed by matter in that evacuated space 224 ; reducing the overall mass of the system; and avoiding losses due to conduction of heat from the heat pipes 220 to the ambient air 226 .
[0013] Within each collection tube 212 , in the space inside the inner cylinder, are two or more heat pipes 220 . Each heat pipe 220 in this embodiment is made of high-purity copper, containing only trace amounts of oxygen and other elements. These and other implementations of the invention will have different and additional advantages as will occur to those skilled in the art.
[0014] In operation, heat pipes 220 function to capture incident radiant energy as heat and transfer that heat to header 217 . Each heat pipe 220 is evacuated, and a small quantity of purified water and/or other fluid (as will occur to those skilled in the art) is added. By evacuating the heat pipes 220 , one lowers the temperature at which the fluid evaporates in the tube. In one embodiment, the heat pipes 220 have a boiling point of only 30° C. (86° F.), so when the heat pipe 220 is heated above that temperature, the fluid vaporizes. This vapor rapidly rises to the condenser 222 located at the top of the heat pipe 220 . This condenser is inserted into header pipe 217 . A mixture 228 of 70% propylene glycol and 30% water is pumped through the header 214 , absorbing via condenser 222 the thermal energy harvested by the heat pipe 220 . As this heat is drawn from the condenser, the vapor in inner tube 220 condenses in condenser 222 and returns to the bottom of the heat pipe 220 to repeat the process.
[0015] Even though heat pipe 220 is evacuated and the boiling point of the fluid inside has been reduced, the freezing point of that fluid is still the same as at sea level (which, in this embodiment, is 0° C. (32° F.)). Because the heat pipe 220 is located within the inner cylinder, protected from losses to ambient air 226 by the vacuum gap 224 , brief overnight temperatures as low as −20° C. (14° F.) will not cause the heat pipes 220 to freeze. Plain water heat pipes may be damaged by repeated freezing. The water used in the heat pipes in the present system still freezes in cold conditions, but it freezes in a controlled way that does not cause swelling of or damage to the copper pipe.
[0016] The use of two or more heat pipes 220 within each collection tube 212 provides additional advantage over other designs. For example, having two or more heat pipes within each solar collection tube provides significantly greater density in the overall collection subsystem than other designs. Further, this aspect of the present design is complimentary to other techniques for improving capture of solar radiation in solar collection systems, and can be combined with techniques like using lenses or reflectors to concentrate the solar radiation before it is captured. Other radiation concentration techniques can be used with this system as will occur to those skilled in the art in view of this disclosure.
[0017] In various embodiments, two, three, four, or more heat pipes may be contained within each outer tube and connected to the closed circulation path via conductive heat transfer. In other embodiments, multiple collection manifolds receive heat from the condenser portions of the heat pipes, running (as a non-limiting example) in parallel through the manifold enclosure.
[0018] While the inventions have been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that the preferred embodiment has been shown and described and that changes and modifications that come within the spirit of the invention are desired to be protected. | A high-efficiency solar radiation collection and conversion system is described. An array of evacuated collector tubes each includes two or more inner heat pipes that capture the solar energy and conduct it as heat through a condenser portion into a manifold that operates as part of a closed-loop circulation system. In another part of the loop, a heat exchanger transfers the heat into a hot-water holding tank or otherwise applies the heat energy in the circulating fluid. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the charging of furnaces and particularly to the delivery of material from the ambient atmosphere to the interior of a furnace and the exercise of control over the distribution of the thus delivered material on the furnace hearth. More specifically, the present invention is directed to charging installations for shaft furnaces and particularly to devices for transmitting material to the interior of a pressurized furnace and controlling the distribution of such material within the furnace. Accordingly, the present invention is directed to novel and improved methods and apparatus of such character.
2. Description of the Prior Art
Generally speaking, charging installations for blast furnaces fall into two classifications. The older type of charging installation is characterized by "bells" which perform a valving and flow control function. The other type of furnace charging installation is the "bell-less" type as exemplified by the apparatus disclosed in U.S. Pat. No. 3,693,812. Furnace charging installations of the "bell" type include a plurality of superimposed charging bells which are individually raised and lowered in accordance with a sequence which permits the material with which the furnace is to be charged to be conveyed from the ambient atmosphere to the interior of the furnace at the top or throat area thereof.
Prior furnace charging installations which employ charging bells are known to possess a number of inherent deficiencies when compared to the "bell-less" type of charging installation. These deficiencies include manufacturing problems and furnace operational difficulties. The seriousness of these problems increases in proportion to the dimensions of the charging apparatus and the furnace pressure. In a bell-type charging installation the lower bell, which is the largest in the series of superimposed bells, functions both as a distributor for the charge material released into the furnace and as a shut-off valve which delimits a chamber in which the charge material is temporarily stored. Because of its size and the multiple functions it must perform, the manufacture of a lower charging bell involves major production problems and these problems are aggravated when it becomes necessary to service the installation by removal and replacement of the bell. Also, during normal operation, a considerable amount of equipment is required for raising and lowering the bells, particularly the lower bell, and for establishing the requisite pressure in the chambers which are in part defined by the bells. The complete charging installation thus requires powerful actuators and is usually of considerable height.
One of the major deficiencies of the prior bell-type charging installations resides in the fact that there is practically no way to exercise control of the distribution of the charge material on the charging surface of the furnace. Since the larger lower bell of a bell-type charging installation is in the shape of a truncated cone, it is impossible to avoid the formation of a cavity or depression at the center of the furnace and usually also about the periphery of the charging surface. Thus, charging installations of the bell type are characterized by the establishment of a charge profile which, when viewed in cross section, has the known "M curve". It is well known in the art that the efficiency of operation of a blast furnace may be maximized by controlling a number of operating parameters including the charge profile. For a further discussion of the reasons why exercise of control over the furnace charge profile is important, reference may be had to U.S. Pat. No. 4,094,494. For purposes of the present discussion it should suffice to point out that it is highly desirable to be able to exercise control over the deposition of charge material on the furnace charging surface or hearth and that this operating parameter cannot be controlled in a conventional prior art bell-type charging installation.
There have been efforts to overcome or reduce the seriousness of the above-discussed inherent problems with bell-type furnace charging installations. These efforts have included the positioning of detectors about the lower bell of the charging installation, increasing the number of superimposed bells and modifying the equipment for operating the bells. These efforts have, to date, been largely unsuccessful and have often resulted in proposed solutions which were either economically impractical or would require an unacceptable increase in the overall height of the charging installation which, of course, is mounted on the top of the furnace. Accordingly, most newly constructed large capacity furnaces are equipped with "bell-less" charging installations which include a rotary and angularly adjustable charge distribution chute located within the furnace.
Economic and/or physical limitations may, however, preclude the replacement of a conventional bell-type charging installation with a "bell-less" type installation in some cases. Thus, by way of example, when an existing blast furnace is being repaired, the ability to retain the auxiliary equipment associated with a bell-type charging installation may dictate that the bell-type charging device not be replaced by a "bell-less" charging installation. There thus remains in the industry a strong desire, previously unanswered, for apparatus and techniques which permit a bell-type charging installation to be upgraded in such a manner that true exercise of control over furnace charge profile is possible.
SUMMARY OF THE INVENTION
The present invention significantly reduces the above-discussed deficiencies of prior art bell-type charging installations by providing novel and improved techniques and apparatus which enable the exercise of control over the distribution of charge material delivered to the interior of a furnace. A charging installation in accordance with the present invention is characterized by moderate height, a comparatively uncomplicated mechanism and ease of service.
Apparatus in accordance with a preferred embodiment of the present invention includes a rotary charging hopper which is positioned within a hermetic casing and which, by means of an isolation valve and a charging bell, may be isolated from the ambient atmosphere or the furnace interior as necessary.
Also in accordance with a preferred embodiment of the present invention, the aforementioned rotary charging hopper is mounted coaxially of the furnace and is provided with a base which is movable relative to the hopper. The charging bell, which preferably has a distributor portion of variable geometry, is vertically movable along the furnace axis with the movable base of the rotary charging hopper.
In accordance with one embodiment of the invention, the vertically movable charging bell includes a charge distributor comprised of a "skirt". This "skirt" consists of a plurality of overlapping segments. The "skirt" is coupled to a control mechanism which enables the geometry, and particularly the angle of opening, of the "skirt" to be varied such that the charging material, which falls in an annular pattern, may be directed so as to be deposited in concentric rings which will approximate the desired charging profile. The control over "skirt" geometry may be effected by establishing a connection between the individual segments of the "skirt" and the control apparatus via an actuator having a plurality of arms which extend radially outwardly to engage the "skirt" segments via cooperating slots and lugs. The actuator is, in turn, connected to a vertically movable control rod.
Also in accordance with a preferred embodiment of the present invention, a tubular deflector is positioned between the discharge end of the hopper and the adjustable "skirt" portion of the charging bell. This deflector guides the flow of material from the hopper onto the "skirt" which, in turn, directs the material in the form of a ring onto the charging surface. The adjustment of the opening angle of the "skirt", by means of sliding the control rod in the vertical direction, enables the angle at which this ring of material is discharged to be adjusted and thus the radius of the annular deposit of the charge material to be varied. After each charging cycle, corresponding to the discharge of the contents of the rotary hopper, it is possible to adjust the discharge flow angle to correct the charge profile in accordance with information which may, for example, be provided by a device which scans the profile of the charging surface.
A further important characteristic of the preferred embodiment of the present invention resides in the fact that the device which actually directs the flow of charge material onto the furnace charging surface may be removed from the furnace with relative ease should a maintenance operation become necessary.
A charging installation in accordance with the present invention is characterized by a single "bell" and the actuating devices therefor are mounted in a prolongation of the control shaft for the bell thereby permitting the height of the entire apparatus to be minimized.
BRIEF DESCRIPTION OF THE DRAWING
The present invention may be better understood and its numerous objects and advantages will become apparent to those skilled in the art by reference to the accompanying drawing wherein like reference numerals refer to like elements in the several figures. and in which:
FIG. 1 is a schematic cross-sectional side elevation view of a furnace charging installation in accordance with a preferred embodiment of the present invention, FIG. 1 depicting the apparatus in the charge material receiving state;
FIG. 2 is a view similar to FIG. 1 but depicting the apparatus in a further stage of a furnace charging cycle;
FIG. 3 is a view similar to FIG. 1, but also representing the charge material, depicting the apparatus in a further phase of a charging cycle; and
FIG. 4 is a view similar to FIG. 3 but depicting the deposition of the charge material at a different point on the furnace hearth.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to FIG. 1, a charging installation in accordance with a preferred embodiment of the present invention is indicated generally at 12. The charging installation 12 is mounted at the top of a blast furnace 10. The furnace 10 has a central axis "0" and the charging installation is supported on a ring-shaped flange 14 which forms part of the throat or neck portion of furnace 10; flange 14 being coaxial with furnace axis "0".
The charging installation includes an open topped charging hopper 18 which forms part of a rotary cage; the rotary cage being indicated generally at 21. Vertical movement of cage 21, including hopper 18, is permitted by means of pairs of guide rollers as indicated at 20 and 22. The rollers of each pair may include cooperating concave and convex surfaces with the vertically oriented roller having the convex surface and being mounted on the hopper 18 as shown. Rotary motion of the cage 21 is produced by a drive motor 24. The motion of the output shaft of motor 24 is coupled to cage 21 via a drive including pinion 26 and bearing 28.
The lower end of hopper 18 is in the form of a funnel 92. Hopper 18 is supported, via funnel 92, on a conical base 30. The base 30, in addition to supporting hopper 18, functions as a wear cone for protecting a bell 32. Base 30 is integral with a tubular cover or housing 34 which is coaxial with the furnace axis "0". The cover 34, in the disclosed embodiment, is formed of a series of segments comprised of a suitable wear-resisting material since cover 34 is exposed to the abrasive action of the furnace charge material. Tubular cover 34 serves as a protective housing for a tubular suspension bar 38 to which the bell 32 is affixed; the connection between cover 34 and tubular bar 38 being by means of a support bearing 36.
For the reason to be set forth below, motor 24 may be energized to impart an oscillatory movement to the assembly comprised of cage 21, the vertical guide members including roller pairs 20 and 22, hopper 18, base 30 and tubular protective cover 34. Vertical movement of the tubular suspension bar 38, produced in the manner to be described below, will cause hopper 18 to move vertically.
The hopper 18 is positioned within a casing 40. Casing 40 is hermetically sealed, at its lower end, to flange 14 via a further ring-shaped flange 94. A valve seat defining member 42 is provided at the lower end of casing 40, about the periphery of the opening in flange 94, and cooperates with the bell 32 to perform a valve function. Thus, with bell 32 in the raised position as shown in FIG. 1, a hermetic seal will exist between the interior of the furnace 10 and the interior of casing 40. Casing 40, at its upper end, communicates with a receiving spout 44 via an extension which houses a shut-off valve 46. With bell 32 in contact with seat 42, the valve 46 may be opened and the material with which the furnace is to be charged dropped into hopper 18 via spout 44 from transport devices of the type known in the art; i.e., skips or a conveyor belt. After hopper 18 has been loaded, the valve 46 will be closed and the interior of casing 40 will be raised to approximately the pressure existing within furnace 10 by means, known in the art, which have been omitted from the drawing in the interest of facilitating understanding of the invention.
In accordance with the present invention, a veriable geometry conical distributor, indicated generally at 48, is suspended from bell 32 by means of a support member 50 which is integral with bell 32. The distributor 48 thus follows the ascending and descending movements of bell 32 which result, in the manner to be described below, from imparting vertical motion to the tubular suspension bar 38. As noted above, in FIG. 1 the bell 32 is shown in its uppermost or sealing position. A lower position for distributor 48 is indicated on FIG. 1 by means of a broken line showing. The distributor 48 includes a segmented "skirt" 52. Each of the segments 54 of skirt 52 consist of a sector of an annular surface, slightly curved, whereby a frusto-conical charge distribution member may be defined when the "skirt" is in the condition depicted in FIG. 1 with minimum overlapping of the segments 54; this frusto-conical distribution surface being coaxial with the axis "0" of the furnace 10.
Continuing with a description of the distributor 48, the support member 50 is provided with a plurality of inwardly extending ribs 56. The number of ribs 56 will correspond to the number of segments 54 of "skirt" 52. Each "skirt" segment 54 is articulated to a corresponding rib 56 via a pivot 58. It will be understood that, as long as support for the pivots 58 is provided, it is not necessary for each of the ribs 56 to extend all the way upwardly to the bell 32. Each of "skirt" segments 54 is provided, extending inwardly from its internal concave surface, with a web 60. The webs 60 may comprise a plate welded to the segment or perpendicular extension formed during casting of the segment. The webs 60 are each provided with a slot 62 which receives a drive pin 64. The drive pins 64 extend transversely from the lower ends of the radial fingers or points 68 of a "star-shaped" plate 66. The number of fingers 68 of the plate 66 will correspond to the number of segments 54 of "skirt" 52. The plate 66 is affixed to the lower end of a control rod 70 which passes through bell 32 and extends upwardly through the tubular suspension bar 38. Control rod 70, in the manner to be described below, is vertically movable relative to the suspension bar 38 and thus plate 66 is vertically movable with respect to bell 32.
The angular position of each of "skirt" segments 54 relative to furnace axis "0"; i.e., the degree of tilt of segments 54 about pivots 58; is determined by the position of plate 66 relative to bell 32. Thus, when plate 66 occupies its lowest position relative to bell 32, the segments 54 pivot outwardly about pivots 58 and the angle of opening of "skirt" 52 is at its maximum as shown in FIGS. 1, 2 and 3. By raising plate 66 toward bell 32, through imparting vertical motion to control rod 70, the outwardly disposed ends of segments 54 are lowered in the direction of furnace axis "0" and the angle of opening of "skirt" 52 decreases progressively until it reaches the position shown in FIG. 4. Between the two extreme positions shown in FIGS. 1 and 4, where the conicity of distributor 48 is generally opposite, the "skirt" 52 passes through a cylindrical position.
In one version of the invention the pivoting angle, indicated at α in FIG. 1, of each of segments 54 of "skirt" 52; i.e., the angle between the extreme positions of FIGS. 1 and 4; is 60°. During the vertical movement of plate 66, the drive pins 64 slide in their respective slots 62 in the webs 60 of "skirt" segments 54 to translate the vertical movement of pins 64 to pivoting movement of segments 54 about pivots 58. When the angle α is equal to 60°, the axis of the slots 62 in webs 60 should preferably occupy an angle of approximately 30° relative to a horizontal plane passing through pivots 58.
The number of segments 54 of "skirt" 52 must naturally be a devisor of 360. The number of segments 54 must also be sufficiently great to minimize the effects of thermally induced expansion and to achieve the desired geometry. Thus, it has been found that there should be at least sixteen, and preferably twenty-four, segments 54 of "skirt" 52. If the width of the individual segments is excessive at their lower ends, obviously "skirt" 52 would not be able to close to a sufficient degree. If the segments are too large, expansion thereof will not be kept within acceptable limits.
The segments 54, since they are exposed to the errosive effects of the falling furnace charge material and to the severe temperature and pressure conditions within the furnace 10, will be comprised of a refractory steel having good wear-resisting properties.
A deflector 72, which has a circular cross section when viewed in the vertical direction, partly circumscribes the distributor 48. Deflector 72, at its lower end, is convergent in the direction of furnace axis "0" and thus directs charge material flowing out of hopper 18 onto the "skirt" 52 of distributor 48.
An actuator unit, indicated generally at 74, controls the vertical position of bell 32 and the angle of opening of "skirt" 52. Control unit 74 is mounted above the hermetically sealed casing 40 in an extension thereof. The tubular suspension bar 38, to which bell 32 is connected, extends through casing 40 via a stuffing box and is connected to the tubular piston rod 80 of a hydraulic jack 78 via a removable collar 82. The control rod 70, to which plate 66 of distributor 48 is connected, passes through suspension tube 38 and the piston rod 80 of jack 78 and is connected to the piston rod of a second hydraulic jack 84 mounted above jack 78. In the disclosed embodiment the upper hydraulic jack 84 is integral with the piston of jack 78 and thus jack 84 follows the vertical movements of the tubular suspension bar 38.
Portions of distributor 48 and the control mechanism therefor may be cooled by the passage of suitable coolant therethrough. The coolant is delivered to the apparatus via conduits 86 and 88. In accordance with one embodiment of the invention, conduit 86 delivers coolant to a plurality of pipes, not shown, which are arranged in a ring between suspension tube 38 and control rod 70. These pipes will convey the coolant to passages which extend through ribs 56, pivots 58, "skirt" segments 54 and possibly also the webs 60. A second cooling liquid circulation system, fed by conduit 88, may be provided through control rod 70 and downwardly into the plate 66 and the fingers 68 thereof. The cooling of plate 66 and the segments 54 of the distributor "skirt" 52 increases the mechanical strength of and thus minimizes the possibility of deformation of these elements.
The operation of the disclosed embodiment of the present invention will now be described. As used herein, the term "cycle" will correspond to a single filling and subsequent emptying of the hopper 18. A complete charging of furnace 10 will require a plurality of such cycles. In order to enable the charging hopper 18 to be loaded with the particulate material which is subsequently to be delivered to the furnace hearth, the lower bell 32 must be urged tightly against the seat 42 by the action of hydraulic actuator 78 so that the interior of casing 40 will be hermetically isolated from the interior of furnace 10. Once this hermetic isolation has been achieved, casing 40 may be depressurized and valve 46 opened so that the charge material may be introduced into hopper 18 via receiving spout 44. In order to insure even filling of hopper 18, motor 24 will be energized to impart either a continuous or intermittant rotary motion to hopper 18 depending upon whether the furnace charge material is being supplied to spout 44 by a conveyor belt or by a skip installation. When hopper 18 is filled the valve 46 is closed and the interior of casing 40 is pressurized, by means known in the art, to a level approximately equal to the pressure existing in the furnace 10. Once the interior of casing 40 has been pressurized, the hydraulic jack 78 will be operated to lower suspension bar 38 and thus bell 32. Since hopper 18 rests on conical base 30, which is connected to suspension bar 38, hopper 18 will initially move downwardly with bell 32; the hopper moving on the guiding system comprising roller pairs 20 and 22. When hopper 18 reaches the position shown in FIG. 2, a flange at the lower end thereof will contact a plurality of dampers such as those indicated at 90 and 91. During the vertical movement of hopper 18 the motor 24 will be inoperative.
In the positon shown in FIG. 2, with further downward movement of hopper 18 prevented by dampers 90 and 91, the funnel portion 92 at the lower end of hopper 18 will form a protective shield about the seating member 42 and particularly the sealing surface thereof which cooperates with bell 32. As the suspension bar 38 continues its downward movement, base 30 separates from funnel 92 and the bottom of hopper 18 is progressively opened until it reaches its maximum opening position as shown in FIG. 3. With bell 32 in its lowermost position as shown in FIG. 3, the charge material previously loaded into hopper 18 is released so as to fall, under the influence of gravity, in a trajectory determined by the combined action of conical base 30, the deflector 72 and the "skirt" 52. As bell 32 moves downwardly from the position shown in FIG. 2 to that of FIG. 3, the jack 84, control rod 70 and variable geometry distributor 48 will also continue to move downwardly.
With "skirt" 52 in the condition shown in FIG. 3, with maximum opening, the material discharged from hopper 18 will be deflected so as to form an annular peripheral deposit on the charging surface of the furnace. In order to deposit material in the central region, about the furnace axis "0", the jack 84 will be actuated to move plate 66 upwardly toward bell 32 whereby "skirt" 52 "folds" until it reaches the position depicted in FIG. 4. In the FIG. 4 position, "skirt" 52 is generally outside of the trajectory of the falling charge material and this trajectory is determined primarily by the convergent lower end of deflector 72. The position of the annular deposit of charge material released from hopper 18 may, of course, be directed to any intermediate region between the regions shown in FIGS. 3 and 4 by selecting an appropriate opening angle for "skirt" 52.
In accordance with one characteristic of the present invention, the seat member 42 is bolted to the upper surface of lower flange 94 of casing 40 and has an inner diameter greater than the maximum outer diameter of bell 32 and distributor 48. This enables the assembly, including bell 32 and distributor 48, to be dismantled and removed via flange 94 subsequent to removal of seat 42 and funnel portion 92 of hopper 18. In order to permit its removal through the opening in flange 94, distributor 48 must be in the condition shown in FIG. 4.
The mounting of actuator unit 74 on top of casing 40 enables the entire charging installation to be characterized by moderate height and also permits dispensing with the usual bell tower. The comparatively low contour of the charging installation also results from the fact that the present invention requires only a single bell and the distributor 48 may be installed comparatively close to bell 32 since there is no storage of material between the bell and distributor.
While a preferred embodiment has been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation. | The profile of material deposited on the hearth of a pressurized furnace is controlled by means of a charging installation including a lower charging bell which has, suspended therefrom, a variable geometry distributor which may be controlled to select the point of deposition of material delivered to the furnace. The charging bell cooperates with an intermediate storage hopper, positioned within a hermetically sealable casing, whereby the hopper may be alternately filled with material and emptied by permitting the material to fall onto the distributor via an annular opening defined when the bell is lowered. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates, in general, to a diffractive micromirror and a method of producing the same and, more particularly, to a diffractive thin-film piezoelectric micromirror, which is operated in a piezoelectric operation manner to assure excellent displacement, operation speed, reliability, linearity, and low voltage operation, and a method of producing the same.
2. Description of the Prior Art
Generally, an optical signal processing technology has advantages in that a great amount of data is quickly processed in a parallel manner unlike a conventional digital information processing technology in which it is impossible to process a great amount of data in real time. Studies have been conducted on the design and production of a binary phase only filter, an optical logic gate, a light amplifier, an image processing technique, an optical device, and a light modulator using a spatial light modulation theory. The spatial light modulator is applied to optical memory, optical display device, printer, optical interconnection, and hologram fields, and studies have been conducted to develop a display device employing it.
The spatial light modulator is embodied by a reflective deformable grating light modulator 10 as shown in FIG. 1 . The modulator 10 is disclosed in U.S. Pat. No. 5,311,360 by Bloom et al. The modulator 10 includes a plurality of reflective deformable ribbons 18 , which have reflective surface parts, are suspended above an upper part of a silicon substrate 16 , and are spaced apart from each other at regular intervals. An insulating layer 11 is deposited on the silicon substrate 16 . Subsequently, a sacrificial silicon dioxide film 12 and a low-stress silicon nitride film 14 are deposited. The nitride film 14 is patterned by the ribbons 18 , and a portion of the silicon dioxide film 12 is etched, thereby maintaining the ribbons 18 on the oxide spacer layer 12 by a nitride frame 20 . In order to modulate light having a single wavelength of λ o , the modulator is designed so that thicknesses of the ribbon 18 and oxide spacer 12 are each λ/4.
Limited by a vertical distance (d) between a reflective surface 22 of each ribbon 18 and a reflective surface of the substrate 16 , a grating amplitude of the modulator 10 is controlled by applying a voltage between the ribbon 18 (the reflective surface 22 of the ribbon 18 acting as a first electrode) and the substrate 16 (a conductive layer 24 formed on a lower side of the substrate 16 to act as a second electrode). In an undeformed state of the light modulator with no voltage application, the grating amplitude is λ/2 while a total round-trip path difference between light beams reflected from the ribbon and substrate is λ o . Thus, a phase of reflected light is reinforced. Accordingly, in the undeformed state, the modulator 10 acts as a plane mirror when it reflects incident light. In FIG. 2 , reference numeral 20 denotes the incident light reflected by the modulator 10 in the undeformed state.
When a proper voltage is applied between the ribbon 18 and substrate 16 , the electrostatic force enables the ribbon 18 to move downward toward the surface of the substrate 16 . At this time, the grating amplitude is changed to λ/4. The total round-trip path difference is a half of a wavelength, and light reflected from the deformed ribbon 18 and light reflected from the substrate 16 are subjected to destructive interference. The modulator diffracts incident light 26 using the interference. In FIG. 3 , reference numerals 28 and 30 denote light beams diffracted in +/− diffractive modes (D +1 , D −1 ) in the deformed state, respectively.
It has been proven that sticking of the ribbon 18 to the substrate 16 is a common problem of the light modulator 10 during a wet process applied to form a space under the ribbon 18 and during operation of the modulator 10 . There are various methods of reducing the sticking: lyophilization, a dry etching of a photoresist-acetone sacrificial layer, an OTS single layer treatment, use of a hard ribbon and/or a tightened nitride film gained by shortening the ribbon, a method of roughing or wrinkling one or both surfaces of two facing surfaces, a method of forming a reverse rail on the lower part of the ribbon, and a method of changing the chemical properties of the surfaces. In a solid-state sensor and actuator workshop held in June, 1994 at the Hilton Head Island in Scotland, prevention of sticking was reported, which is accomplished by reducing the contact area by forming a reverse rail on the lower part of a bridge and by employing a rough polysilicon layer as disclosed in “a process of finely treating the surface of a deformable grating light valve for high resolution display devices” suggested by Sandeyas, et al., and “a grating light valve for high resolution display devices”, suggested by Apte et al.
Moreover, Apte et al. found that mechanical operation of the modulator 10 has a characteristic such that deformation of the ribbon 18 as a function of voltage forms hysteresis. The hysteresis is theoretically based on the fact that an electrostatic attractive force between the ribbon 18 and substrate 16 is a nonlinear function of the deformation, whereas hardness of the ribbon 18 is a substantially linear function of a resilient force by tension. FIG. 4 is a graph illustrating light output (which indirectly indicates the deformation of the ribbon 18 ) as a function of a voltage between the ribbon 18 and substrate 16 , which shows an induced hysteretic characteristic. Accordingly, when the ribbon 18 is deformed into a down position to come into contact with the substrate 16 , they are latched and require a holding voltage smaller than the original applied voltage.
U.S. Pat. No. 5,311,360 by Bloom et al. discloses a latching feature which gives a modulator 10 advantages of an active matrix design without the need for active components. Additionally, Bloom et al. describes that this feature is valuable in low power applications where efficient use of available power is very important. However, Bloom et al. discloses the addition of small ridges below ribbons 18 to reduce a contact area, thereby reducing the sticking problem. However, since the substrate of the modulator 10 is used as an optical surface, a process of adding the small ridges to the surface is complicated in that a reflective element of the substrate 16 must be smooth so as to have high reflectance and must be positioned on a planar surface of the ribbon 18 .
Typical display devices are formed in 2-D arrays of pixels. Discontinuous images formed by a plurality of pixels are integrated by user's eyes, thereby forming an aggregate image of pixels constituting a whole image. Unfortunately, prices of such a display device are high because the pixels are overlapped to form a complete array, so the production cost of each pixel is duplicated. The display device comprising pixels is exemplified by televisions or computer systems. Their pixels may be formed by an LCD device or a CRT device.
Accordingly, there is required a diffractive grating light valve capable of reducing or removing the sticking between the reflective element and the substrate without a complicated surface treatment adopted to reduce the sticking.
As well, a display device is required, which reduces the number of pixels to reduce production costs without reducing image quality while designing a system.
To satisfy the above requirements, a conventional improved technology is proposed in Korean Pat. Application No. 10-2000-7014798, entitled “method and device for modulating incident light beam to form 2-D image”, by Silicon Light Machines Inc.
In the “method and device for modulating the incident light beam to form the 2-D image”, the diffractive grating light valve includes a plurality of elongate elements each having a reflective surface. The elongate elements are arranged on an upper side of a substrate so that they are parallel to each other, have support ends, and their reflective surfaces lie in array (GLV array). The elongate elements form groups according to display elements. The groups alternately apply a voltage to the substrate, resulting in deformation of the elements. The almost planar center portion of each deformed elongate element is parallel to and spaced from the center portion of the undeformed element by a predetermined distance which is set to ⅓-¼ of the distance between the undeformed reflective surface and the substrate. Thus, the deformed elongate elements are prevented from coming into contact with the surface of the substrate. Sticking between the elongate elements and the substrate is prevented by preventing contact between the elements and substrate. Additionally, the predetermined distance between each deformed elongate element and the substrate is limited so as to prevent hysteresis causing deformation of the elongate elements.
FIG. 5 is a side sectional view of an elongate element 100 of a GLV in an undeformed state according to a conventional improved technology. In FIG. 5 , the elongate element 100 is suspended above a surface of a substrate (including constitution layers) by ends thereof. In FIG. 5 , reference numeral 102 denotes an air space.
FIG. 6 is a plan view of a portion of the GLV including six elongate elements 100 . The elongate elements 100 have the same width and are arranged parallel to each other. The elongate elements 100 are spaced close to each other, so that the elongate elements 100 can be deformed independently from other elements. The six elongate elements 100 as shown in FIG. 6 preferably form a single display element 200 . Therefore, an array of 1920 elongate elements forms a GLV array having 320 display devices arranged therein.
FIG. 7 is a front sectional view of a display element 200 having undeformed elongate elements 100 . FIG. 7 is a view taken along the line A-A′ of FIG. 5 . The undeformed state is selected by equalizing a bias on the elongate elements 100 to a conductive layer 106 . Since reflective surfaces of the elongate elements 100 are substantially co-planar, light incident on the elongate elements 100 is reflected.
FIG. 8 is a side sectional view of a deformed elongate element 100 of the GLV. FIG. 8 shows that the deformed elongate element 100 is maintained in the suspended state thereof to be spaced from the surface of the substrate adjacent therebeneath. This is in contrast to the conventional modulator of FIGS. 1 to 3 . Contact between the elongate element 100 and the surface of the substrate is prevented, thereby avoiding the disadvantages of conventional modulators. However, the elongate element 100 is apt to sag in the deformed state. The reason is that the elongate element 100 is uniformly subjected to an electrostatic attractive force acting toward the substrate in directions perpendicular to a longitudinal direction thereof, whereas tension of the elongate element 100 acts along the length of the elongate element 100 . Therefore, the reflective surface of the elongate element is not planar but curvilinear.
However, the center part 102 of the elongate element 100 ( FIG. 8 ) is almost planar, making the contrast ratio of diffracted light, gained by only the center part 102 of the elongate element 100 , desirable. The substantially planar center part 102 has a length that is ⅓ of a distance between post holes 110 . Hence, when the distance between the post holes 110 is 75 μm, the almost planar center part 102 is about 25 μm long.
FIG. 9 is a front view of the display element 200 in which the deformed elongate elements 100 are alternately arranged. FIG. 9 is a view taken in the direction of the arrows along the line B-B′ of FIG. 8 . The elongate ribbons 100 which are not removed are maintained at desired positions by an applied bias voltage. Deformation of the moving elongate ribbons 100 is achieved by alternate applications of operation voltages through the conductive layer 106 to the elongate elements 100 . A vertical distance (d 1 ) is almost constant to the almost planar center part 102 ( FIG. 8 ), thereby limiting the grating amplitude of the GLV. The grating amplitude (d 1 ) may be controlled by adjusting an operation voltage on the operated elongate elements 100 . This results in precision tuning of the GLV in an optimum contrast ratio.
As for diffractive incident light having a single wavelength (λ 1 ), it is preferable that the GLV has a grating width (d 1 ) that is ¼ (λ/4) of the wavelength of incident light to assure a maximum contrast ratio in an image to be display deviceed. However, the grating width (d 1 ) requires only a round trip distance that is the same as the sum of a half of the wavelength (λ 1 ) and the whole number of the wavelength (λ 1 ) (i.e. d 1 =λ 1 /4, 3λ 1 /4, 5λ 1 /4, . . . , Nλ 1 /2+λ 1 /4).
Referring to FIG. 9 , the lower side of each elongate element 100 is spaced upward from the substrate by a distance of d 2 . Accordingly, the elongate elements 100 do not come into contact with the substrate during operation of the GLV. This results in avoidance of the sticking problems between the reflective ribbons and the substrate occurring in conventional modulators.
With reference to a hysteresis curve shown in FIG. 4 , since the elongate elements 100 are moved by a distance that is ⅓-¼ of the distance between the elements and substrate to diffract incident light, hysteresis is prevented.
However, the light modulator which is manufactured by Silicon Light Machines Inc. and adopts an electrostatic method to control the position of a micromirror is disadvantageous in that an operation voltage is relatively high (usually 30 V or so) and a correlation between the applied voltage and a displacement is nonlinear, and thus, reliability is poor in the course of controlling light.
SUMMARY OF THE INVENTION
Therefore, the present invention has been made keeping in mind the above disadvantages occurring in the prior arts, and an object of the present invention is to provide a diffractive thin-film piezoelectric micromirror, which is operated by a piezoelectric operation method, unlike a conventional reflective diffractive light modulator operated by an electrostatic operation method, to assure excellent displacement, operation speed, reliability, linearity, and low voltage operation, and a method of producing the same.
Another object of the present invention is to provide a diffractive thin-film piezoelectric micromirror, which is operated by a thin-film piezoelectric operation method to make various structure designs on a silicon wafer possible, and a method of producing the same.
The above objects can be accomplished by providing a diffractive thin-film piezoelectric micromirror, including a substrate on which a recess is formed to provide an air space to the center thereof; and a piezoelectric mirror layer having a ribbon shape, which is attached to the substrate along both ends of the recess at both ends thereof while being spaced from the bottom of the recess at the center portion thereof and which includes a thin-film piezoelectric material layer to be vertically movable at the center portion thereof when voltage is applied to the piezoelectric material layer, and thus diffracts an incident light beam.
Additionally, the present invention provides a diffractive thin-film piezoelectric micromirror, including a substrate on which a recess is formed to provide an air space to the center thereof; a lower supporter which has a ribbon shape, is attached to an upper side of the substrate along both ends of the recess at both ends thereof while being spaced from the bottom of the recess at a center portion thereof, the center portion being vertically movable; and a piezoelectric mirror layer having a ribbon shape, which is laminated on the lower supporter while being spaced from the bottom of the recess of the substrate at both ends thereof and which includes a thin-film piezoelectric material layer to be vertically movable when voltage is applied to both sides of the thin-film piezoelectric material layer, and thus diffracts an incident light beam.
Furthermore, the present invention provides a diffractive thin-film piezoelectric micromirror, including a substrate on which a recess is formed to provide an air space to the center thereof; a lower supporter which has a ribbon shape, and is attached to an upper side of the substrate along both ends of the recess at both ends thereof while being spaced from the bottom of the recess at a center portion thereof; a first piezoelectric layer which is positioned on an end of the lower supporter at an end thereof and at a location far from a center of the lower supporter toward the end of the lower supporter by a predetermined distance at the other end thereof, and which includes a first thin-film piezoelectric material layer to shrink and expand so as to provide a first vertical actuating force when voltage is applied to the first thin-film piezoelectric material layer; a second piezoelectric layer which is positioned on the other end of the lower supporter at an end thereof and at a location far from the center of the lower supporter toward the other end of the lower supporter by a predetermined distance at the other end thereof, and which includes a second thin-film piezoelectric material layer to shrink and expand so as to provide a second vertical actuating force when voltage is applied to the second thin-film piezoelectric material layer; and a micromirror layer which is positioned at the center of the lower supporter to diffract an incident light beam.
As well, the present invention provides a diffractive thin-film piezoelectric micromirror, including a substrate on which an insulating layer is formed; a lower supporter which has a ribbon shape and is attached to the substrate at both ends thereof while being spaced from the substrate at the center portion thereof by a predetermined distance, the center portion being vertically movable; and a piezoelectric mirror layer which is laminated on the lower supporter while being spaced from the substrate at the center portion thereof, and includes a thin-film piezoelectric material layer to shrink and expand so as to vertically move at the center portion thereof when a voltage is applied to the piezoelectric material layer, and diffracting an incident light beam.
Furthermore, the present invention provides a diffractive thin-film piezoelectric micromirror, including a substrate on which an insulating layer is formed; a lower supporter which has a ribbon shape and is attached to both ends of the substrate at both ends thereof while being spaced from the substrate at the center portion thereof by a predetermined distance, the center portion being vertically movable; a first piezoelectric layer which is positioned on an end of the lower supporter at an end thereof and at a location far from the center of the lower supporter toward the end of the lower supporter by a predetermined distance at the other end thereof, and which includes a thin-film piezoelectric material layer to shrink and expand so as to be vertically moved when voltage is applied to the piezoelectric material layer; a second piezoelectric layer which is positioned on the other end of the lower supporter at an end thereof and at a location far from the center of the lower supporter toward the other end of the lower supporter by a predetermined distance at the other end thereof, and shrinks and expands so as to be vertically moved when a voltage is applied thereto; and a micromirror layer which is positioned at the center of the lower supporter to diffract an incident light beam.
Furthermore, the present invention provides a method of producing a diffractive thin-film piezoelectric micromirror, including a first step of forming a mask layer on a silicon wafer and patterning the mask layer to form a recess; a second step of forming a sacrificial layer so as to fill the recess formed in the first step; a third step of forming a piezoelectric mirror layer on the silicon wafer in which the recess is filled; a fourth step of etching the piezoelectric mirror layer formed in the third step to form a plurality of ribbons and removing the sacrificial layer to form the diffractive thin-film piezoelectric micromirror.
Furthermore, the present invention provides a method of producing a diffractive thin-film piezoelectric micromirror, including a first step of forming a mask layer on a silicon wafer and patterning the mask layer to form a recess; a second step of forming a sacrificial layer so as to fill the recess formed in the first step; a third step of forming a lower supporter on a silicon substrate in which the recess is filled; a fourth step of forming a pair of piezoelectric mirror layers on the lower supporter formed in the third step in such a way that each of the piezoelectric mirror layers is positioned on the remaining portion of the substrate other than the recess at an end thereof and at a location far from the center of the recess outward by a predetermined distance at the other end thereof, and the piezoelectric mirror layers are opposite to each other; a fifth step of forming a micromirror layer on the center portion of the lower supporter; and a sixth step of etching a pair of piezoelectric mirror layers and the lower supporter to form a plurality of ribbons and removing the sacrificial layer to form the diffractive thin-film piezoelectric micromirror.
Furthermore, the present invention provides a method of producing a diffractive thin-film piezoelectric micromirror, including a first step of laminating a sacrificial layer on a silicon substrate, forming a mask layer, and etching the resulting substrate to form a raised part; a second step of laminating a lower supporter on the silicon substrate on which the raised part is formed in the first step; a third step of forming a piezoelectric mirror layer on the lower supporter formed in the second step; and a fourth step of etching the piezoelectric mirror layer formed in the third step to form a plurality of ribbons and removing the sacrificial layer to form the diffractive thin-film piezoelectric micromirror.
Furthermore, the present invention provides a method of producing a diffractive thin-film piezoelectric micromirror, including a first step of laminating a sacrificial layer on a silicon substrate, forming a mask layer, and etching the resulting substrate to form a raised part; a second step of laminating a lower supporter on the silicon substrate on which the raised part is formed in the first step; a third step of forming a pair of piezoelectric mirror layers on the lower supporter formed in the second step in such a way that each of the piezoelectric mirror layers is positioned on the remaining portion of the substrate other than the raised part at an end thereof and at a location far from the center of the raised part outward by a predetermined distance at the other end thereof, and the piezoelectric mirror layers are opposite to each other; a fourth step of forming a micromirror layer on the center of the lower supporter; and a fifth step of etching a plurality of piezoelectric mirror layers and the lower supporter to form a plurality of ribbons and removing the sacrificial layer to form the diffractive thin-film piezoelectric micromirror.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 illustrates a grating light modulator adopting an electrostatic method according to a conventional technology;
FIG. 2 illustrates reflection of incident light by the grating light modulator adopting the electrostatic method according to the conventional technology in an undeformed state;
FIG. 3 illustrates diffraction of incident light by the grating light modulator in a deformed state due to an electrostatic force according to the conventional technology;
FIG. 4 illustrates a hysteresis curve for the grating light modulator adopting the electrostatic method according to the conventional technology;
FIG. 5 is a side sectional view of a column-type diffractive grating light valve adopting an electrostatic method according to a conventional improved technology;
FIG. 6 is a plan view of a portion of the grating light valve (GLV) including six elongate elements corresponding to a single display element according to the conventional improved technology;
FIG. 7 is a front sectional view of the display element of the GLV including the six elongate elements according to the conventional improved technology, which reflects incident light in an undeformed state;
FIG. 8 is a side sectional view of an elongate element of the GLV according to the conventional improved technology, which is deformed by an electrostatic force;
FIG. 9 is a front sectional view of the display element of the GLV including the six alternately arranged elongate elements, which diffracts incident light in a deformed state caused by an electrostatic force according to the conventional improved technology;
FIGS. 10 a to 10 j illustrate production of a diffractive thin-film piezoelectric micromirror having a recess according to an embodiment of the present invention;
FIGS. 11 a to 11 c illustrate various diffractive thin-film piezoelectric micromirrors having recesses, in which piezoelectric materials are not deformed;
FIGS. 12 a to 12 c illustrate various diffractive thin-film piezoelectric micromirrors having recesses, in which piezoelectric materials are deformed;
FIGS. 13 a to 13 b illustrate operation of a display element in which diffractive thin-film piezoelectric micromirrors having recesses and the same or different dimensions are alternately arranged, and FIG. 13 c illustrate operation of a display element in which diffractive thin-film piezoelectric micromirrors having recesses are arranged at regular intervals;
FIGS. 14 a to 14 h illustrate production of a thin-film piezoelectric light modulator having a raised part according to another embodiment of the present invention;
FIGS. 15 a to 15 c illustrate various diffractive thin-film piezoelectric micromirrors having raised parts, in which piezoelectric materials are not deformed;
FIGS. 16 a to 16 c illustrate various diffractive thin-film piezoelectric micromirrors having raised parts, in which piezoelectric materials are deformed; and
FIGS. 17 a to 17 b illustrate operation of a display element in which diffractive thin-film piezoelectric micromirrors having raised parts and the same or different widths are alternately arranged, and FIG. 17 c illustrate operation of a display element in which diffractive thin-film piezoelectric micromirrors having raised parts are arranged at regular intervals.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a detailed description will be given of a preferred embodiment according to the present invention, referring to FIGS. 10 a to 10 j.
FIGS. 10 a to 10 j illustrate production of a diffractive thin-film piezoelectric micromirror having a recess according to an embodiment of the present invention.
Referring to FIG. 10 a , a mask layer 1002 is formed in a thickness of 0.1-1.0 μm through a thermal oxidation process on a silicon wafer 1001 , and then patterned for silicon etching.
With reference to FIG. 10 b , the silicon is etched in a predetermined thickness, using a solution capable of etching the silicon, such as TMAH or KOH, and the mask layer 1002 is then removed. In this regard, it is possible to conduct a dry etching as well as a wet etching.
Referring to FIG. 10 c , an insulating and etching prevention layer 1003 is formed on the etched silicon according to the thermal oxidation process. That is to say, the insulating and etching prevention layer 1003 , such as SiO 2 , is formed on a surface of the silicon wafer.
Referring to FIG. 10 d , a polysilicon (Poly-Si) or an amorphous-Si is deposited on an etched portion of the silicon wafer 1001 according to low pressure chemical vapor deposition (LPCVD) or plasma chemical vapor deposition (PECVD) processes to form a sacrificial layer 1004 for an air space, and the resulting silicon wafer is polished to be flattened at a surface thereof. In this respect, in the case of using a silicon on insulator (SOI), the deposition of the polysilicon and polishing may be omitted.
Subsequently, silicon nitrides, such as Si 3 N 4 , are deposited in a preferable thickness of 0.1-5.0 μm according to the LPCVD or PECVD processes, and SiO 2 is deposited in a thickness of 0.1-5 μm according to thermal oxidation or PECVD processes, but this procedure may be omitted according to necessity.
Referring to FIG. 10 e , a lower supporter 1005 for supporting the piezoelectric material is deposited on the silicon wafer 1001 . A material constituting the lower supporter 1005 may be exemplified by Si oxides (e.g. SiO 2 , etc.), Si nitrides (e.g. Si 3 N 4 , etc.), ceramic substrates (Si, ZrO 2 , Al 2 O 3 and the like), and Si carbides. The lower supporter 1005 may be omitted, if necessary.
Referring to FIG. 10 f , a lower electrode 1006 is formed on the lower supporter 1005 , in which examples of material for the lower electrode 1006 may include Pt, Ta/Pt, Ni, Au, Al, RuO 2 and the like. In this case, the material is deposited in a thickness of 0.01-3 μm using sputtering or evaporation processes.
Referring to FIG. 10 g , a piezoelectric material 1007 is formed in a thickness of 0.01-20.0 μm on the lower electrode 1006 according to a wet process (screen printing, sol-gel coating and the like) or a dry process (sputtering, evaporation, vapor deposition and the like). Both longitudinal type and transverse type piezoelectric materials may be used as the piezoelectric material 1007 . Examples of the piezoelectric material may include PzT, PNN-PT, ZnO and the like, and the piezoelectric electrolytic material contains at least one selected from the group consisting of Pb, Zr, Zn, or titanium.
Referring to FIG. 10 h , an upper electrode 1008 is formed on the piezoelectric material 1007 , in which a material of the upper electrode may be exemplified by Pt, Ta/Pt, Ni, Au, Al, and RuO 2 . In this case, the upper electrode is formed in a thickness of 0.01-3 μm using the sputtering or evaporation processes.
Referring to FIG. 10 i , a micromirror 1009 is attached to the upper electrode 1008 , in which examples of a material of the micromirror include a light-reflective material, such as Ti, Cr, Cu, Ni, Al, Au, Ag, Pt, and Au/Cr.
At this time, the upper electrode 1008 may be used as the micromirror, or a separate micromirror may be deposited on the upper electrode 1008 .
Referring to FIG. 10 j , after such a mother body of a diffractive thin-film piezoelectric micromirror array is patterned using a mask layer, such as a photoresist, the micromirror 1009 , upper electrode 1008 , piezoelectric material 1007 , lower electrode 1006 , and lower supporter 1005 are etched to form the diffractive thin-film piezoelectric micromirror array. Subsequently, the sacrificial layer 1004 is etched using XeF 2 gas.
Heretofore, there has been described removal of the sacrificial layer 1004 after the diffractive thin-film piezoelectric micromirror array is formed from the mother body of the diffractive thin-film piezoelectric micromirror array, but the micromirror array may be formed after the sacrificial layer 1004 is removed.
In other words, a hole is formed in a portion of the mother body of the diffractive thin-film piezoelectric micromirror array, on which the lower supporter 1005 is not formed, and the sacrificial layer 1004 is etched using XeF 2 gas. Subsequently, the mother body of the diffractive thin-film piezoelectric micromirror array is patterned using the mask layer, such as the photoresist, and the micromirror 1009 , upper electrode 1008 , piezoelectric material 1007 , lower electrode 1006 , and lower supporter 1005 are etched to form the micromirror array.
FIGS. 11 a to 11 c illustrate various diffractive thin-film piezoelectric micromirrors having recesses, in which piezoelectric materials are not deformed.
FIG. 11 a illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate and supported by ends thereof. Additionally, a lower electrode 1006 a , a piezoelectric material layer 1007 a , an upper electrode 1008 a , and a micromirror 1009 a are positioned on a lower supporter 1005 a.
FIG. 11 b illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate and supported by ends thereof. In this respect, a micromirror 1009 b is positioned on the center part of a lower supporter 1005 b . Furthermore, a lower electrode 1006 b , a piezoelectric material layer 1007 b , and an upper electrode 1008 b are positioned on both ends of a lower supporter 1005 b. To produce such a diffractive thin-film piezoelectric micromirror, after the upper electrode 1008 b is formed, the center portions of the lower electrode 1006 b , piezoelectric material layer 1007 b , and upper electrode 1008 b are etched, and the micromirror 1009 b is then formed on the center part.
FIG. 11 c illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate and supported by ends thereof. In this regard, a lower electrode 1006 c , a piezoelectric material layer 1007 c , an upper electrode 1008 c , and a micromirror 1009 c are positioned on the center part of a lower supporter 1005 c.
FIGS. 12 a to 12 c illustrate various diffractive thin-film piezoelectric micromirrors having recesses, in which piezoelectric materials are deformed.
FIG. 12 a shows that when voltage is applied to upper and lower parts of a piezoelectric material 1007 a , a lower supporter 1005 a , a lower electrode 1006 a , a piezoelectric material layer 1007 a , an upper electrode 1008 a , and a micromirror 1009 a are warped downward by contractile and expansive forces of the piezoelectric material. At this time, the contractile force acts on the piezoelectric material 1007 a in a horizontal direction, causing the piezoelectric material 1007 a to shrink in a horizontal direction. However, since a lower side of the piezoelectric material 1007 a is firmly attached to the lower supporter 1005 a , the contractile force causes the piezoelectric material 1007 a to be warped downward.
FIG. 12 b shows that when voltage is applied to upper and lower sides of a piezoelectric material layer 1007 b positioned on both ends of a lower supporter 1005 b , a contractile force is generated in a horizontal direction. At this time, the contractile force acts on the piezoelectric material 1007 b in the horizontal direction, causing the piezoelectric material 1007 b to shrink in the horizontal direction. However, since a lower side of the piezoelectric material 1007 b is firmly attached to the lower supporter 1005 b , the contractile force causes the piezoelectric material 1007 b to be warped upward. As a result, the lower supporter 1005 b and a micromirror 1009 b positioned on the center of the lower supporter 1005 b are warped upward.
FIG. 12 c shows that when voltage is applied to upper and lower sides of a piezoelectric material 1007 c positioned on the center of a lower supporter 1005 c , a lower electrode 1006 c , a piezoelectric material layer 1007 c , an upper electrode 1008 c , and a micromirror 1009 c are warped upward.
FIG. 13 a illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having recesses and the same dimensions are arranged. The diffractive thin-film piezoelectric micromirrors are vertically moved by the application of voltage.
FIG. 13 b illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having recesses and different dimensions are alternately arranged. The diffractive thin-film piezoelectric micromirrors are vertically moved by the application of voltage.
FIG. 13 c illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having recesses and the same dimension are arranged. At this time, the micromirrors are formed on a whole upper side of an insulating layer to diffract incident light.
FIGS. 14 a to 14 h illustrate production of a thin-film piezoelectric light modulator having a raised part according to another embodiment of the present invention.
Referring to FIG. 14 a , an insulating and etching prevention layer 2002 is formed on a silicon wafer according to the thermal oxidation process. That is to say, the insulating and etching prevention layer 2002 made of SiO 2 is formed on a surface of the silicon wafer.
Additionally, a polysilicon (Poly-Si) or an amorphous-Si is deposited on the insulating and etching prevention layer 2002 of the silicon wafer 2001 according to LPCVD or PECVD processes to form an air space, and the resulting silicon wafer is polished to be flattened at a surface thereof to form a sacrificial layer 2003 .
Subsequently, a mask layer 2004 is formed in a thickness of 0.1-3.0 μm through a thermal oxidation process on the sacrificial layer 2003 , and then patterned for silicon etching.
With reference to FIG. 14 b , silicon is etched using a solution capable of etching silicon, such as TMAH or KOH, in a predetermined thickness, and the mask layer 2004 is then removed.
Next, after silicon nitrides, such as Si 3 N 4 , are deposited in a preferable thickness of 0.1-5.0 μm according to the LPCVD or PECVD processes, SiO 2 is deposited in a thickness of 0.1-3 μm according to thermal oxidation or PECVD processes, but this procedure may be omitted according to necessity.
Successively, referring to FIG. 14 c , a lower supporter 2005 for supporting a piezoelectric material is deposited on the insulating and etching prevention layer 2002 and sacrificial layer 2003 . In this case, a material constituting the lower supporter 2005 may be exemplified by Si oxides (e.g. SiO 2 , etc.), Si nitrides (e.g. Si 3 N 4 , etc.), ceramic substrates (e.g. Si, ZrO 2 , Al 2 O 3 and the like), and Si carbides. The lower supporter 2005 may be omitted, if necessary.
Referring to FIG. 14 d , a lower electrode 2006 is formed on the lower supporter 2005 , in which examples of material for the lower electrode 2006 may include Pt, Ta/Pt, Ni, Au, Al, RuO 2 and the like, and the material is deposited in a thickness of 0.01-3 μm using sputtering or evaporation processes.
Referring to FIG. 14 e , a piezoelectric material 2007 is formed in a thickness of 0.01-20.0 μm on the lower electrode 2006 according to a wet process (screen printing, sol-gel coating and the like) or a dry process (sputtering, evaporation, vapor deposition and the like). Both longitudinal type and transverse type piezoelectric materials may be used as the piezoelectric material 2007 . Examples of the piezoelectric material may include PZT, PMN-PT, PLZT, AIN, ZnO and the like, and the piezoelectric electrolytic material contains at least one selected from the group consisting of Pb, Zr, Zn, or titanium.
Referring to FIG. 14 f , an upper electrode 2008 is formed on the piezoelectric material 2007 , in which a material of the upper electrode may be exemplified by Pt, Ta/Pt, Ni, Au, Al, Ti/Pt, IrO 2 and RuO 2 , and the upper electrode is formed in a thickness of 0.01-3 μm using the sputtering or evaporation processes.
Referring to FIG. 14 g , a micromirror 2009 is attached to the upper electrode 2008 . Examples of a material of the micromirror include a light-reflective material, such as Ti, Cr, Cu, Ni, Al, Au, Ag, Pt, and Au/Cr.
At this time, the upper electrode 2008 may be used as the micromirror, or a separate micromirror may be deposited on the upper electrode 2008 .
Referring to FIG. 14 h , after such a mother body of a diffractive thin-film piezoelectric micromirror array is patterned using a mask layer, such as a photoresist, the micromirror 2009 , upper electrode 2008 , piezoelectric material 2007 , lower electrode 2006 , and lower supporter 2005 are etched to form the diffractive thin-film piezoelectric micromirror array. Subsequently, the sacrificial layer 2003 is etched using XeF 2 gas.
Heretofore, there has been described removal of the sacrificial layer 2003 after the diffractive thin-film piezoelectric micromirror array is formed from the mother body of the diffractive thin-film piezoelectric micromirror array, but the micromirror array may be formed after the sacrificial layer 2003 is removed.
In other words, a hole is formed in a portion of the mother body of the diffractive thin-film piezoelectric micromirror array, in which the lower supporter 2005 is not formed, the sacrificial layer 2003 is etched using XeF 2 gas. The mother body of the diffractive thin-film piezoelectric micromirror array is patterned using the mask layer, such as the photoresist, and the micromirror 2009 , upper electrode 2008 , piezoelectric material 2007 , lower electrode 2006 , and lower supporter 2005 are etched to form the micromirror array.
FIGS. 15 a to 15 c illustrate various diffractive thin-film piezoelectric micromirrors having raised parts, in which piezoelectric materials are not deformed.
FIG. 15 a illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate and supported by ends thereof. Additionally, a lower electrode 2006 a , a piezoelectric material layer 2007 a , an upper electrode 2008 a , and a micromirror 2009 a are positioned on a lower supporter 2005 a . FIG. 15 a is different from FIG. 11 a in that a portion of the piezoelectric material is raised upward and spaced from an insulating and etching prevention layer.
FIG. 15 b illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate and supported by ends thereof. In this respect, a micromirror 2009 b is positioned on the center part of a lower supporter 2005 b . Furthermore, a lower electrode 2006 b , a piezoelectric material layer 2007 b , and an upper electrode 2008 b are positioned on both ends of the lower supporter 2005 b . To produce such a diffractive thin-film piezoelectric micromirror, after the upper electrode 2008 b is formed, the center portions of the lower electrode 2006 b , piezoelectric material layer 2007 b , and upper electrode 2008 b are etched, and the micromirror 2009 b is then formed on the center part. FIG. 15 b is different from FIG. 11 b in that a portion of the piezoelectric material is raised upward and spaced from an insulating and etching prevention layer.
FIG. 15 c illustrates that a sacrificial layer of a silicon wafer is replaced with an air space, and thus, a piezoelectric material is partially spaced from a surface of a substrate by ends thereof. In this regard, a lower electrode 2006 c , a piezoelectric material layer 2007 c , an upper electrode 2008 c , and a micromirror 2009 c are positioned on the center part of a lower supporter 2005 c. FIG. 15 c is different from FIG. 11 c in that a portion of the piezoelectric material is raised upward and spaced from an insulating and etching prevention layer.
FIGS. 16 a to 16 c illustrate various diffractive thin-film piezoelectric micromirrors having raised parts, in which piezoelectric materials are deformed.
FIG. 16 a shows that when voltage is applied to upper and lower sides of a piezoelectric material 2007 a , a lower supporter 2005 a , a lower electrode 2006 a , a piezoelectric material layer 2007 a , an upper electrode 2008 a , and a micromirror 2009 a are warped downward by contractile and expansive forces of the piezoelectric material. At this time, the contractile force acts on the piezoelectric material 2007 a in a horizontal direction, endeavoring the piezoelectric material 2007 a to shrink in a horizontal direction. However, since a lower side of the piezoelectric material 2007 a is firmly attached to the lower supporter 2005 a , the contractile force causes the piezoelectric material 2007 a to be warped downward.
FIG. 16 b shows that when voltage is applied to upper and lower sides of a piezoelectric material layer 2007 b positioned on both ends of a lower supporter 2005 b , a contractile force is generated in a horizontal direction. At this time, the contractile force acts on the piezoelectric material 2007 b in the horizontal direction, causing the piezoelectric material 2007 b to shrink in the horizontal direction. However, since a lower side of the piezoelectric material 2007 b is firmly attached to the lower supporter 2005 b , the contractile force enables the piezoelectric material 2007 b to be warped upward. As a result, the lower supporter 2005 b and a micromirror 2009 b positioned on the center of the lower supporter 2005 b are warped upward.
FIG. 16 c shows that when voltage is applied to upper and lower parts of a piezoelectric material 2007 c positioned on the center of a lower supporter 2005 c , a lower electrode 2006 c , a piezoelectric material layer 2007 c , an upper electrode 2008 c , and a micromirror 2009 c are warped upward.
FIG. 17 a illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having raised parts and the same width are arranged. The diffractive thin-film piezoelectric micromirrors are vertically moved by the application of voltage.
FIG. 17 b illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having raised parts and different widths are alternately arranged. The diffractive thin-film piezoelectric micromirrors are vertically moved by the application of voltage.
FIG. 17 c illustrates operation of a display element in which diffractive thin-film piezoelectric micromirrors having raised parts are arranged at regular intervals. The micromirrors are formed on an upper side of an insulating layer to diffract incident light.
Meanwhile, the specification of the present invention describes only a piezoelectric material layer consisting of a single layer, but the piezoelectric material layer may comprise multiple layers so as to realize low voltage operation. At this time, the lower and upper electrodes consist of multiple layers.
In other words, it is possible to construct in such a manner that a first lower electrode, a first piezoelectric material layer, a first upper electrode, a second lower electrode, a second piezoelectric material layer, a second upper electrode, a third lower electrode . . . are sequentially laminated upward.
As described above, use of a piezoelectric sensor makes a correlation between voltage and displacement linear, whereas the correlation is nonlinear in the case of an electrostatic method according to a conventional technology.
Compared to the electrostatic method, the present invention is advantageous in that it is possible to gain the desired displacement at a relatively low voltage and to gain a high operation speed.
Another advantage of the present invention is that since it is possible to reliably control displacement of a ribbon, it is possible to achieve a gray scale control unlike the electrostatic method.
Furthermore, in the present invention, in the course of producing a piezoelectric micromirror array, it is possible to design various lengths and widths of ribbons, and thus, it is easy to tune light efficiency so as to satisfy requirements of relevant applications.
The diffractive thin-film piezoelectric micromirror and the production of the same according to the present invention have been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. | Disclosed is a diffractive micromirror and a method of producing the same. More particularly, the present invention pertains to a diffractive thin-film piezoelectric micromirror, which is operated in a piezoelectric operation manner to assure excellent displacement, operation speed, reliability, linearity, and low voltage operation, and a method of producing the same. The diffractive thin-film piezoelectric micromirror includes a silicon substrate on which a recess is formed to provide an air space to the center thereof, and a piezoelectric mirror layer having a band shape, which is attached to the silicon substrate along both ends of the recess at both ends thereof while being spaced from the bottom of the recess at a center portion thereof and which includes a thin-film piezoelectric material layer to be vertically movable when voltage is applied to the piezoelectric material layer, and thus diffracts an incident light beam. | 6 |
This is a division of application Ser. No. 08/593,296 , filed Jan. 29, 1996, now U.S. Pat. No. 5,707,708 which is a continuation of application Ser. No. 08/350,349, filed Dec. 6, 1994, abandoned, which is a continuation-in-part of application Ser. No. 08/126,149, filed Sep. 23, 1993, abandoned, which is a continuation of application Ser. No. 07/809,843, filed Dec. 18, 1991, abandoned, which is a continuation-in-part of application Ser. No. 07/626,885, filed Dec. 13, 1990, now abandoned.
FIELD OF THE INVENTION
The present invention relates to polyamide textile substrates treated with stain-resistant compositions comprising water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers, and processes for their synthesis. The substrates of this invention possess stain-resistance but do not suffer from yellowing to the extent that some previously known materials do.
BACKGROUND OF THE INVENTION
Polyamide substrates, such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages. An especially troublesome staining agent is FD&C Red Dye No. 40, commonly found in soft drink preparations. Different types of treatments have been proposed to deal with staining problems. One approach is to apply a highly fluorinated polymer to the substrate. Another is to use a composition containing a sulfonated phenol-formaldehyde condensation product.
For example, Liss et al., in U.S. Pat. No. 4,963,409, disclose stain-resistant synthetic polyamide textile substrates having deposited on them sulfonated phenol-formaldehyde polymeric condensation products. However, sulfonated phenol-formaldehyde condensation products are themselves subject to discoloration; commonly they turn yellow. Yellowing problems are described by W. H. Herrunpel in a Mar. 19, 1982 article in America's Textiles, entitled Reversible Yellowing Not Finisher's Fault. Hemnmpel attributes yellowing to exposure of a phenol-based finish to nitrogen oxides and/or ultraviolet radiation. To deal with the yellowing problem, the condensation products were modified by Liss et al. by acylation or etherification of some of the phenolic hydroxyls. In a preferred embodiment disclosed by Liss et al., the modified condensation products were dissolved in a hydroxy-containing solvent, such as ethylene glycol prior to there being applied to the textile substrate.
Allen et al., in U.S. Pat. No. 3,835,071, disclose rug shampoo compositions which upon drying leave very brittle, non-tacky residues which are easily removed when dry. The compositions comprise water-soluble metal, ammonium or amine salt of a styrene-maleic anhydride copolymer, or its half ester, and a detergent. Water-soluble metal salts of Group II and the alkali metals (particularly magnesium and sodium) are preferred and ammonium salts are most preferred by Allen et al.
On the other hand, Fitzgerald et al., in U.S. patent application Ser. No. 07/502819, filed Apr. 2, 1990, now U.S. Pat. No. 5,001,004 disclose the usefulness of aqueous solutions of hydrolyzed vinylaromatic/maleic anhydride copolymers in the treatment of textiles to render them resistant to staining. The preferred copolymer of Fitzgerald et al. is a hydrolyzed styrene/maleic anhydride copolymer. Fitzgerald et al. disclose that the monoalkyl ester of their maleic anhydride/vinyl aromatic polymer was ineffective as a stain-resist.
Maleic anhydride/alpha-olefin polymers are known. Reissue U.S. Pat. No. 28,475 discloses copolymerization of maleic anhydride and 1-olefins, such as, 1-hexene, 1-tetradecene and 1-octadecene. European Patent Application No. 306.992 published 15 Mar. 1989 discloses maleic anhydride/-1-alkene Terpolymerization of Maleic Anhydride With Vinyl Monomers, J. Polymer SGI., Part A: Polym. Chem., 27 (12). 4099-108, disclose terpolymers of maleic anhydride with (i) 1-hexene, propylene, isobutylene, styrene, isoprene or 1,3-butadiene, and (ii) methyl methacrylate, methyl acrylate or acrylonitrile.
BRIEF SUMMARY OF THE INVENTION
The present invention provides polyamide fibrous substrates treated with water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers so as to impart stain-resistance to the substrates, and methods for preparing the same. Commonly, prior are materials known to be useful as stain-blockers were sulfonated phenol-formaldehyde condensates (excepting those of Fitzgerald et al., supra). Finding a non-sulfonated material, such as the water-soluble or water-dispersible alpha-olefin/maleic anhydride polymers of this invention, to be useful for this purpose was unexpected.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the use of water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers, or mixtures of the same, as stain-resists for fibrous polyamides. A variety of linear and branched chain alpha-olefins can be used for the purposes of this invention. Particularly useful alpha-olefins are 1-alkenes, containing 4 to 12 carbon atoms, preferably C 4-10 , such as isobutylene, 1-butene, 1-hexene, 1-octene, 1-decene, and dodecene, with isobutylene and 1-octene being preferred and 1-octene being most preferred. A part of the alpha-olefins can be replaced by other monomers, with isobutylene being most preferred. A part of the alpha-olefins can be replaced by other monomers, e.g. up to 50 wt. % of alkyl(C 1-4 ) acrylates, alkyl(C 1-4 ) methacrylates, vinyl acetate, vinyl chloride, vinylidine chloride, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixtures of the same.
In accordance with the present invention, it has been unexpectedly found that water-soluble or water-dispersible interpolymers (i.e. copolymers, terpolymers, and the like) of maleic anhydride and one or more 1-alkenes having 4 to 12 carbon atoms, particularly isobutylene and 1-octene, impart excellent stain-resistance to polyamide substrates (e.g. carpeting) at low pH. Copolymers of maleic anhydride with butadiene, ethylene, propylene or a 1-alkene containing having 14 to 24 carbon atoms were found by the inventor to be unsatisfactory for commercial purposes as stain-resists on such substrates.
A part of the maleic anhydride (up to 30 weight %) can be replaced by acrylic or methacrylic acid. In another embodiment, a part (1-75%) of the maleic anhydride can be replaced by maleimide, N-alkyl(C 1-4 ) maleimides, N-phenylmaleimide, fumaric acid, crotonic acid, cinnamic acid, alkyl(C 1-18 ) esters of the foregoing acids, cycloalkyl(C 3-8 ) esters of the foregoing acids, sulfated castor oil, or the like. At least 95 wt. % of the maleic anhydride co- or terpolymers having a number average molecular weight of in the range between about 700 and 200,000, preferably between about 1000 and 100,000.
The maleic anhydride polymers useful in the present invention can be prepared according to methods well-known in the art. The maleic anhydride polymers thus obtained can be hydrolyzed to the free acid or their salts by reaction with water or alkali, or they can also be reacted with C 1-4 alkyl alcohol to provide polymeric alpha-olefin/maleic acid monoesters, which have stainblocking properties. Generally, the hydrolyzed maleic anhydride polymer, or the monoester polymer, should be sufficient water-soluble that uniform application to a fibrous polyamide surface can be achieved at an appropriate acidity. However, applications using water dispersions of the polymer mixed with a suitable surfactant may be used to impart stain-resistance.
One can blend the stain-resists of the present invention with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in U.S. Pat. Nos. 4,833,009 and 4,965,325; methaclylic acid polymers disclosed in U.S. Pat. No. 4,937,123; or hydrolyzed polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald et al., supra.
The polymers suitable for the purposes of this invention contain between about 0.4 and 1.3 polymer units derived from one or more olefin monomers per polymer unit derived from maleic anhydride. The alpha-olefin content of the polymers of this invention comprise between (a) 100 and 80 mol % of at least one 1-alkene containing 4 to 12 carbon atoms and (b) 0 to 20 mol % of at least one 1-alkene containing 3, or 14 to 24, carbon atoms. Polymers containing about one polymer unit derived from one or more olefin monomers per polymer unit derived from maleic anhydride are most effective in imparting stain resistance to textile substrates. The molecular weight of the polymers useful in the invention does not appear to be a limitation so long as the polymers are water-soluble or water-dispersible. Thus, for example, hydrolyzed isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 impart good stain-resistance to polyamide substrates. Even at a pH as low as 1.5, water-soluble isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 remained in solution in water at 60° C.
The polymers suitable for the purposes of this invention can be prepared by hydrolyzing the maleic anhydride/olefin polymers according to methods well-known in the art. For example, they can be hydrolyzed to the free acid or their salts by reaction with water of alkali. Generally, the maleic anhydride polymer should be sufficiently water-soluble that uniform application to a fiber surface can be achieved at an appropriate acidity. However, applications using dispersions of the polymers with suitable surfactants may be used to impart stain-resistance.
Suitable maleic anhydride polymers can be conveniently obtained by hydrolysis of "Isobam"-01, an isobutylene maleic anhydride copolymer of molecular weight around 10,000, "Isobam"-04 a similar polymer having a molecular weight of around 40,000 or "Isobam"-10 a similar polymer having a molecular weight of around 100,000 with sodium hydroxide. Other suitable maleic anhydride polymers include BM-30 available from Kuraray Co. (Japan). BM-30 is an isobutylene/maleic anhydride/N-phenylmaleirnide terpolymer having a molecular weight of around 40,000. Other suitable copolymers include monoesters of C 4-12 alpha-olefin/maleic anhydride copolymers. The monoesters can be obtained by a range of reactions well known to those skilled in the art. A preferred method is by reaction with an alcohol by heating under reflux with the alcohol and then removing excess alcohol. Preferred alcohols are C 1-4 alcohols, especially methanol and ethanol.
Preparation of maleic anhydride/alpha-olefin polymers is also described in Reissue U.S. Pat. No. 28,475, in EP 306992 and by Florjanczyk et al. in J. Polymer SCI., Part A, Polymer Chem., 27 (12) pages 4099 to 4108, the disclosure of which is specifically incorporated by reference. These references contain further teaching of techniques for the preparation of such polymers.
The olefin/maleic anhydride polymers of this invention can be used as such in treating polyamide textile substrates. They can be effectively applied to polyamide fibrous substrates by a wide variety of methods known to those skilled in the art, such as:
padding,
spraying,
foaming in conjunction with foaming agents,
batch exhaust in beck dyeing equipment, or
continuous exhaust during a continuous dyeing operation.
They can be applied by such methods to dyed or undyed polyamide textile substrates. In addition, they can be applied to such substrates in the absence or presence of a polyfluoroorganic oil-, water-, and/or soil-repellent materials. In the alternative, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the polymers of this invention thereto.
The quantities of the polymers of this invention which are applied to the textile substrate are amounts effective in imparting stain-resistance to the substrate. Those amounts can be varied widely; in general, one can use between 1 and 5% by weight of them based on the weight of the textile substrate, usually 2.5% by weight or less. The polymers can be applied, as is common in the art, at pHs ranging between about 2 an d7. However, more effective exhaust deposition can be obtained at a pH as low as 1.5. When the latter low pH is used, the preferred level of application to the textile substrate is about 2.5% by weight, based on the weight of the textile substrate. In an embodiment, a pH between about 2 and 3 is used. More effective stainblocking is obtained if the polymers are applied to the textile substrate at either 20° C. followed by heat treatment at a temperature in the range between about 50 and 150° C. for about 1 to 60 minutes, or applied at temperatures in the range between about 40° and 95° C. for about 1 to 60 minutes. For example, at a pH between about 2 and 3, a temperature between about 70° and 90° C. is preferred. However, stain-blocking can be obtained when application is effected even at that of cold tap water (10°-15° C.
The polymers of this invention can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation or in the form of aqueous shampoo preparation, with or without one or more polyfluoroorganic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described 10 above, at temperatures described, and at a pH between about 1 and 12, preferably between about 2 and 9.
The following Examples are given to illustrate the invention not limit it. Unless otherwise indicated, all parts and percentages are by weight and temperature sin the Examples and Tests are in degrees Celsius. In the examples that follow, stain resistance was measured by the technique described below.
EXAMPLE 1
An isobutylene/maleic anhydride copolymer (10 g) having a number average molecular weight (GPC) of 32,600 and an MW/M n of 2.96, commercially available from Kuraray Co. (Japan) as "Isobam"-04, was hydrolyzed to a 10 wt. % solution in accordance with the method described in Example 2. A 1% aqueous solution of the resulting isobutylene/maleic acid copolymer remained clear down to pH 1.5 at 60° C.
EXAMPLE 2
An isobutylene/maleic anhydride copolymer (10 g) having a number average molecular weight (GPC) of 91,400 and an MW/M n of 2.86, commercially available from Kuraray Co. (Japan) as "Isobam"-10, was hydrolyzed to a 10 wt. % solution in accordance with the method described in Example 2. A 1% aqueous solution of the resulting water-soluble maleic anhydride/isobutylene copolymer at 60° C. became cloudy at pH 1.6.
EXAMPLE 3
An isobutylene/maleic anhydride/ N-phenylmaleimide terpolymer (10 g) having a molecular weight 40,000 (GPC), commercially available from Kuraray Co. (Japan) as BM-30 polymer, was hydrolyzed to a 10 wt. % solution by the method described in Example 2. A 1% aqueous solution of the resulting water-soluble maleic anhydride/isobutylene/maleimide terpolymer at 60° C. became cloudy at pH 2.5.
EXAMPLE 4
A solution of maleic anhydride (9.8 g-0.1 mol) and 1-hexene (8.4 g-0.1 mole) in propylene glycol methyl ether acetate (30 g) was heated under agitation and nitrogen to 60 deg.C. A solution of 2.5 g of 75 wt. % t-butyl peroxyneodecanoate in 6 g of propylene glycol methyl ether acetate was then injected into the reaction vessel within half hour via a syringe pump. The reactants were agitated for another 2 hours at 60° C. before being cooled to room temperature. The product was the poured into methanol which caused precipitation of a white solid which was filtered and air dried to give 10.5 g of a maleic anhydride/1-hexene copolymer. Hydrolysis was carried out by a procedure similar to that described in Example 2.
EXAMPLE 5
A solution of 9.8 g of maleic anhydride (0.1 mole) and 11.2 g of 1-octene (0.1 mole) in 30 g of propylene glycol methyl ether acetate was heated under agitation and nitrogen to 95° C. A solution of 2 g of t-butyl peroxy-2-ethylhexanoate in 6 g of propylene glycol methyl ether acetate was then injected into the reaction vessel within half hour via a syringe pump. The reactants were agitated for another 2 hours at 95° C. before being cooled to room temperature. The product was then poured into methanol which caused precipitation of a white solid which was filtered and air-dried to give 12.7 g of a maleic acid/1-octene copolymer having a number 2 0 average molecular weight by vapor phase osmometry (VPO) of 2800. The approximate composition of the copolymer by 13 CNMR:
1-octene/maleic anhydride=0.72/1.00. Hydrolysis was carried out by a procedure similar to that of Example 2. A 1% aqueous solution of the resulting maleic acid/1-octene copolymer at 60° C. became cloudy at about pH 2.7.
EXAMPLE 6
The procedures for preparation and hydrolysis were similar to those of Example 5.
Reactants: 9.8 g of maleic anhydride (0.1 mole) 16.8 g 1-dodecene (0.1 mole).
EXAMPLE 7
An isobutylene/maleic anhydride copolymer (50 parts) having a number average molecular weight (GPC) of 32,000, commercially available from Kuraray Co. (Japan) as "Isobam"-04, was reacted under agitation with methanol (50 parts) at reflux temperature (about 65° C.) for 23 hours. Excess methanol was then removed at reduced pressure (20 mm Hg) at 70°-90° C. to give the isobutylene/maleic acid monomethyl ester which was then dissolved at room temperature in dilute ammonium hydroxide (2.5 parts of ammonia in 356 parts of water) to give a 14.5 wt. % solution.
EVALUATION METHOD
Nylon fiber was treated with 1.2 wt. % or 2.4 wt. % stain resist at a good-to-liquor ratio of 1:32 at a pH of 2.0 or 2.35 for 45 minutes at 80 or 95° C. The fiber was then washed, air-dried and exposed at room temperature to a dye solution consisting of 0.2 g of FD&C Red Dye No. 40 and 3.2 g of citric acid in 1 liter of deionized water at a goods-to-liquor ratio of 1:40. After approximately 65 hours, the dye adsorbed onto the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of the Control. Thus a number of 90 means 90% of the dye is adsorbed, indicating little stain resistance to the dye. The lower the number, the better is the resistance to stain. The results of the evaluation are in TABLE 1.
TABLE 1______________________________________ % Dye Adsorbed At 80° C. At 95° C.EXAMPLE pH 2.0 pH 2.35 pH 2.35 pH 2.35*______________________________________1 2 3 32 2 1 13 2 3 14 3 30 15 4 2 16 14 227 6 39 12CONTROL** 89 89______________________________________ *Fiber treated with 2.4 wt % stain resist **No stainblocker | A polyamide fibrous substrate having deposited on it an amount of a composition effective to impart stain-resistance comprising a water-soluble or water-dispersible alpha-olefin/maleic anhydride polymer or a mixture of said polymers, and processes for preparing the substrates. The maleic anhydride polymer is used either in hydrolyzed form or in the form resulting from reacting it with a lower alkyl alcohol so as to form an alpha-olefin/maleic acid monalkyl ester polymer. | 8 |
BACKGROUND
1. Technical Field
This disclosure relates to a system and method for impact mitigation of sudden carrier frequency shifts in OFDM receivers.
2. Description of the Related Art
In a GSM mobile phone with an integrated DVB-H (digital video broadcast-handheld) receiver for mobile TV reception it is desirable to share a common reference clock for reduction of cost, size, and power consumption. Certain GSM mobile phone implementations tune the reference clock by a few Hz in order to adapt to the reference clock of the base station. This tuning of the reference clock may occur as sudden frequency jumps. As a consequence, the local oscillator frequency of the DVB-H receiver will jump by the same relative amount as the reference frequency. For DVB-H reception, the amount of frequency jump may be up to about ¼ of the sub-carrier spacing of the underlying orthogonal frequency division multiplexing (OFDM) transmission method. If this amount of frequency shift is not compensated for, it causes severe interference between adjacent OFDM sub-carriers, such that the error probability at the receiver increases dramatically, causing loss of information in the video stream.
BRIEF SUMMARY
A subject of this disclosure provides a method and an arrangement for quickly detecting suddenly occurring frequency shifts of the received signal, measuring the amount of frequency offset, and compensating accordingly, in order to minimize the impact of the frequency jump.
A DVB-H receiver complies to ETSI EN 300744, V1.5.1: Digital Video Broadcasting (DVB): “Framing structure, channel coding and modulation for digital terrestrial transmission”, 2004; and in ETSI EN 302304, V1.1.1: Digital Video Broadcasting (DVB): “Transmission system for handheld terminals (DVB-H)”, 2004.
Certain GSM mobile phone transceiver implementations adapt their reference clock to the reference clock of the associated GSM base station. The reference clock is typically adapted by a voltage control, e.g., by a voltage controlled temperature compensated crystal oscillator (VCTCXO). This adaptation may occur as jumps, especially during handover from one GSM base station to another one.
In a DVB-H receiver implemented in a GSM device, several clocks are generated within a clock generation unit using a phase locked loop (PLL). The local oscillator (LO) frequency as well as the sampling clock are fixedly related to the reference clock. Since the DVB-H receiver uses the same reference clock, the change of the reference frequency will cause a proportional change of the LO frequency which controls the selected received frequency band as well as the sampling clock and all other frequencies derived from it.
FIG. 1 shows a OFDM receiver which employs phase tracking (also called common phase error correction) to reduce the impact of low frequency phase noise in the LO carrier of both the receiver and the transmitter, and frequency tracking to adapt to a slow mutual drift of transmitter and receiver LO carrier frequencies.
As is further shown in FIG. 1 , the input signal is a complex digital baseband receive signal. It is frequency-shifted by multiplication with a complex rotating exponential function with a constant phase increment from sample to sample. After removing the guard interval, the Fast Fourier Transform converts a block of received samples into corresponding frequency-domain symbols. The common phase error, i.e., the average phase rotation in the complex plane from one OFDM symbol to the next, is estimated, and it is used as an input for both phase tracking and frequency tracking. For frequency tracking, the phase delta is fed into a loop filter which adjusts the compensation frequency value at the frequency offset compensation unit. For phase tracking, the phase delta is accumulated and used as a compensation phase in the common phase error compensation. After this, the channel transfer function is estimated and used to demodulate the data. Demodulated data are fed into a combined de-interleaving and error correcting decoding to obtain the received data. In DVB-H, this combined de-interleaving and error correcting decoding typically has three layers, a bit and symbol de-interleaver with a Viterbi decoder, a convolutional de-interleaver with a Reed-Solomon decoder, and a large block de-interleaver with a second Reed-Solomon decoder.
A fast jump of the down-converter frequency in the DVB-H receiver causes only a slow adaptation of the frequency tracking. As a result, the frequency offset is compensated for slowly, meaning that a large number of OFDM symbols is severely affected by inter-carrier interference. This may result in erroneous receive data and visual errors or dropouts of TV reception.
An embodiment reduces the impact of frequency shifts caused by reference clock adaptation in a GSM device on OFDM symbol reception in a DVB-H receiver implemented in the GDM device. An embodiment of a method comprises the steps of determining a frequency jump in preparation of the complex digital baseband receive signal by comparing the phase change of the signal with a threshold value of the phase and, during signal transformation, preventing failures caused by such frequency jump.
In an embodiment, the method comprises the steps of: compensating a frequency offset of a complex digital baseband receive signal at an input of the arrangement; removing a guard interval from the frequency shifted signal; converting a block of received samples of the signal with the guard interval removed into corresponding frequency-domain symbols; estimating the average phase rotation in the complex plane from one OFDM symbol to the next one and generating a phase delta as an output; adjusting the compensation frequency value at the frequency offset compensation unit using the phase delta as an input; accumulating the phase delta and generating a compensation phase; compensating common phase error of the signal with the frequency-domain symbols; estimating the channel transfer function from the phase error compensated signal; demodulating data from the phase error compensated signal using the estimated channel transfer function; de-interleaving and error correcting the demodulated data and decoding same to obtain received data; comparing an absolute value of the estimated common phase error with an adjustable threshold; and determining that a frequency jump has been detected if the threshold is exceeded.
Three example methods of compensating for a detected frequency jump are discussed below. The three example methods may be employed separately or combined with each other or with other methods of addressing a detected frequency jump in various embodiments.
A first example embodiment of a method of compensating for a detected frequency jump comprises the steps of: forcing a pause of frequency tracking and keeping the last compensation frequency value; concurrently forcing common phase error estimation, in case it was not used by default; estimating the frequency offset based on the phase delta between two subsequent OFDM symbols once the frequency jump has settled; adding the frequency offset to the last setting of the compensation frequency and adopting the summed value as the new compensation frequency; once, this new value has been set, switching on again the frequency tracking.
A second example embodiment of a method of compensating for a detected frequency jump comprises adapting a time-interpolation across several OFDM symbols during channel estimation such that corrupted OFDM symbols are determined, wherein the time-interpolation across several OFDM symbols inside the channel estimator may be adapted such that corrupted OFDM symbols which contain severely distorted pilot symbols are ignored in channel estimation during one cycle of frequency jump exception states.
A third example embodiment of a method of compensating for a detected frequency jump comprises enabling dedicated algorithms inside the demodulation unit which improve reception in presence of inter-carrier interference, such as inter-carrier interference subtraction during one cycle of frequency jump exception states.
In one embodiment, a system comprises means for determining a frequency jump in preparation of the complex digital baseband receive signal by comparing the phase change of the signal with a threshold value of the phase, and means for preventing failures caused by a frequency jump during signal transformation.
In one embodiment, the system comprises: means for compensating a frequency offset of a complex digital baseband receive signal at an input of the arrangement, for instance a frequency offset compensation unit; means for removing the guard interval from the frequency shifted signal, for instance a guard interval removal unit; means for converting a block of received samples of the signal with the guard interval removed into corresponding frequency-domain symbols, for instance a Fast Fourier Transformation unit; means for estimating the average phase rotation in the complex plane from one OFDM symbol to the next one and for generating a phase delta at its output, for instance a common phase error estimation unit; means for adjusting the compensation frequency value at the frequency offset compensation unit using the phase delta at an input, for instance a frequency tracking loop filter; means for accumulating the phase delta and generating a compensation phase, for instance a phase error integrator; means for compensating the common phase error of the signal with the frequency-domain symbols, for instance a common phase error compensation unit; means for estimating the channel transfer function from the phase error compensated signal, for instance a channel estimation unit; means for demodulating data from the phase error compensated signal using the estimated channel transfer function, for instance a demodulation unit; means for de-interleaving and error correcting the demodulated data and for decoding to obtain received data, for instance a de-interleaver/error correcting decoder; means for comparing an absolute value of the estimated common phase error with an adjustable threshold, for instance a frequency offset estimator; and means for determining that a frequency jump has been detected if the threshold is exceeded, for instance a frequency jump detector.
Three example embodiments of systems for compensating for a detected frequency jump are discussed below. The three example embodiments may be employed separately or combined with each other or with other systems and subsystems of addressing a detected frequency jump in various embodiments. Compensating for frequency jumps may, for example, prevent failures caused by a frequency jump during signal transformation.
A first example embodiment of a system comprises means for determining that a frequency jump has been detected if the threshold is exceeded and means for performing the following actions: forcing a pause of frequency tracking and keeping the last compensation frequency value; concurrently forcing common phase error estimation, in case it was not used by default; estimating the frequency offset based on the phase delta between two subsequent OFDM symbols once the frequency jump has settled; adding the frequency offset to the last setting of the compensation frequency and taking the summed value as the new compensation frequency; once this new value has been set, switching on again the frequency tracking.
These means are implemented for instance by a frequency jump detector, a frequency offset estimator, and an exception controller which runs a state machine triggered by a detected frequency jump and which is connected with the frequency offset estimator and the frequency tracking loop filter.
A second example embodiment of a system comprises means for adapting a time-interpolation across several OFDM symbols during channel estimation such that corrupted OFDM symbols are determined, wherein the time-interpolation across several OFDM symbols within channel estimator may be adapted such that corrupted OFDM symbols which contain severely distorted pilot symbols are ignored in channel estimation during one cycle of frequency jump exception states. Those means are implemented for instance by an exception controller which runs a state machine triggered by a detected frequency jump and which is connected with the channel estimation unit.
A third example embodiment of a system comprises means for enabling dedicated algorithms inside the demodulation unit which improve reception in presence of inter-carrier interference, such as inter-carrier interference subtraction during one cycle of frequency jump exception states, for instance an exception controller which runs a state machine, triggered by a detected frequency jump, the exception controller being connected to the demodulation unit.
In one embodiment, a method of decoding a complex digital baseband signal in an OFDM receiver comprises: receiving a complex digital baseband signal; transforming the received signal; detecting a frequency jump by comparing a phase change of the transformed signal with a threshold phase value; compensating for the detected frequency jump; and decoding data from the transformed signal. In one embodiment, the method comprises: compensating for a frequency offset of the received complex digital baseband signal, generating a frequency shifted signal; removing a guard interval from the frequency shifted signal; converting a block of received samples of the signal with the guard interval removed into corresponding frequency-domain symbols; estimating an average phase rotation in a complex plane from one OFDM symbol to a next OFDM symbol and generating a phase delta as an output; adjusting a compensation frequency value using the phase delta as an input; accumulating the phase delta and generating a compensation phase; compensating for common phase error of the signal with the frequency-domain symbols; estimating a channel transfer function from the phase error compensated signal; demodulating data from the phase error compensated signal using the estimated channel transfer function; de-interleaving and error correcting the demodulated data and decoding same to obtain received data; comparing an absolute value of the phase delta with an adjustable threshold; and determining that a frequency jump has been detected if the threshold is exceeded. In one embodiment, compensating for a detected frequency jump comprises: pausing frequency tracking and keeping a last compensation frequency value; forcing common phase error estimation; estimating the frequency offset based on the phase delta between two subsequent OFDM symbols after the frequency jump has settled; adding the estimated frequency offset to the last compensation frequency value and adopting the summed value as a new compensation frequency value; and once this new compensation frequency value has been set, switching on again the frequency tracking. In one embodiment, compensating for a detected frequency jump comprises: adapting a time-interpolation across several OFDM symbols during channel estimation such that corrupted OFDM symbols are determined, wherein corrupted OFDM symbols which contain heavily distorted pilot symbols are ignored in channel estimation during one cycle of frequency jump exception state. In one embodiment, compensating for a detected frequency jump comprises: enabling dedicated algorithms during demodulation which improve reception in presence of inter-carrier interference. In one embodiment, compensating for a detected frequency jump comprises performing inter-carrier interference subtraction during one cycle of frequency jump exception state. In one embodiment, compensating for a detected frequency jump further comprises: pausing frequency tracking and keeping a last compensation frequency value; forcing common phase error estimation; estimating the frequency offset based on the phase delta between two subsequent OFDM symbols after the frequency jump has settled; adding the estimated frequency offset to the last compensation frequency value and adopting the summed value as a new compensation frequency value; and once this new compensation frequency value has been set, switching on again the frequency tracking. In one embodiment, compensating for a detected frequency jump further comprises: ignoring OFDM symbols which contain heavily distorted pilot symbols during one cycle of a frequency jump exception state.
In one embodiment, a system comprises: means for transforming a complex digital baseband signal; means for decoding data coupled to the means for transforming; means for detecting frequency jumps including means for comparing a phase change to a threshold value; and means for compensating for detected frequency jumps during signal transformation coupled to the means for detecting frequency jumps. In one embodiment, the system comprises means for compensating for frequency offsets; means for removing guard intervals coupled to the means for compensating for frequency offsets; means for converting blocks of received samples into corresponding frequency-domain symbols coupled to the means for removing guard intervals; means for estimating average phase rotation in a complex plane from one OFDM symbol to a next OFDM symbol and for generating a phase delta; means for adjusting a compensation frequency value coupled to the means for estimating and the means for compensating for frequency offsets; means for accumulating the phase delta and generating a compensation phase; means for compensating for common phase error of frequency-domain symbols; means for estimating channel transfer functions coupled to the means for compensating for common phase error; means for demodulating data coupled to the means for compensating for common phase error and to the means for estimating channel transfer functions; means for de-interleaving, error correcting and decoding demodulated data coupled to the means for demodulating; and means for comparing an absolute value of the phase delta with an adjustable threshold. In one embodiment, the means for compensating for detected frequency jumps is configured, in response to a detected frequency jump, to: pause frequency tracking; force common phase error estimation; estimate a frequency offset based on a phase delta between two subsequent OFDM symbols once the frequency jump has settled; add the estimated frequency offset to a last compensation frequency and adopting the summed value as a new compensation frequency; and resume frequency tracking based on the new compensation frequency. In one embodiment, the means for compensating for detected frequency jumps comprises: means for detecting and ignoring corrupted OFDM symbols which contain severely distorted pilot symbols during one cycle of frequency jump exception state. In one embodiment, the means for compensating for frequency jumps comprises: means for enabling dedicated algorithms during demodulation which improve reception in a presence of inter-carrier interference. In one embodiment, the means for compensating for frequency jumps is configured to perform inter-carrier interference subtraction during one cycle of a frequency jump exception state. In one embodiment, the system comprises: a frequency offset compensation unit configured to receive a complex digital baseband signal frequency-shifted by multiplication with a complex rotating exponential function with constant phase increment from sample to sample; a guard interval removing unit; a Fast Fourier Transformation unit configured to convert a block of received samples into corresponding frequency-domain symbols; a common phase error estimation unit configured to estimate an average phase rotation in a complex plane from one OFDM symbol to a next OFDM symbol and to generate a phase delta; a frequency tracking loop filter configured to adjust a compensation frequency value at the frequency offset compensation unit based on the phase delta; a phase error integrator configured to accumulate the phase delta and generate a compensation phase; a common phase error compensating unit configured to generate a phase error compensated signal; a channel estimation unit configured to estimate a channel transfer function from the phase error compensated signal; a demodulation unit configured to demodulate the data; and a decoder configured to de-interleave, error correct and decode the demodulated data. In one embodiment, the system comprises: a frequency jump detector; a frequency offset estimator; and an exception controller including a state machine triggered by a detected frequency jump. In one embodiment, the means for de-interleaving, error correcting and decoding the demodulated data comprises three layers: a bit and symbol de-interleaver with a Viterbi decoder; a convolutional de-interleaver with a Reed-Solomon decoder; and a large block de-interleaver with a second Reed-Solomon decoder.
In one embodiment, a system comprises: a transform block configured to transform a received complex digital baseband signal; a decoding block configured to decode the transformed signal; a frequency jump detector configured to detect a frequency jump by comparing phase changes in the transformed signal to a threshold; and a frequency jump compensation block configured to compensate for a detected frequency jump. In one embodiment, the frequency jump compensation block comprises: an exception controller; and a frequency offset estimator. In one embodiment, the exception controller comprises a state machine. In one embodiment, the transform block comprises: a frequency offset compensator; a guard interval remover; a Fourier transform block; a phase error estimator; a frequency tracking loop filter; a phase error integrator; and a common phase error compensator. In one embodiment, the decoding block comprises: a channel estimator; a demodulator; and a decoder.
In one embodiment, a computer readable storage medium stores instructions that, when executed, cause an OFDM receiver to perform a method comprising: detecting a frequency jump by comparing a phase delta of a transformed signal to a threshold; and compensating for the detected frequency jump. In one embodiment, compensating for the detected frequency jump comprises: performing inter-carrier interference subtraction. In one embodiment, compensating for the detected frequency jump comprises: ignoring corrupted OFDM symbols. In one embodiment, compensating for the detected frequency jump comprises: pausing frequency tracking; forcing common phase error estimation; estimating a frequency offset based on a phase delta between two subsequent OFDM symbols; adding the estimated frequency offset to a last compensation frequency and adopting the summed value as a new compensation frequency; and resuming frequency tracking based on the new compensation frequency.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
For a more complete understanding of the present disclosure and further objects and advantages thereof, reference is now made to the following description of exemplary embodiments as shown in the accompanying drawings, in which:
FIG. 1 shows a schematic diagram of an OFDM receiver used as a DVB-H receiver; and
FIG. 2 shows a schematic diagram of an embodiment of an OFDM receiver incorporating concepts discussed herein.
DETAILED DESCRIPTION
In the following description, numerous specific details are given to provide a thorough understanding of embodiments. The embodiments can be practiced without one or more of the specific details, or with other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the embodiments.
Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” “according to an embodiment” or “in an embodiment” and similar phrases in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The headings provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
The OFDM receiver 100 shown in FIG. 1 receives a complex digital baseband receive signal at an input 1 . Input 1 is an input of a frequency offset compensation unit 2 . The compensated signal from frequency offset compensation unit 2 is fed to a guard interval removal unit 3 . After removing the guard interval, a Fast Fourier Transform unit 4 converts a block of received samples into corresponding frequency-domain symbols. A phase error estimation unit 5 performs phase tracking on the signal from Fast Fourier Transform unit 4 . Furthermore, the receiver includes a frequency tracking loop filter 6 . The common phase error, i.e., the average phase rotation in the complex plane from one OFDM symbol to the next one, is estimated by the common phase error correction unit 5 , and the calculated phase delta is used as an input for both phase tracking in a phase error integrator 7 and a phase error compensation unit 8 and frequency tracking in frequency tracking loop filter 6 which adjusts the compensation frequency value at the frequency offset compensation unit 2 . For phase tracking, the phase delta is accumulated in phase error integrator 7 and is used as a compensation phase in common phase error compensation unit 8 . Then, the channel transfer function is estimated in a channel estimation unit 9 and is used to demodulate the data in a demodulation unit 10 . Demodulated data are fed into a combined de-interleaving and error correcting decoder 11 to obtain the received data at an output 12 . In DVB-H, this combined de-interleaving and error correcting decoder 11 typically comprises three layers, a bit and symbol de-interleaver with a Viterbi decoder, a convolutional de-interleaver with a Reed-Solomon decoder, and a large block de-interleaver with a second Reed-Solomon decoder.
A fast jump of the down-converter frequency in the DVB-H receiver depicted in FIG. 1 causes only a slow adaptation of frequency tracking loop filter 6 . As a result, the frequency offset is compensated only slowly in frequency offset compensation unit 2 . This results in a large number of OFDM symbols being severely affected by inter-carrier interference. This may result in erroneous receive data and visual errors or dropouts of TV reception.
The embodiment of a system 200 shown in FIG. 2 comprises a frequency jump detector 13 , a frequency offset estimator 14 , and an exception controller 15 which runs a state machine triggered by a detected frequency jump.
Frequency jump detector 13 compares the absolute value of the estimated common phase error with an adjustable threshold. If the threshold is exceeded, a frequency jump has been detected and the exception controller state machine 15 is triggered. The following actions are taken:
Frequency tracking is turned off, keeping the last compensation frequency value, and common phase error estimation is turned on in case it was not used by default.
Once the frequency jump has settled, the frequency offset is estimated based on the phase delta between two subsequent OFDM symbols. Then, the estimated frequency offset is added to the last setting of the compensation frequency, and the summed value is adopted as the new compensation frequency. Once this new value has been set, frequency tracking is switched on again.
During one cycle of frequency jump exception states, the time-interpolation across several OFDM symbols within channel estimation unit 9 may be adapted such that corrupted OFDM symbols which contain severely distorted pilot symbols are considered only as little as possible for channel estimation. The purpose of this is to provide an as clean as possible channel estimation for all OFDM symbols during the occurrence of the jump.
During one cycle of frequency jump exception states, the demodulation may enable dedicated algorithms within demodulation unit 10 which improve reception in presence of inter-carrier interference, such as an inter-carrier interference subtraction.
In one embodiment, the occurrence of a carrier frequency jump is detected by comparing the absolute value of the common phase error between two subsequent OFDM symbols with a defined threshold.
In another embodiment, the amount of frequency offset is estimated by multiplying the estimated common phase error between two subsequent OFDM symbols by a value, which may be an implementation specific constant.
In another embodiment, time interpolation within channel estimation unit 9 is adapted in a manner such that those OFDM symbols which are severely distorted by inter-carrier interference caused by the frequency offset are as little as possible considered for channel estimation.
In another embodiment, demodulation is controlled such that dedicated algorithms are enabled which improve reception in presence of inter-carrier interference, e.g., an inter-carrier interference subtraction.
The embodiments discussed herein may find application in mobile phones, personal digital assistants (PDA) and generally in any orthogonal frequency division multiplexing (OFDM) receivers.
The detailed description has set forth various embodiments of the devices and/or processes via the use of block diagrams and examples. Insofar as such block diagrams and examples contain one or more functions and/or operations, it will be understood by those skilled in the art that each function and/or operation within such block diagrams, flowcharts, or examples can be implemented, individually and/or collectively, by a wide range of hardware, software, firmware, or virtually any combination thereof. In one embodiment, the present subject matter may be implemented via Application Specific Integrated Circuits (ASICs). However, those skilled in the art will recognize that the embodiments disclosed herein, in whole or in part, can be equivalently implemented in standard integrated circuits, as one or more computer programs executed by one or more computers (e.g., as one or more programs running on one or more computer systems), as one or more programs executed by on one or more controllers (e.g., microcontrollers) as one or more programs executed by one or more processors (e.g., microprocessors), as firmware, or as virtually any combination thereof, and that designing the circuitry and/or writing the code for the software and or firmware would be well within the skill of one of ordinary skill in the art in light of the teachings of this disclosure.
When logic is implemented as software and stored in memory, logic or information can be stored on any computer-readable medium for use by or in connection with any processor-related system or method. In the context of this disclosure, a memory is a computer-readable medium that is an electronic, magnetic, optical, or other physical device or means that contains or stores a computer and/or processor program. Logic and/or the information can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions associated with logic and/or information.
In the context of this specification, a “computer-readable medium” can be any element that can store the program associated with logic and/or information for use by or in connection with the instruction execution system, apparatus, and/or device. The computer-readable medium can be, for example, but is not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus or device. More specific examples (a non-exhaustive list) of the computer readable medium would include the following: a portable computer diskette (magnetic, compact flash card, secure digital, or the like), a random access memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM, EEPROM, or Flash memory), a portable compact disc read-only memory (CDROM), digital tape. Note that the computer-readable medium could even be paper or another suitable medium upon which the program associated with logic and/or information is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in memory.
The various embodiments described above can be combined to provide further embodiments. All of the U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet are incorporated herein by reference, in their entirety. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments.
These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure. | This disclosure relates to a method and system for impact mitigation of sudden carrier frequency shifts in OFDM receivers that transforming a received complex digital baseband signal and decoding data from the transformed signal. | 7 |
BACKGROUND OF THE INVENTION
Field of the Invention
The invention concerns a measuring instrument in accordance with the claims.
In martial arts, in particular in full contact sports and in self defense, one is anxious to increase by physical training the “impact effect”. Beside the physiological, psychological and tactical component, the physical component, i.e. physical parameters, like e.g. force, is the main aspect for the evaluation of the impact effect. The impact effect describes in principle the transmission of energy during this impact process. It concerns thereby dynamic processes, since the person affects the impact directly before, while and after the hit, for example by body exertion, influence of the times of contact etc. Besides that, also the person, who holds the target, affects the hit effect at mobile solutions. The simultaneous consideration of force, time and space and/or impact depth can be used for the determination of the so-called shock strength, i.e. a very high force occurring during a very short time period.
Forces in the biomechanics are mainly measured with force surface plates. Such plates are firmly connected with a reference system i.e. fastened to a rigid wall and measure the application of force on this rigid plate. However, such systems in the biomechanics can deal only with static or quasi-static forces, i.e. when slow changes of force and/or small amounts of force occur, since impacts with a large force and large acceleration are risky for injuries on such a rigid plate. In addition such systems can be used in measurements, where the applied forces move the exercising body away of the plate, e.g. during jump power measurement. Therefore, such systems are only conditionally or even not at all suited for impact force measurement. Besides such systems are very expensive in the acquisition, and usually not mobile, but assume an assembly at an immovable, rigid and massive body, e.g. a wall.
The direct application of such transducers in handheld equipment is therefore not possible (moving, not reproducibly flexible target) and requires a consideration of force and kinetic parameters. The available invention does make the determination possible for the first time, partially of the directly measurable characteristics substantial for the impact process. The realization takes place in accordance with the patent claims.
Particularly for the martial arts, there are already some beginnings, in order to objectivate training progress concerning the impact force. However, these are accommodated either in rigid constructions, which increases the danger of substantial injury, or only individual, parameters suitable to only a limited extent can be determined. For example the determination of the “impact effect” is missing, i.e. transfer of energy and their course of time.
So for example in GB 2,372,220, DE 20001615 U1 or EP 1 221 333 fixed surface plates mounted on walls are mentioned. Thereby the dangers of injury described above at impacts against a rigid obstacle are unfavourable. Besides, a yielding goal better simulates the real situation of a hit e.g. on a body.
Furthermore, measurement of force of an impact or the acceleration of the impact is well-known from the state of the art.
Thus for example a box bag with integrated Acceleration sensor is described in the DE 103 23 348 A1. From U.S. Pat. No. 6,611,782, a measuring instrument using a force sensor is well-known for the impact effect. Also the surface plates mentioned above measure either only force of the impact or its acceleration. All further necessary parameters are then deduced from this quantity.
However, such a measurement of only one value, thus of force or acceleration, works only with a constant well-known mass, as this is known, for example, with fixed mounted measuring plates and, hence, is not suited for a “hand held function” with which the measuring setup is held in the hand. Similar Handheld devices are known for example from U.S. Pat. No. 3,270,564 or U.S. Pat. No. 6,441,745 B1 at golf clubs or tennis racquets; however, also in those cases, either only force or acceleration is measured.
BRIEF SUMMARY OF THE INVENTION
Task of the invention is to create a constructively simple and light measuring instrument with which the impact effect can be measured and judged. Furthermore, it is a task of the invention to design the measuring instrument constructionally in such a way that this is applicable as hand held equipment, which can be used particularly in martial arts training without danger of injury.
This task is solved by the characteristics of claim 1 . The invention describes in favourable manner a portable hand held equipment, which measures and registers values of both force and acceleration, for example of an impact, and determines from this the affected mass, speed, way, momentum, transferred energy and power. These are meaningful parameters for the evaluation of the effect of a strike movement. By the registration of values of both parameters, i.e. force and acceleration, the measuring instrument becomes mass independent and thus is suited for hand held applications.
For the measurement of force and acceleration, sensors are included directly in the device. A controller system takes over the remaining processing. The arrangement of force and acceleration sensors directly in the impact pad allows an absolutely training-everyday life-suited employment without danger of injury. No preparations are to be carried out inevitably around the measurements, this leads to a plug-and-play-function. Moreover, the production costs are very small in comparison to other devices. The accessory can be held, as it is usual in the training, by a training partner and must not be mounted on a bearer or a wall what reduces, in addition, the danger of injuries considerably.
The number of directly measured parameters is with force and acceleration higher than for known devices, which determine only one size; therefore, the system is more meaningful. Thus, primarily force and acceleration are acquired. From this, a plurality of further parameters can be determined through physical connections. Beside the primary, actually already important parameters force and acceleration, in further consequence the speed, way, momentum, transferred energy, power can be computed. These parameters are essential for the evaluation of the impact and its effect, since these actually represent the parameters to optimize in training by motion technique.
A time- and track-dependent “pseudo inertia mass” respectively is assumed, which unite the effects of the genuine inertia mass, i.e. the system impact pad retaining arm and the additionally arising resistive forces, i.e. the additional muscle power of the holding arm. This value is not determinable with other one dimensional measuring systems, whereby the values specified above cannot be determined. This “pseudo inertia mass” is determined at each time in accordance with the sampling rate, whereby the system with the application of the physical connections already mentioned, e.g. the determination of the energy, the momentum etc., can be made independent of the knowledge of the mass and the resistance strengths.
Further favourable arrangements of the invention are demonstrated in the dependent claims. The favourable arrangement of the sensors in accordance with claim 2 ensures that the forces released by possible hits and/or impulses are easy and well measurable.
Favourable arrangements of the measuring instrument are given by the characteristics of claim 3 . Like that it is possible to measure different performance parameters in different kinds of sport in order to judge and optimize the performance of the athlete objectively.
In order to avoid dangers of injury and to allow an effective arrangement of the sensors, it is favourable to realize the characteristics of the claim 4 . Favourably applicable force sensors are given by the characteristics of claim 5 .
In this context, it is particularly favourable to realize the characteristics of claim 6 since thereby a good force measurement can be achieved.
A favourable kind of acceleration sensors, with which accelerations are good and reproducibly measurable, is given by the characteristics of claim 7 .
The acceleration sensors can be arranged in favourable way on the measuring instrument and/or target surface in accordance with claim 8 to 10 . Thus it is possible to evaluate the acceleration of a strike or an impact in the best possible way and/or to analyze, even if the strike does not hit each time on the same position of the target surface and/or is placed somewhat decentralized. The arrangement of the acceleration sensors in accordance with these claims ensures also high reproducibility of the results of measurement.
The characteristics of the claims 11 to 14 describe favourable arrangements and designs of the force sensors. Thus it becomes possible to measure the forces, which affect the target surface, as reproducibly and well as possible and to achieve a high accuracy in relative independence from the exact position of the hit. This can be achieved particularly favourably by the characteristics of the claims 12 to 14 .
An alternatively designed target surface, which is used in particular with Hand Mitts with a handle, is designed in accordance with claim 15 .
A further possibility for the favourable arrangement of force sensors is given in accordance with the characteristics of claim 16 .
The characteristics of claim 17 ensure a multifaceted processability of the results.
In claim 18 a training device is described, which covers a measuring instrument according to the invention, with which in different kinds of sport active or passive impact or impact processes can be analyzed. Thus, the measuring instrument is variously applicable.
Further advantages and arrangements of the invention result from the description and the enclosed designs. The invention is represented on the basis of implementation examples in the drawings schematically and is described in the following with reference to the drawings by way of example.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 shows the back of a measuring instrument according to the invention in form of a Coaching Mitt.
FIG. 2 shows a side view in accordance with FIG. 1 .
FIG. 3 shows a front view in accordance with FIG. 1 .
FIG. 4 shows the arrangement of the force sensors and the acceleration sensors of the measuring instrument inside the Coaching Mitts.
FIG. 5 shows the application of the measuring instrument in form of a Coaching Mitt.
FIG. 6 shows a measuring instrument according to the invention in form of a Hand Mitt.
FIG. 7 shows the force sensors and the acceleration sensors of the Hand Mitt in accordance with FIG. 6 .
FIG. 8 shows the application of the Hand Mitt.
FIG. 9 shows arrangement possibilities for acceleration sensors.
FIG. 10 shows arrangement possibilities for force sensors.
DESCRIPTION OF THE INVENTION
In the drawings, two different implementation forms of a measuring instrument according to invention 1 are represented. In the FIG. 1 to 5 , a so-called Coaching Mitt is described, in the FIG. 6 to 8 a so-called Hand Mitt is displayed.
A Coaching Mitt is a training device used in particular for training of martial arts techniques. Such a Coaching Mitt is tightened like a glove and/or fastened to the hand or lower arm 5 . In FIG. 1 and FIG. 2 , the attachment on a hand 5 is represented. With this implementation form the hand 5 is connected at the palm with the Coaching Mitt 1 by a fixation 3 at the lower arm and a fixation 4 . On the side of the measuring instrument and/or the Coaching Mitt 1 opposite to the hand 5 , a target surface 2 is designed, which takes up the expected punch or kick and/or on which the punch or kicks has an effect.
In FIG. 5 the application of the Coaching Mitt 1 is shown. The right person in FIG. 5 holds the Coaching Mitt 1 in the hand 5 with the target surface 2 turned to a second person, which is the training person. This person hits the target surface 2 . Thus, the impact vector goes through the part of the body holding, i.e. e.g. through the hand 5 of the right person. Such a Coaching Mitt 1 is used above all when it is necessary to be able to oppose more resistance to the blows.
If an impact meets the target surface 2 , the Coaching Mitt 1 is pressed to the right in an circle-arc-shaped course from its starting position into a final position. As axis of rotation and/or turning center works thereby, as in FIG. 5 represented, the elbow of the right person. By this movement of the Coaching Mitt 1 , a movement plane is defined. This movement plane runs through the center of the target surface 2 in the starting position, through the center of the target surface 2 in the final position as well as through the turning center and/or the elbow. In FIG. 5 , the movement plane is aligned vertically to the ground.
FIG. 3 shows the Coaching Mitt 1 from the front, whereby the front is protected by a dirt- and humidity-rejecting cover. In FIG. 4 , the Coaching Mitt with removed cover is shown, whereby the arrangement of the sensors 6 , 7 of the measuring instrument 1 is recognizable. Three force sensors 6 are intended, implemented as capacitive, inductive, piezo- or FSR force sensors in this example. The three force sensors 6 are arranged circular around the center of the target surface 2 and cover almost the entire target surface 2 .
In addition, two acceleration sensors 7 , located on the target surface 2 , are, on a vertical, in particular perpendicular, line in the prospective movement plane of the Coaching Mitt 1 caused by the impact with regard to the axis of rotation and/or the turning center, i.e. in this case the elbow, are arranged. The two acceleration sensors 7 lie both in the same distance and diametrically to the center of the target surface 2 .
In FIG. 6 to 8 , a further implementation form of a measuring instrument 1 is represented, which is out-arranged in form of a Hand Mitt. Such a Hand Mitt 1 is, as shown in FIG. 8 , held by a training partner like a racquet. In FIG. 8 , the left person, which is the training person, hits the target surface 2 of the Hand Mitt 1 . In contrary to the Coaching Mitt 1 , the impact vector does not go through the part of the body holding, i.e. the hand 5 , but only through the target surface 2 . Such a Hand Mitt 1 is above all used, if a goal with less resistance is to be needed, to achieve larger accelerations and/or velocities.
If an impact hits the target surface 2 , the Hand Mitt 1 is brought, like the Coaching Mitt 1 , in a circle-arc-shaped course from its starting position to the right into a final position in accordance with FIG. 5 . However, not the elbow works thereby as axis of rotation and/or turning center, but rather the shoulder joint of the right person. By this movement of the Hand Mitt 1 , a movement plane is defined. This movement plane runs through the center of the target surface 2 in the starting position of the Hand Mitt 1 , through the center of the target surface 2 in the final position as well as through the turning center and/or the shoulder joint. In FIG. 5 , the movement plane is aligned diagonally and/or almost horizontal to the ground.
In FIG. 6 , the fundamental structure of such a Hand Mitt 1 is represented, whereby a handle 8 is intended, to which the target surface 2 connects. The target surface 2 of this in FIG. 6 represented implementation form is not circular or oval out-arranged, but has a rather oblong basic form. At differently arranged Hand Mitts 1 the target surface 2 can also be out-arranged in a circle or oval shape.
In FIG. 7 , the target surface 2 of FIG. 6 is displayed in detailed view. The target surface 2 is divided into two ranges: in a right subrange, which essentially exhibits circle or an oval surface area, and a left essentially triangular subrange near the hand grip 8 .
In the right subrange, three force sensors 6 are arranged, similar to the implementation form in accordance with FIG. 1 to 5 as concentric rings around a center of the right subrange of the target surface 2 . Also in this implementation form, the force sensors 6 are designed flatly.
A further force sensor 6 is arranged in the left subrange of the target surface 2 and represents an essentially triangular surface area.
In addition, two acceleration sensors 7 , located on the target surface 2 , are arranged in a straight line, in particular in an extension of the handle 8 , in the movement plane presumably caused by the impact with regard to the axis of rotation and/or the turning center. The two movement sensors 7 can be arranged in same distance and/or diametrically to the center of the right part of the target surface 2 . Further arrangement possibilities for the force sensors 6 and the acceleration sensors 7 are displayed in FIGS. 9 and 10 .
As force sensors 6 , capacitive receivers can be used, with which forces affecting them cause a change in distance of a plate capacitor and thus a change in the capacity and impedance, Moreover, there is conceivable the usage of inductive receivers, which work according to the moving coil principle or Hall sensors. Furthermore, also so-called FSR (Force Sensing Resistance and/or Force Sensitive Resistor) sensors are possible, with which the resistance value changes by the application of force, and/or foils, whereas voltages are generated proportionally to the mechanical influence by the piezoelectric effect.
As acceleration sensors, advantageously MEMS (Micro Electro Mechanical System) sensors are used. These are characterised by a far measuring range, good linearity as well as its small and durable design.
With the measuring instrument according to invention 1 two parameters, i.e. on the one hand the concrete force values and on the other hand the concrete acceleration values, are determined directly. Thus the system becomes more meaningfully, because, besides, from only one parameter at mobile applications, the further interesting values can not derived. Also the measuring instrument 1 thereby becomes mass-independent and is suitable for the use as handheld equipment, which for is favourable for training devices. The force values and the acceleration values are accordingly registered on a value basis and the concrete values flow into the evaluation and the calculation of the characteristics for the qualitative evaluation of the impact, like e.g. the power, etc. Thus, with the measuring instrument according to invention 1 it is not only determined whether a certain threshold and/or a certain limit value is crossed, for example whether the impact exceeds a certain minimum strength and only then is at all seized.
From the determined values force and acceleration, a plurality of further parameters are determined through well-known physical connections, which supply a statement about the quality of the hit. Beside the primary, actually already important parameters force and acceleration, know so speed, way, momentum, transferred energy, power can be computed:
Velocity v(t)=a(t)*dt (including determination of the maximum speed) Covered distance of the target s(t)=∫v(t)*dt=∫∫a(t) dt 2 Momentum p(t)=∫F(t)*dt Transferred energy W(t)=F(t)*s(t)=F*a*t 2 =F(t)*∫∫a(t) dt 2 Power P(t)=W(t)/t=F*a*t=F(t)*a(t)*dt
Furthermore, time conditions can be determined, for example the relationship between contact- and die time. In addition also the affected mass dm(t)=dF(t)/da(t), depending upon the resistance of the training partner, can be computed.
In addition, all parameters are given in their time course, not only for example as scalar maximum value. So from the morphologic course of the curve and/or the profile, important information about the performance of the implemented impact can be determined.
Additionally, it is possible to judge aim- and hit accuracy by the use of several sensors distributed over the entire Target surface. For this, different algorithms, e.g. triangulation, can be used. In the case of appropriate resolution, i.e. number of force sensor areas, also the pressure as force per surface of the area can be determined. With the realization of the measuring instrument 1 as a Hand Mitt, two acceleration sensors 7 in the equipment can be installed, in order to determine also rotation speeds and turning radii.
The measuring instrument 1 possesses advantageously an integrated display, on which the results can be displayed. Besides, the connection through a data interface (e.g. over cables, radio, NFC, optical or other methods) to a data processing equipment (for example PC, PDA, mobile telephone etc.) is possible, to indicate results and store them in a data base, for example to support assessment of physical performance. In addition, also whole training programs and set points can be integrated.
The power supply is made preferably by means of integrated accumulators, which can be recharged, either conventionally or by admission of kinetic energy.
The conversion for other kinds of sport is just as possible with an appropriate adaptation. In principle, each sport equipment, which is actively or passively involved in impact processes, can be equipped with the system, for example all kinds of sport, with which a played object is hit by a racquet or a part of the body, like e.g. Football, Volleyball, tennis, table tennis, baseball, Hockey, ice hockey, gulf, Cricket, Polo etc., whereby the measuring instrument 1 and/or the sensors 6 . 7 in the racquet and/or Part of the body (clothing, e.g. shoe, glove) accommodated and/or are fastened to the racquet/part of the body.
The measuring instrument is also applicable for the diagnostics of the release behavior for kinds of sports, in which an object is thrown or pushed, for example for ball pushing, javelin, discus etc.
In principle two cases are to be distinguished: in the first case an active part (part of the body, racquet, object) hits a target with measurement unit (e.g. fist on Mitt, ball on glove, racquet on ball). In this case the collection takes place in the target, which is naturally not rigidly embodied. In the second case a moved, active part, equipped with the measuring instrument (part of the body/article of clothing, racquet) hits a target (ball, object, etc.).
In both cases, the capture of the parameters is generally only allowed by the invention-appropriate measuring arrangement, because in all cases, movable/moved objects are to be looked which are partially connected with a body part and lead, in particular through this coupling, to dynamically variable parameters, which are not detectable by present methods. | A measuring device for detecting and evaluating an impact, jolt or the like is formed with an impact face, against which the impact, jolt or pulse which is to be evaluated strikes. A sensor, for example a force sensor, detects values of the force which act on the impact face as a result. A sensor, for example an acceleration sensor, detects values of the acceleration which act on the impact face as a result. An evaluation unit processes the determined force and acceleration values. | 0 |
BACKGROUND OF THE INVENTION
This invention relates generally to a fastener of the screw type used in conventional applications to hold structural elements or components in position relative to each other and more particularly, to a self-aligning threaded screw which reduces the danger of cross-threading when the screw is inserted into a mating tapped hole or threaded nut. Generally, there is no difficulty in starting a threaded machine screw in a tapped hole or nut when the two mating parts meet with the longitudinal axes in alignment. However, when the screw meets the entrance to the tapped hole with a mis-alignment between the longitudinal axes, the person directing the screw begins a process, perhaps even subconsciously, of "jiggling" the screw to start the threading process. A grossly mis-aligned screw quickly informs the person of the unacceptable condition and adjustment is made. However, a slight mis-alignment can easily allow the start of an engagement between the threads which results in cross-threading, wherein the threads on the screw or in the tapped hole or both are damaged. In severe cases, the hole may need retapping and the screw may have to be discarded. Thus, losses, especially in mass production with highly repetitive operations, can be worthy of attention both in terms of lost time and direct material costs.
What is needed is a screw fastener which performs the conventional functions of such machine type fasteners and minimizes or eliminates the loss and waste associated with mis-alignment and cross-threading.
SUMMARY OF THE INVENTION
Generally speaking, in accordance with the invention, a screw fastener especially suitable for overcoming the problems associated with mis-alignment and cross-threading between screw and tapped hole at the initiation of engagement is provided. The machine screw has a conventional straight threaded body and a leading end, that is, the end away from the screw head, which is tapered. The tapered end is rounded or conical or may be of many other concave and convex contours such that the leading end of the machine screw has lesser diametrical dimensions than the threaded body. Therefore, the tapered end of the machine screw easily enters a tapped hole.
A projection extends radially from the tapered end portion of the machine screw such that when the longitudinal center lines of the screw and hole are mis-aligned, the projection tends to make first contact with the threads on the tapped hole. As the screw is turned, the projection follows the tapped threads of the hole acting on the thread surfaces to bring the machine screw into alignment. Continued turning of the screw leads the screw thread and hole entrance into contact which results in an aligned threaded, insertion of the screw in the hole. The positional relationship between the projection and the first screw thread brings the starting point of the first screw thread into contact with the starting point of the first thread at the entrance of the tapped hole when the projection tracks the internal hole threads.
Accordingly, it is an object of this invention to provide an improved screw fastener which performs the conventional functions of screw type fasteners and is self-aligning.
Another object of this invention is to provide an improved screw fastener which eliminates the dangers of cross-threading.
A further object of this invention is to provide an improved screw fastener which improves assembly line efficiency.
Still other objects and advantages of this invention will in part be obvious and will in part be apparent from the specification.
The invention accordingly comprises the features of construction, combination of elements, and arrangement of parts which will be exemplified in the construction hereinafter set forth, and the scope of the invention will be indicated in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the invention, reference is had to the following description taken in connection with the accompanying drawings, in which:
FIG. 1 is a partial perspective view of the leading end of a self-aligning screw in accordance with the invention;
FIG. 2 is an end view of the screw fastener of FIG. 1;
FIG. 3 illustrates mis-aligned entrance of the screw of FIG. 1 into a tapped hole;
FIG. 4 is a view similar to FIG. 3 after the screw has been rotated 180°;
FIG. 5 illustrates the screw of FIGS. 3 and 4, seated in the tapped hole after a plurality of rotations; and
FIG. 6 is a view similar to FIG. 3 illustrating another condition of mis-alignment between the self-aligning screw of the instant invention and a tapped hole.
FIG. 7 is a view similar to FIG. 2 of an alternative embodiment of a self-aligning screw in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the Figures, the self-aligning screw 10 or bolt in accordance with the invention includes a conventional body 12 of extended length having conventional threads 14 spiralled therearound in the conventional manner. The threads 14 extend along the length of the body 12 for varying distances depending upon the type of bolt and its application in the known manner. The profile of the threads 14 may be of any type suitable to the application and do not constitute a novel portion of this invention. Accordingly, the description herein of the threads is detailed only to the extent necessary to describe the novel features of the invention.
Further, in the Figures, the threads are not drawn to any scale and no particular thread standard is represented as all types of threaded bolts can be adapted to include the construction in accordance with the invention disclosed herein. Thus, in the Figures the conventional threads are shown, for example, in FIG. 5 with pointed roots and crests whereas in many standard threads the roots and crests are flattened or rounded in fabrication so as to provide a degree of clearance at these locations. Such clearances are not shown in the Figures herein since the conventionally threaded portions of the screw, as stated, are not a novel portion of this invention.
The leading end of the threaded portion of the body 12 FIGS. 1 and 2 includes a rounded surface 16 which tapers inwardly toward the longitudinal center line axis 18 of the screw 10. A projection 20 extends from the rounded surface 16, generally in a radial direction toward the outermost circumference of the threaded portion of the screw body 12. The projection 20 is in the general shape of a truncated cone, being broad at the base 22 and thin and rounded at the tip 24, similar to the construction of old-fashioned phonograph needles. Projection 20 is integral with the rounded surface 16 at the leading end of the screw 10 to provide strength against shock and bending forces. It should be understood that the intersection of the projection 20 with the surface 16 may be filleted for additional strength. The radial height of the projection 20 as measured from the axis 18 is less than the height at the crest 26 of the threads 14. The base 22 of the projection 20 at its highest point 28 is closer to the axis 18 than is the root 30 of the threads 14.
Thus, when the screw 10 is seated in a tapped hole 30 having internal threads 32, the projection 20, as best illustrated in FIG. 5, is not in contact with the internal surfaces of the threads 32.
As illustrated (FIG. 3), the projection 20 has its tip 24 spaced a distance 34 away from the crest 26 of the first one of the threads 14 on the self-aligning screw 10, which distance 34 equals the pitch distance P of the threads 14. In other words, the projection 20 may be considered as the remnant of an additional thread at the leading edge of the screw 10 which has been almost entirely machined away leaving only the projection 20 and the curved surface 16.
A line 36 (FIG. 1) from the tip 24 of the projection 20 parallel to the screw axis 18 intersects each thread at the starting point 38 of that thread. Thus, when the projection 20 has been threaded into the tapped hole 30 such that the projection 20 is cradled within the V-shaped cavity of the first internal thread, the starting point 38 of the first one of threads 14 on the self-aligning screw 10 will be adjacent to the exposed surface of the mating tapped hole at the starting point of the first internal thread thereof. This condition is illustrated in FIG. 4. Further turning of the screw 10 produces the normal threaded condition illustrated in FIG. 5.
As explained more fully hereinafter the distance 34 of the projection tip 24 from the crest 26 in the first thread is not limited to the pitch distance P of the threads 14.
FIGS. 4 and 5 illustrate conditions wherein the axis 18 of the screw 10 is in alignment, that is, coaxial with the axis 40 of the tapped hole 30. When the screw 10 approaches the hole 30 with center lines 18, 40 coaxial, the projection 20 may possibly make first contact with the outer surface of the tapped hole 30, especially at the inlet lip 42. But rotation of the screw 10 while in coaxial alignment quickly brings the projection 20 within the groove of the internal threads 32 as seen in FIG. 4, and further threading is in a completely conventional manner, the position after the next screw revolution being shown with broken lines in FIG. 4.
On the other hand, when the screw 10 approaches the tapped hole 32 with a mis-alignment between the screw axis 18 and the hole axis 40 as illustrated, for example, in FIG. 3, the projection 20 in a favorable condition will strike against the first exposed sloped surface 44 at the entrance to the tapped hole 32. At that condition, no interengagement between the threads 14 and 32 is produced. As the screw 10 is rotated, as will be done in normal driving of the screw 10, the tip 24 of the projection rides along the surface 44 as the surface spirals its way continuously inward in the hole 30. In this way, the projection 20 rides on the surface somewhat as the aforementioned needle in the groove of a phonograph record until the condition illustrated in FIG. 3 results in the condition shown in FIG. 4 after turning the screw by 180°. Sliding the tip 24 of the projection 20 on the surface 44 brings the axes 18,40, originally mis-aligned, into alignment. Then, continued turning of the screw 10 threads the screw 10 into the hole 30 in the normal manner to produce the condition shown in FIG. 5.
A worst case entrance condition occurs with mis-alignment when, upon initial contact between the screw 10 with the outer surface of the tapped hole 30, the projection 20 strikes the outside of the inlet lip 42 as illustrated in FIG. 6. However, conventional turning of the screw 10 causes the projection 20 to ride along the outer surface of the inlet hole 30, the lip 42 developing into the sloped surface 44. Thus, the projection finds its way into the first thread of the internally tapped hole 30 and further turning brings the mis-aligned axes 18, 40 into alignment as shown in FIG. 5.
In this manner, the screw 10 is brought into alignment with the internally tapped hole by the projection 20 before there is engagement between threads 14 of the screw 10 and threads 32 of the internally tapped hole 30. The shocks, if any, of mis-alignment are borne by the projection 20 and there is no mis-alignment or cross-threading between the threads 14, 32.
It should be understood that although a tapped hole is used in illustration, the self-aligning screw 10 operates in the same manner when engaging a threaded nut. In such a case, the projection 20 may extend beyond the boundaries of the nut after the screw and nut have been fully engaged.
As described above, the distance between the projection 20 and the starting point 38 of the first thread on the screw 10 is one thread pitch distance P and the projection 20 is longitudinally aligned with the starting point of the first thread. In other words, when the projection 20, by tracking on the internal thread surface 44 of the hole 30, brings the first thread 14 of the screw 10 into contact with the first thread 32 of the hole 30, this initial contact occurs at the thread starting point 38 where the first thread of the screw 10 begins engagement with the starting point of the first thread 32 of the hole 30. Thus, an alternative projection 20' (not shown) may be provided at any integral number of pitch distances P from the starting point 38 of the first thread 14 when longitudinally aligned to said starting point 38 as described above and illustrated in FIG. 1. Also, the projection may be 1/2 of the pitch distance P away from the first thread provided that the projection 20 is positioned circumferentially 180° away rotationally from the starting point 38 on the first thread 14 of the screw 10. An unlimited number of angular positions of the projection relative to the starting point 38 of the first thread are feasible provided that the distance 34 is correspondingly adjusted such that initial contact between the threads 14 and 32 occurs at the starting points of both threads whereby further turning of the screw provides engagement between them.
In alternative embodiments of a self-aligning screw in accordance with the invention, more than one projection may be provided on the rounded surface 16 so long as the conditions for the location of the projections relative to the starting point for the first thread 14 on the screw 10, as described above are satisfied by every projection.
Also, in alternative embodiments (FIG. 7), the projection 20" rather than coming to a rounded point as illustrated in FIGS. 1 and 2, may be a ridge extending circumferentially around the surface 16 through an arc β. A relatively narrow arc β provides the minimum hazard of cross-threading and thread damage in the tapped hole. However, a narrow arc represents a weaker construction for the projection than does a projection of greater arc. Angles β in a range from 0°-180° may be used effectively. An arc of large magnitude may require that the crest of the ridge-like projection have spiralling curvature corresponding to the curvature of the threads in the tapped hole to avoid interference between the thread and the projection. Further, with reference to FIG. 5, the projection 20 may be contoured such that actual contact is made with at least some portions of the surfaces of the threads 32.
It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, since certain changes may be made in the above constructions without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. | The screw has a conventional threaded body, and a tapered leading end for easy entry to a tapped hole. A projection extends radially from the tapered end portion and when the longitudinal center lines of the screw and hole are misaligned, makes first contact with the threads on the tapped hole. As the screw is turned, the projection follows the tapped threads of the hole to bring the machine screw into alignment. When the projection tracks the internal hole threads, the positional relationship between the projection and the first screw thread brings the starting point of the first screw thread into contact with the starting point of the first thread at the entrance of the tapped hole. | 5 |
This is a division of application Ser. No. 752,609 filed on Dec. 20, 1976, now U.S. Pat. No. 4,104,508.
BACKGROUND OF THE INVENTION
This invention relates to apparatus and a method for supporting, without marring an article such as an opthalmic frame, which softens while being heated and which is subject to being marred while being heated.
The heating device this subject matter is concerned with, is radiant type heating or convectional hot air heating or both.
Particularly in radiant type heating are we concerned with the distance the object or article is from the radiation source. Since the temperature varies inversely to the square of the distance we want to be at a certain place relatively to the infrared generator so as not to be too cool or get too hot. Too close might mean scorching at a certain temperature setting of the machine while too far away would mean slower heating. Small variations in position when heating by convection makes little temperature difference and is not critical.
In radiant heating to keep the article close also means that physical contact with the heater parts is likely. This can mean heat dents, scratching and marring of the article, thus damaging it to some degree. The operator then tends to keep the article too far away or he sets the machine to a low setting thus taking longer to heat and at times underheating the article.
The present invention can accomplish the close positioning of the article to the radiator in the heater and at the same time eliminate any marring or damage to the article.
A prime object is to support a heat softened article while being exposed to heat without deformation or marring of its surface.
Another object is to provide tens of thousands of upwardly projecting but resilient filaments in carpet like arrangement which individually in supporting never press upwardly hard enough to impress their shape into the soft article and yet in their multitude effort are able to support the whole article.
Another important object is to provide a support which is transparent to infrared rays to allow their transmission past and through the support to the article.
Still another object is to take advantage of the phenomenon of fiber optics to transmit infrared rays to the article being supported through the carpet itself.
A further object is to provide a grid structure which allows free flow of air while serving as a support.
Another object is to support an article at a fixed distance from its radiant heat source to establish uniformity of heating of subsequent articles placed there, with the machine heating at a particular heat setting.
SUMMARY
This invention relates to carpet supports for articles composed of heat softening material whose surfaces are easily subject to deformation or other deleterious effects by reason of the weight of the article bearing down upon the supports when the article reaches its softening temperature. Fine filaments of glass fibers, vertically set, on end, in line with the direction of radiation and air flow serve to support an article set upon them. These pliant upstanding fibers in great multitude adapt to whatever conformity is needed to bear the object or article, each bearing upwardly with a pressure insufficient to indent its own form into the soft surface of the article while at the same time being greatly transparent to infrared rays but also transmitting the infrared rays from their bottom end to their top end, to the article by fiber optics effect.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan of an article heater showing a pair of eyeglass frames in dotted lines, being heated.
FIG. 2 is a front elevation of FIG. 1.
FIG. 3 is a vertical sectional view taken along line 3--3 in FIG. 1.
FIG. 4 is another vertical sectional view taken at 90° to FIG. 3 along line 4--4 in FIG. 1.
FIG. 5 is a greatly enlarged fragmentary section of the article support similar to FIG. 3.
FIG. 6 is a fragmentary vertical cross section of a modified form of the invention.
FIG. 7 is a vertical section of another modified form.
FIG. 8 is a plan view of a form jig.
FIG. 9 is a side elevation of FIG. 8.
FIG. 10 is a vertical section on line 10--10 of FIG. 8.
FIG. 11 is a vertical section of impregnated tapes.
FIG. 12 is another vertical section of a tape.
DETAILED DESCRIPTION
A heater housing 10 is shown in FIGS. 1 and 2 as having a flat top 11 provided with an opening 12 and is fastened upon a heater housing 13 by screws 14.
The housing contains regulated heating means 20 which may be electrical or otherwise, operable through a switch 21 to turn it on or off and controlled in temperature by a setting lever 22 rotatable over a dial 23 to read the setting.
Legs 24 lift the housing 10 above the surface it is placed upon for entrance of air into the housing interior 25 through an opening (not shown) in its bottom 15. Air pressurizing means (not shown) is provided in the housing to cause an out flow of heated air past and through the heating means 20. The arrows 27 indicate this out flow of heated air as shown in FIGS. 3 and 4 as well as the direction of infrared radiation, which may be supplied by the heating means 20. The heater and housing may be of hot air type shown in U.S. Pat. No. 2,789,200 or of the radiant type shown in U.S. Pat. No. 3,816,705.
A frame member 30 is held to the top 11 by screws 31 and has an opening 32 which is larger than the opening 12 in the top 11. This frame member 30 provides a holding means for a grid carpet generally indicated at 40.
The grid 40 is the foundation for the subject matter of this application and in this form comprises a glass fiber fabric 41 having the usual woof yarns 42 interwoven with the warp yarns 43. The lower portion as seen in FIG. 5 has the woof and warp yarns impregnated with a thermosetting or other suitable resin or cementitious binder 45 thus fixing this lower portion in a rigid monolithic structure. The upper warp yarns 43 are removed as seen in FIG. 5 to provide the woof yarns 42 with an individual freedom characteristic of the hairs of a tuft of a camel hair brush and is indicated as 46.
Since an individual glass fiber has an outside diameter of about 0.0005" (five ten thousandths of an inch) it has great tensile strength, resiliency, great softness and is a carrier of infrared radiation.
A successful carpet support illustrated and described herewith was made, starting with a two inch wide fiberglass tape doubled upon itself to be one inch wide. The warp yarns numbered eighteen to the inch while the woof yarns numbered thirty four to the inch. Each of the warp and woof strands were comprised of three twisted threads and each thread was comprised of approximately one hundred fifty continuous monofilaments, thus giving each strand about four hundred fifty individual fibers five ten thousandths of an inch in diameter.
After manufacture and assembly into the grid 40 the rigid bound portion equalled three eights of an inch high and the tuft portion equalled three eights of an inch, giving a total of three quarters of an inch finished height. In making such a carpet support the density or number of vertically disposed fibers per square inch determine its support capability, thus it can be designed for supporting heavier or lighter articles.
As seen in FIG. 1 this grid 40 is the form of many lateral bars 50 across the narrow span of the frame 30 and opening 12. These bars 50 meet and join at their ends to a perimeter band 51 totally surrounding all of the bar ends. A cross section through the perimeter band would look just like that in FIG. 5.
FIG. 3 shows the perimeter band 51 fitting inside the opening 32 of the frame member 30 while the bars 50 cross over and span the opening 12 in the top 11 of the housing 10. In FIG. 4 it is clearly seen how a lateral bar 50 spans across the opening 12. These bars 50 provide the rigid support necessary to carry an opthalmic frame F shown in dotted lines in FIG. 1 and FIG. 2.
The grid 40 is fitted into the opening 32 of the frame 30 in any suitable way, is possibly cemented in place or the frame 30 might be molded around and with the grid 40.
It will be seen in FIG. 1 that the frame assembly 30 with grid 40 with the bars 50 and perimeter 51 are held in place by the screws 31.
The manner in which the just described grid was made will now be described.
METHOD OF MANUFACTURE
In FIG. 8 can be seen a form jig 300 which essentially comprises a base 301 and a plurality of dowels or pegs 302. These dowels might be placed in various locations and spacing other than those shown to get many other contours or grid configurations.
Shown in FIGS. 8 and 10 are a tape 41 wound about the jig 300 in the following manner. Starting at 310 the tape 41 is wound downwardly and around the lowermost dowel 302a and up and around dowel 302b, then down to 302c around and up and down over the pegs 302 as the dotted, arrowed, lines 350 illustrate until the dowel 302d in the lower right hand corner is reached. The tape 41 is then wrapped up and around dowel 302e and then over to the left, around dowel 302b and down to 302a, then over to the right to dowel 302d and then up to 302e where it is fastened to hold its end in place.
In FIG. 8 the up and down lines 350 would represent the lateral bars 50 while the dotted lines 351 represent the perimeter band 51 previously described.
The windings may be made of tapes of heavy or light, double or single, whatever density is required to support these particular articles, the carpet is to be used for.
The completely wound tape 41 on the form 300 is now inverted and dipped, as shown in FIG. 10 into an impregnating and hardening liquid 345. Of course instead of being dipped the liquid 345 could be painted on. This liquid may be an epoxy resin, other thermosetting compound or other cementitious material which will impregnate the fibers to bind them together mechanically. The form 300 with the wound and impregnated tape 41 is now removed from the liquid and the cement is allowed to harden or set. A rigid grid 40 has now been formed and it can be removed from the form 300 because it now is self supporting.
A cross section of a portion of the grid 40 is shown in FIG. 11 and would be typical of the locale of the section line 10--10 in FIG. 8. A section through the perimeter 51 and a looped portion of one of the bars 50 would look like FIG. 4, the loop portion now being joined to the perimeter 51 by the cement to make all of the runs 50 and 51 integral.
The lower edges 349, FIG. 11, of the gird 40 are next ground off and polished to form the optically receptive faces 47, shown in FIG. 5 and the upper ends of the woof strands 42 are cut at 348, FIG. 11, to form the upper terminal ends 46, in FIG. 5. These ends 46 may be trimmed flush with each other or may be cut to give a textured surface.
Upper warp strands 43 are now stripped off from their inter-weaving with the woof strands 43, down to the upper limit of the cemented and impregnated portion 45, FIG. 5.
Since the lower ends of all of the individual fibers are ground and polished they are now receptive to receiving of infrared radiation from the heating means 20 and will readily transmit these rays to their upper tips 46 contacting the article such as the frames F to deliver the energy rays to the article by the principles of fiber optics.
The arrows 60 in FIG. 6 indicate the entrance and exit of rays transmitted through the fibers 42 and 142.
A modified form of the invention is disclosed in FIG. 6 wherein the vertical fiber strands 142 are set on end and then have their lower ends impregnated with a suitable binding agent 145 such as an epoxy resin and with a slight change in procedure the just described steps of manufacture are used to make this form of the invention. Again a form jig 300 and a woven tape 41 are used. The tape 41 is wound on the jig as previously described to form the runs 350, 351 in FIG. 8 with the tape end then fastened in place. The extending edges 349 of the tape are cut at the selvage through the bends of the woof strands 142 at 449, FIG. 12. Several weaves of warp strands 143 are then stripped off to expose the woof strands 142 alone. This stripped portion is then impregnated with a hardening cement and left until hardened. Again an integral grid 40 has been made, the bars 50 being integral with the perimeter 51. The upper selvage bends of the woof strands 142 are now cut and the warp strands 143, see FIG. 12, that remain are removed to leave just woof strands 142 bound together at 145 and as shown in FIG. 6. The bottom 147 is then ground and polished and the top 146 may be trimmed or textured. Thus the warp strands 143 that are removed completely have served to position and hold the woof strands 142 in position until formed as described in the grid 40.
Another modified form is illustrated in FIG. 7 wherein the vertically disposed strands 242 are gripped in a channel member 245 which is then fabricated into a suitable grid.
From the foregoing it can be realized that even with careless handling of an article on the carpet support, the article will not be marred. Also, that it is now possible to lay the article on the carpet while being heated instead of hand holding it and that the article will not be harmed even when softened. This carpet will also aid in heating the article since it is transparent to the infrared rays, even transmits the rays and allows for convectional air heating at the same time.
Also it has been demonstrated in what manner a carpet of this type and use can be easily and economically produced and varied in texture to be adapted to fit a product need.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention, in that use of such terms and expressions of excluding any equivalents of the features shown and described, or portions thereof, it being recognized that various modifications are possible within the scope of the invention claimed. | A soft non-marring carpet type support for articles while being heated into a softened condition consisting of either an intermittent or a continuous line of fine fiberglass fibers to accommodate either a flat or uneven surface in contact with the flexible tips, the support being so gentle and so distributed so as not to leave any impression on the articles softened surface. The support transmits a minimum of heat or cold by conduction, is transparent to infrared radiation across its thickness and also at the same time transmits infrared radiation through the length of its optical fibers. | 3 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority from German Patent Application Nos. 102 42 391.1 and 103 29 837.1, which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The invention relates to an apparatus at a draw frame or other textile machine having a drawing mechanism for the doubling and drafting of fibre slivers.
Certain known forms of draw frame have a drawing mechanism frame for accommodating the drawing mechanism, which has at least two pairs of rollers each comprising an upper roller and a lower roller, and means for adjusting the spacing of at least one of the lower rollers in relation to another lower roller, in each case having a mounting device for accommodating the lower roller, and lower rollers are arranged to be driven by at least one drive element endlessly revolving around pulley wheels.
In a known apparatus (DE-OS 20 44 996), the mountings of the intake and middle lower rollers are displaceable on the frame of the machine so that the extent of the drawing zone can be matched to the particular fibre staple. A tensioning pulley wheel, which is displaceable in a guideway in the frame of the machine, allows the length of the toothed belt to be modified in accordance with the changed spacing between the axes of the middle roller and a guide pulley wheel, brought about by displacement of the intake roller. The middle roller is driven by a further toothed belt. The latter toothed belt is tensioned by a tensioning pulley wheel which is fastened to the machine frame and which can pivot about one axis; as a result, it can also be matched to changed spacings between the axes of the intake roller and middle roller. It is disadvantageous that displacing devices for displacement of the intake roller and the middle roller and additional tensioning devices for re-tensioning of the toothed belts after the displacement operations are necessary, requiring a considerable outlay in terms of construction. In addition, it is disadvantageous that a number of work steps are required for the displacement operations and the subsequent re-tensioning operations. The belt tension is destroyed by the displacement process. Where the displacement is carried out manually, spacers are inserted between the mountings, the mountings being pushed against the spacers so that, in this case too, the amount of set-up work is considerable. Finally, the displacement and re-tensioning operations result in a doubling of potential error sources when setting the spacings and belt tensions.
It is an aim of the invention to provide an apparatus of the kind described at the beginning that avoids or mitigates the disadvantages mentioned and that especially is of simple construction and allows a considerable reduction in the work and time required for adjustment of the lower roller(s) and, accordingly, of the extent(s) of the drawing zone(s).
SUMMARY OF THE INVENTION
The invention provides a drawing mechanism having a drawing mechanism frame, at least two pairs of rollers each comprising an upper roller and a lower roller and having a mounting device for accommodating the lower roller, means for adjusting the spacing of at least one of the lower rollers in relation to another lower roller, and at least one drive device comprising a drive element endlessly revolving around pulley wheels, wherein the drive device can be used for adjusting the position of said at least one lower roller.
The measures according to the invention make it possible, by simple means, for the mountings and, as a result, the extents of the drawing zones (nip line spacings) to be adjusted in a short time. For the purpose of adjusting the extents of the drawing zones, elegant use is made of existing structural elements necessarily present in the draw frame, for example, a pulley wheel and the drive belt. Separate apparatuses for adjustment are not required. As a result of the fact that the drive belt can be in tension before, during and after adjustment, further apparatuses for re-tensioning the drive belt after the adjustment are not required, which allows the extents of the drawing zones of the drawing mechanism to be changed in a short time by means that are especially simple in terms of construction.
Advantageously, a said mounting device of a said lower roller is adjustable by means of a moving force applied to a pulley wheel of said drive device, which moving force is converted into an adjusting movement for the mounting device. As well or instead, a said mounting device of a said lower roller is advantageously adjustable by means of a moving force applied to a drive element of said drive device, which moving force is converted into an adjusting movement for the mounting device. Advantageously, the drive element is stationary and the pulley wheel is rotated. Advantageously, the pulley wheel is stationary and the drive element is moved. Advantageously, the rotation of the pulley wheel or the movement of the drive element is converted into the adjusting movement of the slider. Advantageously, at least one guide pulley wheel is attached to each slider (mounting); and the roller-driving pulley wheel or guide pulley wheel(s) act, in each case one after the other, on both sides of the tensioned drive element. Advantageously, the rotation of the pulley wheel or the movement of the drive element is accomplished manually. Advantageously, the slider is linearly displaceable.
Advantageously, the drive element is a toothed belt. Advantageously, an endless flexible toothed belt is present. Advantageously, the pulley wheels comprise toothed belt wheels. Advantageously, the pulley wheels comprise guide pulley wheels. Advantageously, at least one driving pulley wheel is provided. Advantageously, driven pulley wheels are present. Advantageously, the drive element loops around the pulley wheels. Advantageously, the drive element and the pulley wheel are in engagement with one another. Advantageously, the pulley wheel for adjustment of a slider is the drive pulley wheel of a lower roller (roller-driving pulley wheel). Advantageously, the slider is displaceable during adjustment. Advantageously, the slider is arranged to be stopped. Advantageously, the stopping arrangement is releasable. Advantageously, a display device for the position of the slider is present.
Advantageously, a drive motor is used for rotation of the pulley wheel. Advantageously, a drive motor is used for movement of the drive element. Advantageously, the drive motor is used for the lower rollers. Advantageously, a separate drive motor is used. Advantageously, belt shortening or belt lengthening is arranged to be automatically evened out during adjustment. Advantageously, the evening-out of belt length is carried out at a slider by two guide pulley wheels.
Advantageously, the lower rollers are arranged to be adjusted singly and independently of one another. Preferably, a roller-driving pulley wheel and a guide pulley wheel are attached to the slider of the intake roller and a roller-driving pulley wheel and a guide pulley wheel are attached to the slider of the middle roller. Advantageously, the drive element runs around the pulley wheels at the slider of the intake roller and around the pulley wheels at the slider of the middle roller in a mirror-reflected arrangement. Advantageously, the drive element is in tension before, during and after the displacement. Advantageously, the drive motor is in communication with an electronic control and regulation device. Advantageously, a measuring element is connected to the control and regulation device. Advantageously, the measuring element is capable of registering fibre-related and/or machinery-related measurement variables. Advantageously, adjustment of the slider is carried out when the drawing mechanism is in operation. Advantageously, adjustment of the slider is carried out when the drawing mechanism is not in operation. Advantageously, adjustment of the slider is carried out during can-changing. Advantageously, the draw frame is self-adjusting. Advantageously, adjustment of the slider is carried out by inputting adjustment variables. Advantageously, the adjustment variables can be input manually. Advantageously, a memory for adjustment variables is connected to the control and regulation device. Advantageously, the slider for the intake roller and the slider for the middle roller are arranged to be connected by a rigid connecting element. Advantageously, the connecting element is releasably connected. The spacing of the pairs of rollers in relation to one another may be adjustable without fibre material. The spacing of the pairs of rollers in relation to one another may be adjustable with fibre material. Advantageously, the extent of the preliminary draft zone can be adjusted. Advantageously, the extent of the main draft zone can be adjusted. Advantageously, the extent of the preliminary draft zone and the extent of the main draft zone can be adjusted. Advantageously, each lower roller has its own associated drive motor. Advantageously, the intake and middle lower rollers are arranged to be driven by one drive motor. Advantageously, a brake, stopping arrangement or the like is associated with the stationary pulley wheel. The brake, stopping arrangement or the like may be mechanical, electrical or electromagnetic. Advantageously, the drive motor is a self-braking motor. Advantageously, the drive motor drives a further drive train, which has a free-wheel arrangement or the like.
Advantageously, the mounting device consists of the mounting and the slider. The mounting and the slider may be fastened to one another, for example by bolts. The mounting and the slider may be of integral construction.
The invention further provides an apparatus at a draw frame having a drawing mechanism for the doubling and drafting of fibre slivers, having a drawing mechanism frame for accommodating the drawing mechanism, which has at least two pairs of rollers each comprising and upper and a lower roller, having means for adjusting the spacing of at least one of the lower rollers in relation to another lower roller, in each case having a mounting device for accommodating the lower roller, wherein lower rollers are arranged to be driven by at least one drive element endlessly revolving around pulley wheels, characterised in that at least one pulley wheel and the tensioned drive element are used for adjusting the mounting device, wherein a moving force applied to the pulley wheel or to the drive element can be converted into the adjusting movement for the mounting device.
The invention further provides a draw frame comprising a drawing mechanism according to the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic side view of an autoleveller draw frame for use with an apparatus according to the invention together with a general circuit diagram;
FIG. 2 is a perspective view of a side of the draw frame showing the displaceable mounting of the intake and middle lower rollers;
FIGS. 3 a and 3 b show the drive for the intake and middle lower rollers for the draw frame according to FIG. 1 , in a side view ( FIG. 3 a ) and plan view ( FIG. 3 b );
FIG. 3 c is a partial side view of a drive belt;
FIGS. 4 a to 4 d show, in diagrammatic form, the sequential procedure for shortening of the preliminary and main draft zones;
FIGS. 5 a and 5 b show the intake and middle lower rollers before displacement ( FIG. 5 a ) and after displacement ( FIG. 5 b );
FIGS. 6 a and 6 b show, in diagrammatic form, an electromagnetic braking apparatus for a toothed belt wheel;
FIG. 7 shows a locking device for a slider;
FIG. 8 shows a connection element (bridge) for connecting two sliders;
FIG. 9 is a partial side view of an embodiment comprising a drawing mechanism having three roller combinations, each having its own drive motor;
FIG. 10 is a side view of a drawing mechanism with input devices for manual and/or memory-assisted input of adjustment values for changing the nip line spacings in the drawing mechanism; and
FIG. 11 is a front view of a roller pair with an upper roller lifted off from a lower roller.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with FIG. 1 , a draw frame 1 , for example a draw frame known as an HSR draw frame (trade mark) made by Trützschler GmbH & Co. KG, has a drawing mechanism 2 , upstream of which is an intake 3 of the drawing mechanism and downstream of which is an exit 4 from the drawing mechanism. The fibre slivers 5 , coming from cans (not shown), enter the sliver guide 6 and, drawn by the draw-off rollers 7 , 8 , are transported past the measuring element 9 . The drawing mechanism 2 is designed as a 4-over-3 drawing mechanism, that is to say it consists of three lower rollers I, II, III (I delivery lower roller, II middle lower roller, III intake lower roller) and four upper rollers 11 , 12 , 13 , 14 . Drafting of the fibre sliver combination 5 ′ from a plurality of fibre slivers 5 is carried out in the drawing mechanism 2 . Drafting is composed of preliminary drafting and main drafting. The roller pairs 14 /III and 13 /II form the preliminary draft zone and the roller pairs 13 /II and 11 , 12 /I form the main draft zone.
The attenuated fibre slivers 5 reach a web guide 10 in the exit 4 from the drawing mechanism and, by means of the draw-off rollers 15 , 16 , are drawn through a sliver funnel 17 , in which they are combined to form one fibre sliver 18 , which is then deposited in cans. Reference letter A denotes the work direction.
The draw-off rollers 7 , 8 , the intake lower roller III and the middle lower roller II, which are connected to one another mechanically, for example by toothed belts, are driven by the control motor 19 , it being possible, in the process, for a desired value to be specified. (The associated upper rollers 14 and 13 , respectively, revolve by virtue of the motion of the lower rollers.) The delivery lower roller I and the draw-off rollers 15 , 16 are driven by the main motor 20 . The control motor 19 and the main motor 20 each have their own controller 21 and 22 , respectively. Control (speed-of-rotation control) is carried out in each case by means of a closed control loop, a tachogenerator 23 being associated with the control motor 19 and a tachogenerator 24 being associated with the main motor 20 . At the intake 3 of the drawing mechanism, a variable proportional to the weight of the fibre slivers 5 fed in, for example their cross-section, is measured by an intake measuring element 9 known, for example, from DE-A-44 04 326. At the exit 4 from the drawing mechanism, the cross-section of the delivered fibre sliver 18 is ascertained by an exit measuring element 25 associated with the sliver funnel 17 and known, for example, from DE-A-195 37 983. A central computer unit 26 (control and regulation device), for example a microcomputer with a microprocessor, sends a setting for the desired value for the control motor 19 to the controller 21 . The measurement values of the two measuring elements 9 and 25 are sent to the central computer unit 26 during the drawing process. The desired value for the control motor 19 is determined in the central computer unit 26 from the measurement values of the intake measuring element 9 and from the desired value for the cross-section of the delivered fibre sliver 18 . The measurement values of the exit measuring element 25 are used for monitoring of the delivered fibre sliver 18 (delivered sliver monitoring). By means of this control system, it is possible for variations in the cross-section of the fibre slivers 5 fed in to be compensated, and for the fibre sliver to be made more uniform, by appropriately regulating the drafting process. Reference numeral 27 denotes a display monitor, 28 an interface, 29 an input device, 30 a pressure rod and 31 a memory.
With reference to FIG. 2 , each of lower rollers II, III has an associated mounting device comprising a respective mounting 33 a , 34 a . The trunnions Ia, IIa, IIIa (see FIG. 3 b ) of the lower rollers I, II and III are mounted so as to be capable of rotation in mountings 32 a , 33 a , 34 a ( 32 b , 33 b , 34 b are located on the other side of the drawing mechanism and are not shown). The mountings 33 a and 34 a are bolted onto sliders 35 a and 36 a , respectively, which are displaceable in the direction of the arrows C, D and E, F, respectively, along a bar 37 a . The two ends of the bar 37 a are fixedly mounted in mounting blocks 38 ′ ( 38 ″ not shown), which are attached to the frame 39 of the machine.
Displacement of the sliders 35 a , 35 b ; 36 a , 36 b at the same time causes the mountings 33 a , 33 b ; 34 a , 34 b and, as a result, the lower rollers II and III, respectively, to be displaced and moved in directions C, D and E, F, respectively. The associated upper rollers 13 and 14 are correspondingly moved (in a manner not shown) in directions C, D and E, F, respectively. By that means, the nip line spacings between the roller combinations are modified and set.
Locking of the sliders 35 a , 35 b ; 36 a , 36 b is accomplished by means of a catch device, stopping device or the like, one suitable form of stopping device being shown in FIG. 7 .
Referring to FIG. 3 a , the lower rollers II and III are driven from the right-hand side of the draw frame, seen in the direction of material flow A, by means of a common loop mechanism in the form of toothed belt wheels 40 , 41 and a toothed belt 47 . The different speeds of rotation of the lower rollers II and III are achieved by means of change-gearwheels at the drive trunnions Iia, IIIa provided with different numbers of teeth. The toothed belt 47 runs in direction B (that is to say contrary to the work direction) onto the control drive, which is in the form of a servo motor 19 . The lower roller I is driven from the left-hand side of the machine by means of a loop mechanism in the form of toothed belt wheels and a toothed belt 47 ′. For that purpose, the toothed belt 47 ′ runs on the left-hand side from the toothed belt disc 40 ′ at the lower roller I in direction G onto the servo motor 20 .
In operation, that is to say when the fibre slivers are running in direction A, the toothed belt 47 moves in direction G. Starting from the toothed belt wheel 47 arranged on the drive motor 19 , the toothed belt 47 runs successively over a toothed belt wheel 45 , a smooth guide pulley wheel 46 , the toothed belt wheel 40 (roller-driving pulley wheel for the lower roller III), the toothed belt wheel 41 (roller-driving pulley wheel for the lower roller II), a smooth guide pulley wheel 42 and a toothed belt wheel 43 . As shown in FIG. 3 c , the belt 47 has a toothed side 47 a and a smooth side 47 b . By means of its teeth, the toothed belt 47 , by means of teeth 47 a ( FIG. 3 c ), is in positive engagement with the toothed belt wheels 40 , 41 , 43 , 44 , and 45 . The smooth side 47 b (reverse) ( FIG. 3 c ) of the toothed belt 47 , opposite the toothed side, is in contact and in engagement with the smooth guide pulley wheels 46 and 42 . The toothed belt 47 loops around all the pulley wheels 40 to 46 . In operation (when the fibre slivers are running in direction A during drafting), the toothed belt wheels 40 , 41 , 43 , 44 , and 45 rotate clockwise and the guide pulley wheels 42 and 46 rotate anti-clockwise.
The toothed belt wheels 40 , 41 are associated with the mountings 34 a and 33 a , respectively, whereas the guide pulley wheels 42 , 46 are attached to the sliders 35 a and 36 a , respectively, in a manner allowing rotation. Because of the rigid attachment between the mounting 34 a and the slider 36 a and between the mounting 33 a and the slider 35 a (for example, by means of bolts), there are associated with the lower rollers II and III, in each case, one toothed belt wheel 40 and 41 , respectively, and one guide pulley wheel 46 and 42 , respectively. The toothed belt 47 runs around the pulley wheels 40 , 46 , on the one hand, and around the pulley wheels 41 , 42 , on the other hand, in a mirror-reflection arrangement (see FIG. 3 b ).
The zone between the pairs of rollers 13 /II and 14 /III is designated VV (preliminary drafting) and the zone between the pairs of rollers 12 /I and 13 /II is designated HV (main drafting) (see FIG. 4 a ). When, in accordance with FIG. 3 a , the nip line spacing between the roller pairs 14 /III and 13 /II is to be increased, at least one pair of rollers must be moved away from the respective other pair of rollers. For that purpose the slider 35 a may be displaced towards the right, which may be accomplished in two ways:
a) The slider 35 a is unlocked. A pulley wheel, for example the toothed belt wheel 44 , is stopped so that there is no possibility of rotation. Stopping may be accomplished, for example, by mechanical or electromagnetic means. As a result the toothed belt 47 is stationary and cannot be moved. The toothed belt wheel 41 is then rotated anti-clockwise, for example manually using a crank or the like, whereupon the guide pulley wheel 42 likewise rotates, clockwise, as a matter of necessity. In the process, the rotary movement of the toothed belt wheel 41 is converted into a longitudinal movement of the slider 35 a in direction C, the toothed belt wheel 41 and the guide pulley wheel 42 winding along opposite sides of the stationary toothed belt 47 , thereby “shortening”, as it were, the toothed belt 47 at one pulley wheel and “lengthening” it at the other pulley wheel. The length of belt required during that “winding along” at the toothed belt wheel 41 is made available at the guide pulley wheel 42 . The lower roller II is thereby displaced in direction C by means of the slider 35 a and the mounting 33 a. b) The slider 35 a is unlocked. The toothed belt wheel 41 is stopped so that there is no possibility of rotation. As a result the guide pulley wheel 42 is also stopped of necessity. Then, clockwise rotation is brought about by means of the drive motor 19 . The toothed belt 47 moves in direction G, likewise “shortening” the belt 47 at one pulley wheel and “lengthening” it at the other pulley wheel. The length of belt actually required between the toothed belt wheels 40 and 41 is made available between the toothed belt wheels 43 and pulley wheel 42 . The rotary movement of the toothed belt wheel 44 and the movement of the toothed belt 47 is thereby converted into a longitudinal movement of the slider 35 a in direction C. The lower roller II, mounted in the mounting 33 a (which is rigidly connected to the slider 35 a ), is likewise moved in direction C as a result.
In practice, it is often the case that, in accordance with FIGS. 4 a to 4 d , first the preliminary draft zone VV is modified and then the main draft zone HV. In the case of shortening of the draft zones VV and HV, the slider 36 a is displaced in the direction of the arrow E from the position according to FIG. 4 a into the position according to FIG. 4 b . As a result, the nip line spacing in the preliminary draft zone VV is reduced from “a” to “a′”. Then, in accordance with FIG. 4 c , the sliders 36 a and 35 a are rigidly connected to one another by means of a bridge 50 . Finally, the rigidly coupled sliders 36 a and 35 a are moved, in accordance with FIG. 4 d , in the direction of the arrows E and C, from the position shown in FIG. 4 c into the position shown in FIG. 4 d . As a result, the nip line spacing in the main draft zone HV is shortened from “b” to “b′”.—A corresponding procedure is used in the case of lengthening the preliminary and main draft zones, that is to say the coupled sliders 35 a and 36 a are displaced in the direction of the arrows F and D (see FIG. 2 ), as a result of which the main draft zone HV is lengthened. Then, the sliders 35 a and 36 a are uncoupled from the bridge 50 . Finally, the slider 36 a is moved in the direction of the arrow F (see FIG. 2 ), as a result of which the preliminary draft zone VV is lengthened.
With regard to the fibre slivers 5 in the drawing mechanism 2 , it should be noted that, in the case of shortening of the draft zones VV and HV, a small amount of stretching, in direction B, of the fibre slivers 5 IV upstream of the pair of rollers 14 /III can occur on displacement in accordance with FIGS. 4 a , 4 b , but because of the length (about 1.5 m) of the spacing between the transport rollers 7 , 8 and the pair of rollers 14 /III this is without significance. In the case of shortening, a sagging loop does not form in the preliminary draft zone VV because in the case of displacement referring to the pairs of rollers 14 /III and 13 /II either one or both pairs of rollers are rotatable because the drives to both pairs of rollers are coupled by way of the toothed belt 47 . In contrast, in the case of shortening of the main draft zone HV, a sagging loop is formed in fibre slivers 5 ″, which is drawn out or drawn straight by rotation of the pair of rollers 12 /I in the work direction A by means of the main motor 20 .—In the case of lengthening of the draft zones VV and HV, the pair of rollers 12 /I is, in a first step, rotated backwards in direction B, whereupon a sagging loop is intentionally formed in the fibre slivers 5 ″. When the main draft zone HV is subsequently lengthened by displacement of the coupled sliders 35 a and 36 a in direction D and F, the artificially formed loop is, in the process, once again drawn out or drawn straight. Finally, after uncoupling of the bridge 50 , the slider 36 a is displaced in direction F. As a result of the above-mentioned coupling of the drives to the intake and middle lower roller pairs by means of the toothed belt 47 , the length of the fibre slivers 5 ′ in the preliminary draft zone VV remains unaffected. Possible slight longitudinal compression of the fibre slivers 5 IV upstream of the pair of rollers 14 /III is, in respect of the drafting and the constitution of the fibre slivers 5 IV without significance.
FIGS. 5 a , 5 b show a suitable construction for bringing about the displacement of the sliders 36 a and 35 a . The nip line spacing in the preliminary draft zone VV is lengthened from “a” ( FIG. 5 a ) to “a″” ( FIG. 5 b ). The sliders 36 a and 35 a are displaced one after the other according to the arrows E and C, respectively. Displacement is accomplished by stopping the toothed belt wheel 40 or fixing it with a holding brake or the like and then actuating the drive motor 19 , whereupon the toothed belt 47 moves. In continuation thereof, the sliders 36 a and 35 a are displaced in accordance with FIGS. 4 a , 4 b and, subsequently, FIGS. 4 c , 4 d.
In FIG. 6 a there is shown an electromagnetic holding brake for braking the toothed belt wheel 44 . The brake has a rod-shaped iron core 53 surrounded by a plunger coil 54 . Mounted on one end face of the iron core 53 is a brake shoe 55 , for example made of plastics material or the like. The iron core 53 is displaceable in the direction of the arrows M, N. When current flows through the plunger coil 54 , the iron core 53 is moved in direction M, in accordance with FIG. 6 b , so that the brake shoe 55 is pressed against the smooth cylindrical surface of the shaft 44 a of the toothed belt wheel 44 . As a result, the toothed belt wheel 44 is fixed (stopped) so that it cannot rotate, for as long as voltage is applied to the plunger coil 54 .
In FIG. 7 there is shown a stopping device for slider 36 a and corresponding lower roller III. A pneumatic cylinder 60 having a piston rod 61 is attached to the slider 36 a . When subjected to pressure from the pneumatic cylinder 60 , the piston rod 61 is moved out in the direction of the arrow P and comes to rest, with a high degree of contact pressure, against the machine frame 61 . The slider 36 a is fixed (stopped) so that it cannot be displaced with respect to the bar 37 a , for as long as compressed air is applied to the pneumatic cylinder 60 . Lower roller II may be provided with an analogous arrangement.
In accordance with FIG. 8 , there is provided, as the bridge 50 between the sliders 35 a and 36 a , a flat piece of metal (plate), which is fastened in the region of one of its ends 50 a to the slider 36 a , for example using bolts. In its region 50 b facing the slider 35 a , the flat piece of metal has an elongate hole 50 c , through which a bolt 62 can engage in a threaded hole (not shown) in the slider 35 a . By means of this bridge 50 , the sliders 35 a and 36 a can be rigidly connected to one another, releasably, at different spacings with respect to one another.
In accordance with FIG. 9 , in contrast to FIG. 1 , each lower roller I, II and III is driven by its own drive motor 20 , 52 and 19 , respectively, as shown, for example, in DE-OS 38 01 880. The motor 20 drives the toothed belt wheel 55 of the lower roller I by way of the toothed belt 56 ; the motor 52 drives the toothed belt wheel 41 of the lower roller II by way of the toothed belt 57 ; and the motor 19 drives the toothed belt wheel 40 of the lower roller III by way of the toothed belt 47 . Attached to the slider 36 a , in addition to the smooth guide pulley wheel 46 , is a further smooth guide pulley wheel 51 . The endless toothed belt 47 loops around, in succession, the pulley wheels 44 , 46 , 40 , 51 and 43 . The toothed belt wheels 44 , 40 and 43 are in engagement with the teeth of the toothed belt 47 , whereas the smooth guide pulley wheels 46 and 51 are in engagement with the smooth reverse side of the toothed belt 47 . The sliders 35 a and 36 a are rigidly connected to one another, releasably, by means of the bridge 50 . When they are not connected by the bridge 50 , the sliders 35 a and 36 a are individually displaceable and when they are connected by the bridge 50 they are jointly displaceable.
In accordance with FIG. 10 , the drive motor 19 for lower rollers II and III is in communication with the electronic control and regulation device 26 . Adjustment values for modification of the draft zones VV and HV (that is to say the extents of the drawing zones) either can be entered manually by way of the input device 29 or can be called up from a memory 31 for particular categories of fibre material.
Adjustment of the nip line spacing in the preliminary draft zone VV and/or the main draft zone HV can be carried out with the fibre slivers 5 inserted.
Displacement can be carried out with the upper rollers 11 to 14 in the loaded state. FIGS. 1 and 10 show inserted fibre slivers 5 and loaded upper rollers 11 to 14 . With the fibre slivers inserted and the upper rollers 11 to 14 loaded, the sliders 35 a , 36 a or mountings of at least one lower roller II, III are unlocked, the sliders or mountings are set to the desired nip line spacing a, a′; b, b′ by means of a displacement device, for example in accordance with FIGS. 3 a , 3 b ; 5 a , 5 b and then the sliders 35 a , 36 a or mountings are locked again (for example in accordance with FIG. 7 ).
Displacement can also be carried out with the upper rollers 11 to 14 lifted off. The upper rollers 11 to 14 may be lifted off completely from the lower rollers I to III in the manner shown in DE-OS 197 04 815, the upper roller 14 being swung out on a portal 58 about a pivot mounting 59 . However, it may also be sufficient for the upper rollers 11 to 14 to be unloaded and to be lifted off from the lower rollers I to III only to a slight degree such that the fibre slivers 5 are not caught by the pairs of rollers during displacement of the draft zones VV and HV but can slide through the roller nip without being adversely affected.
The invention has been illustrated using the example of the adjustment of the nip line spacings of a drawing mechanism of a draw frame. It likewise encompasses the adjustment of drawing mechanisms of other machines, for example carding machines, combing machines, fly frames and ring spinning frames. | A drawing mechanism for the doubling and drafting of fibre slivers, has a drawing mechanism frame for accommodating the drawing mechanism, which has at least two pairs of rollers each comprising an upper roller, and a lower roller, and has means for adjusting the spacing of at least one of the lower rollers in relation to another lower roller, in each case having a mounting device for accommodating the lower roller, wherein lower rollers are arranged to be driven by a drive device comprising at least one drive element endlessly revolving around pulley wheels.
In order, by simple means in terms of construction, to make possible a considerable reduction in the work and time required for adjustment of the lower roller(s) and, accordingly, of the extent(s) of the drawing zone(s), the mounting device(s) are made adjustable by the drive device. | 3 |
REFERENCE TO RELATED APPLICATION
This application is a National Phase of International Application No. PCT/US2012/056346, filed Sep. 20, 2012, which claims priority to U.S. Provisional Patent Application No. 61/536,957, filed Sep. 20, 2011, which is incorporated herein by reference.
GOVERNMENT RIGHTS
This invention was made with government support under R01-CA120316,R01-DK056108, and 5U01-CA-116937 awarded by the NIH. The U.S. Government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention relates to novel splicing variants of a number of genes associated with prostate cancer risk and survival, and also the risk assessment, detection, diagnosis, or prognosis of prostate cancer (CaP). More specifically, this invention relates to the detection of certain splicing variants in genes PIK3CD, FGFR3, TSC2, ITGA4, MET, NF1, BAK1, and RASGRP2 to determine the risk, detect, diagnose, or prognosticate prostate cancer, particularly in the African American population. Research for the present invention was supported in part by American Cancer Society grant ACS-IRG-08-091-01.
BACKGROUND OF THE INVENTION
Prostate cancer (PCa) is the most common form of cancer among males. Overwhelming clinical evidence shows that human prostate cancer has the propensity to metastasize to bone, and the disease appears to progress inevitably from androgen dependent to androgen refractory status, leading to increased patient mortality. This prevalent disease is currently the second leading cause of cancer death among men in the U.S.
There are striking population (race) disparities in prostate cancer risk and survival outcome borne out of current health statistics data. This is particularly evident between African Americans (AA) and their Caucasian American (CA) counterparts. Epidemiologic studies have shown that higher mortality and recurrence rates of prostate cancer are still seen in AA men even after adjustment for socioeconomic status, environmental factors and health care access. Thus, it is likely that intrinsic biological differences account for some of the cancer disparities. Identifying these differences has been identified as a high-priority research area by the NIH, NCI and the Center to Reduce Cancer Health Disparities (CRCHD).
There are currently very few diagnostics methods available for the diagnosis and prevention of prostate cancer, particularly which can be used as predictor of risk and survival in African American population. Thus, the identification of genetic differences between AA and their CA counterparts, that are responsible for predisposition of prostate cancer would provide for a better understanding of the mechanisms of cancer causation (including ethnic and individual susceptibility), and ultimately lead to ways of prostate cancer prevention.
SUMMARY OF THE INVENTION
Prostate cancer (PCa) is a disease conferred by multiple gene mutations, numerous alternations in gene expression and aberrant changes in genome composition/architecture. The African American (AA) population exhibits higher incidence and mortality rates compared to Caucasian Americans (CA). The present invention, through systematic mRNA expression profiling, characterizes the global mRNA expression profiles in AA and CA prostate tissue samples. A large number of genes are shown to have differential expression between AA and CA patients. Notably, several genes residing within the 5 oncogenic signaling pathways have been identified as exhibiting differential splicing, which includes but not limited to PIK3CD, FGFR3, TSC2, FGFR2, PDGFRA, ITGA4, MET, EPHA3, NF1, RASGRP2, CTNNB1, TSC2, ATM, CDK4, and RB 1 between AA and CA PCa specimens. Quantitative analysis of the expression profiles of PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1 in prostate samples confirm differential splicing between the AA and CA patients. With certain splicing variants predominantly exist in AA patients. As a non-limiting example, PIK3CD is expressed predominantly as a long variant in CA patients, whereas the AA patient would have higher portion of a short variant. The alternatively spliced short variant of PIK3CD is found to be a more aggressive form. Increasing the short to long variants ratio in a PCa cell line (MDA PCa 2b) that is representative to the AA PCa PIK3CD expression profile, by knocking down PIK3CD long variant expression increases cell proliferation and cell migration. Selectively knocking down the expression of PIK3CD short variant in the same cell line, decreases the short to long variants ratio, and results in marked decrease of cell proliferation and cell migration. Similarly AA predominant variants of FGFR3, TSC2 and RASGRP2 are also shown to be the more aggressive variant.
It is thus discovered by the inventors that alternative splicing variants for genes in the oncogenic signaling pathways, such as PIK3CD, FGFR3, TSC2, FGFR2, PDGFRA, ITGA4, MET, EPHA3, NF1, RASGRP2, CTNNB1, TSC2, ATM, CDK4, and RB1 are strong predictors of prostate cancer risk and survival, particularly in the AA patient population. It is thus an aim of the present invention to predict the risk and survival of a patient, by detecting the presence or absence of AA predominant variants of the genes in the oncogenic signaling pathways, particularly for PIK3CD, FGFR3, TSC2, FGFR2, PDGFRA, ITGA4, MET, EPHA3, NF1, RASGRP2, CTNNB1, TSC2, ATM, CDK4, and RB1, and more particularly for PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1. It is also an aspect of the present invention to utilize relative proportions of splicing variants of a certain gene as a predictor for PCa risk and survival in a patient.
Another aspect of the present invention is directed to isolated polynucleotide sequences of novel splicing variants of PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1. These novel splicing variants are particularly useful for the detection of the presence or absence of splicing variants in these genes that are in oncogenic signaling pathways. Detection of the presence or absence of splicing variants may be by polymerase chain reaction, by oligonucleotide probes hybridization, particularly high throughput DNA micro array analysis, or high throughput DNA sequencing, or any other means known to one skilled in the art. The isolated novel splicing variants sequences are also useful for targeted silencing of certain splicing variants of these genes. Targeted gene silencing may be by siRNA, miRNA, or other complementary RNA constructs.
Additionally, polypeptide products of the novel splicing variants of the present invention may be analyzed for determining the presence or absence of certain splicing variants. Mass spectrometry may be used to identify peptide fragments specific to certain splicing variants. Antibodies specifically recognize specific amino acid sequences of the novel splicing variants may be developed for the detection of the protein products of these splicing variants. The antibodies may be monoclonal antibodies, polyclonal antibodies, Fab, single chain antibody, or other engineered antibody constructs known to one skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic drawing for prostate biopsy core sampling;
FIG. 2 shows differentially expressed exons between AA and CA populations;
FIG. 3 shows differential splicing events in AA and CA PCa specimens;
FIG. 4 shows quantitative RT-PCR validation of differentially expressed exons in AA and CA specimens;
FIG. 5 illustrates alternative splicing events were found in various signaling molecules in the cell survival and proliferation pathways;
FIG. 6 shows relative expression levels of PIK3CD, FGFR3, TSC2, ITGA4, MET, NF1, BAK1, and RASGRP2 splicing variants;
FIG. 7 shows the effect of PIK3CD splicing variants on cell proliferation and invasion;
FIG. 8 shows effect of knockdown RASGRP2 splicing variants on cell proliferation and invasion;
FIG. 9 shows effect of knockdown PIK3CD “long” variant on the AKT pathway; and
FIG. 10 shows 4 novel PIK3CD variants.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Alternative splicing dramatically expands the protein coding repertoire of higher eukaryotes. Current estimates suggest that greater than 60% of all human genes have more than one isoform/splice variant. The expression of specific splice variants is regulated in a developmentally and tissue-specific manner (Black DL: Mechanisms of alternative pre-messenger RNA splicing. Annu Rev Biochem 2003, 72:291-336). Alternatively spliced isoforms from the same gene can produce proteins with drastically different properties. For example, the bcl-x gene utilizes different 5′ splice sites, resulting in proteins that have antagonistic functions. The short form of bcl-x promotes apoptosis, while the long form inhibits cell death (Boise L H, Gonzalez-Garcia M, Postema C E, Ding L, Lindsten T, Turka L A, Mao X, Nunez G, Thompson CB: bcl-x, a bcl-2-related gene that functions as a dominant regulator of apoptotic cell death. Cell 1993, 74:597-608).
Characterization of Clinical Specimens
Needle biopsy cores were collected by GWU Medical Faculty Associates urologists from right-base, left-base, right-mid, left-mid, right-apex, left-apex, right-transition, and left-transition zones of the prostate gland of individual patients presenting with high serum levels (>7 ng/ml) of prostate specific antigen (PSA). A schematic for 18 core biopsy is shown in FIG. 1 . Collected cores were immediately examined by a board certified PCa pathologist. PCa cores were determined to have a pathologic tumor stage of 2, and Gleason scores ranging from 6-9. There was no significant difference between the two racial groups (AA versus CA) with respect to age and tumor grade. Paired normal biopsy cores were also available from the same patients for genomic analysis (normal cores typically 1-2 cm away from cancer cores and deemed cancer free by pathologists). Each core contains sufficient RNA material for Affymetrix Human Exon 1.0 ST GeneChip profiling (i.e. 1 μg total RNA).
Exon Expression Profiling of AA and CA PCa and Normal Specimens
Total RNA was isolated from PCa and paired normal prostate cores. Exon profiling was performed on the Affymetrix Human Exon 1.0 ST GeneChip. The GeneChip represents an optimal platform for both expression profiling and splice variant detection (Kwan T, Benovoy D, Dias C, Gurd S, Provencher C, Beaulieu P, Hudson T J, Sladek R, Majewski J: Genome-wide analysis of transcript isoform variation in humans. Nat Genet 2008, 40:225-231; Network TCGAR: Comprehensive genomic characterization defines human glioblastoma genes and core pathways. Nature 2008, 455:1061-1068), as exon level annotations are derived from empirically determined, highly curated mRNA sequences and ab-initio computational predictions (see www.affymetrix.com/support/technical/whitepapers.affx). The GeneChip contains approximately 5.4 million 5-1 μm features (probes) grouped into 1.4 million probe sets interrogating over one million exon clusters. A 4-way statistical design (t-test with 10% false discovery rate (FDR) for multiple test correction) was employed to identify differentially expressed exons (corresponding to differentially expressed splice variants) in the following comparisons: AA normal vs. CA normal, AA cancer vs. CA cancer, AA cancer vs. AA normal, and CA cancer vs. CA normal. See FIG. 1A for comparison of AA cancer vs. CA cancer at the exon level.
The inventor through exon level analysis has identified 861 genes (e.g. PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1) exhibiting differential splicing patterns between the AA and CA populations. Differentially expressed exons between AA and CA populations are shown in FIG. 2 . FIG. 2(A) shows Principle Components Analysis (PCA) plots and clustering analysis of differentially expressed exons between AA and CA PCa specimens. 20 AA and 15 CA PCa specimens were analyzed for global alternative splicing patterns (i.e. differentially expressed exons) using the Affymetrix human Exon 1.0 ST arrays. These splice variants represent candidate markers mediating PCa disparities. An example of a gene exhibiting population-specific splicing is integrin α4 (ITGA4) which has been postulated to be a metastasis suppressor, since blocking its activity with antisense RNA enhances oral squamous carcinoma cell motility (Zhang Y, Lu H, Dazin P, Kapila Y: Functional differences between integrin alpha4 and integrins alpha5/alphaV in modulating the motility of human oral squamous carcinoma cells in response to the V region and heparin-binding domain of fibronectin. Exp Cell Res 2004, 295:48-58.).
FIG. 3 shows relative expression of individual exons of PIK3CD, FGFR3, and TSC2 in AA and CA prostate cancers. FIG. 3( a ) shows PIK3CD (phosphoinositide-3-kinase, catalytic, delta polypeptide) variants expression, FIG. 3( b ) shows FGFR3 (fibroblast growth factor receptor 3) variants expression, and FIG. 3( c ) shows TSC2 (tuberous sclerosis 2). Arrows indicate exons that are missing in the AA variant but present in the CA variant for each gene. Specifically, PIK3CD variants that lack exons 10 and 23, FGFR3 variant lack exon 14, and TSC2 variant lacks exon 19 are more prevalent in AA PCa patients.
FIG. 4 shows quantitative RT-PCR validation of differentially expressed exons in AA and CA specimens. AA and CA patient samples are analyzed using quantitative RT-PCR, using primers listed in Table 1. Preferential expression of a particular exon in either AA or CA PCa specimens for the PIK3CD, FGFR3, TSC2, ITGA4, MET, NF1, BAK1, and RASGRP2 genes is seen. E1F1AX and PPA1 served as internal RT-PCR control genes, which are expressed equally in AA and CA PCa specimens.
TABLE 1
Primers for qRT-PCR validations of splice variants
(-L and -S forms)
PIK3CD
Primer-f (SEQ ID No. 2):
CAAACTGAAGGCCCTGAATGA
Primer-r (SEQ ID No. 3):
TCTCGGATCATGATGTTGTCG
FGFR3
Primer-f (SEQ ID No. 20):
ACAACGTGATGAAGATCGCA
Primer-r (SEQ ID No. 21):
AGGTCGTGTGTGCAGTTGG
TSC2
Primer-f (SEQ ID No. 29):
TTTGACTTCCTGTTGCTGCT
Primer-r (SEQ ID No. 30):
TGAGCACTTTATAGCGCAG
RASGRP2
Primer-f (SEQ ID No. 38):
TCACGGTGTCTCTGGATCAGT
Primer-r (SEQ ID No. 39):
CCACCATCTTCTCGATGTGCT
ITGA4
Primer-f (SEQ ID No. 53):
TCTTGCTGTTGGGAGTATGAA
Primer-r (SEQ ID No. 54):
TGATACTGAGGTCCTCTTCCG
MET
Primer-f (SEQ ID No. 66):
TGGTGGAAAGAACCTCTCAA
Primer-r (SEQ ID No. 67):
ATCTTGGCTCACTGCAACCT
NF1
Primer-f (SEQ ID No. 71):
GCATTTTGGAACTGGGTAGAA
Primer-r (SEQ ID No. 72):
AACCACCATGGACTGAACAA
BAK1
Primer-f (SEQ ID No. 80):
CCTGTTTGAGAGTGGCATCAA
Primer-r (SEQ ID No. 81):
TTGATGCCACTCTCAAACAGG
Recently, genome sequencing efforts as part of the Cancer Genome Atlas Project has demonstrated that a number of genes (e.g. RAS, PTEN, p53, PI3K, APC, etc.) exhibiting frequent mutational hits in cancers can be found primarily residing in 3-5 major signaling pathways (Network TCGAR: Comprehensive genomic characterization defines human glioblastoma genes and core pathways. Nature 2008, 455:1061-1068; Parsons D W, Jones S, Zhang X, Lin J C, Leary R J, Angenendt P, Mankoo P, Carter H, Siu IM, Gallia G L, et al: An integrated genomic analysis of human glioblastoma multiforme. Science 2008, 321:1807-1812; Ding L, Getz G, Wheeler D A, Mardis E R, McLellan M D, Cibulskis K, Sougnez C, Greulich H, Muzny D M, Morgan M B, et al: Somatic mutations affect key pathways in lung adenocarcinoma. Nature 2008, 455:1069-1075). Of interest from a cancer disparities perspective is our observation that many of these same genes are prone to population-specific splicing patterns. FIG. 5 indicates genes marked with (AS) define differential alternative splicing events occurring in AA versus CA PCa. (Copy number amplifications (A) and deletions (D) are also indicated). At least 11 out of 26 genes residing in the 5 oncogenic signaling pathways have been identified by the inventors as exhibiting differential splicing between AA and CA PCa specimens. These genes include FGFR2, PDGFRA, MET, EPHA3, NF1, RASGRP2, CTNNB 1, TSC2, ATM, CDK4, and RB 1. The inventors further show that differential mRNA splicing in racial populations plays an important role in cancer health disparities.
FIG. 6 shows quantification of differential splicing in PIK3CD, FGFR3, TSC2, ITGA4, MET, NF1, BAK1, and RASGRP2 in AA and CA PCa patients. For each of these genes, one variant is predominant in AA patients. Also, proportions of variants, such as short and long form of PIK3CD are markedly different between AA and CA patients. AA patients have a higher S/L ration than CA patients.
Functional Consequences of Splice Variants in PCa Cell Lines Derived from AA and CA Patients
Inventors demonstrate that the splice variant (short form or S variant) for phosphoinositide-3 kinase delta (PIK3CD) found in AA PCa specimens encodes a more aggressive version of the gene (i.e. leading to greater proliferation and invasion of cancer cells) compared to the variant counterpart (long form or L variant) found in CA PCa specimens ( FIG. 7 ). In the CA PCa cell line VCaP, the L form is the only variant found, while very little to no expression of the S variant is seen (and hence the reason we refer to the L variant as the ‘CA isoform’) ( FIG. 7A ). The predominant expression of the L variant and very little to no expression of the S variant in the CA PCa cell line is consistent with the CA patient samples (see PIK3CD in FIG. 4 ). SiRNA-mediated knockdown of the L variant in VCaP cells leads to a decrease in Matrigel invasion and a decrease in proliferation ( FIG. 7A ). By comparison, the AA PCa cell line MDA PCa 2b expresses both an L and S variant, and knockdown of the L variant leads to an increase in Matrigel invasion and an increase in proliferation ( FIG. 7A ). Since VCaP cells express very little to no S variant, targeted siRNA-mediated knockdown of this variant leads to no change in Matrigel invasion and proliferation ( FIG. 7B ). In contrast, targeted knockdown of the S variant in MDA PCa 2b cells leads to decreased Matrigel invasion and decreased proliferation (since the S variant is found almost exclusively in AA patient samples, it is referred to as the ‘AA variant’) ( FIG. 7B ). These data indicate that the balance of S to L isoforms in MDA PCa 2b cells dictates the oncogenic profile of the AA PCa cell line. Namely, knocking down the L variant in MDA PCa 2b cells increases the S/L ratio, leading to a higher proportion of the aggressive S variant and consequently increased invasiveness and proliferation of the cell line. In contrast, knocking down the S variant in MDA PCa 2b cells decreases the S/L ratio, leading to a higher proportion of the less aggressive L variant and consequently decreased invasiveness and proliferation of the cell line. Analogous findings were obtained in MDA PCa 2b cells when the ratio of the ‘AA variant’ (S or b isoform) was increased over the ‘CA variant’ (L or an isoform) for the FGFR3, TSC2.
For RASGRP2, the long variant (with exon 10) is common to both AA and CA patients, whereas the short variant (without exon 10) is unique to AA. Targeted knockdown of the long splicing variant in VCaP cells reduced Matrigel invasion and an increase in proliferation ( FIG. 8 ). In contrast, target knockdown of the RASGRP2 long variant in MDA PCa 2b Cells has the opposite effect.
Activation of AKT is known to promote cell growth and mRNA translation ( FIG. 9 a ). When the expression of PIK3CD “long” variant is knocked down by siRNA targeting of Exon 23 in the VCaP cell line, which only expresses the long variant, there is a decrease of phosphorylation of AKT, compared to nonsense siRNA control, and also decrease of phosphorylation of downstream signaling proteins mTOR and S6 ( FIG. 9 b ). However, in MDA PCa 2b cells, which express the short variant of PIK3CD, knocking down the long variant of PIK3CD markedly increases AKT phosphorylation, both on Thr308 and Ser473, and increases phosphorylation of mTOR and S6 ( FIG. 9 b ). In other words, increasing S/L variants proportion in MDA PCa 2b cells activates the AKT pathways.
The inventor discovered four novel PIK3CD variants ( FIG. 10 ), where variant 1 lacks exon 10 (SEQ ID No. 7), which can be shown as the deletion of nt2430-2592 compared to full length PIK3CD cDNA sequence (SEQ ID. No. 1), variant 2 lacks exon 23 (SEQ ID No. 11, deletion of nt931-1020), variant 3 lacks both exon 10 and 23 (SEQ ID No. 14, deletion of nt931-1020 and nt2430-2592), and variant 4 contains a deletion from nt1329-2627 (SEQ ID No. 16). The nucleotide sequence of PIK3CD full length cDNA sequence is shown in Table 2. Exon 10 and exon 23 are marked with double underline and wave underline, respectively. cDNA sequence of variants 1-4 (SEQ ID Nos. 7, 11, 14, and 16) are shown in Tables 3-6. Exemplary primers across the junctions of the splicing variants (SEQ ID Nos. 6, 10, and 15) that are useful for detecting the presence of these variants are shown in Table 7. Exemplary siRNAs for selective knockdown of PIK3CD full length (targeting exon 23, SEQ ID Nos. 4 and 5)) and variants (targeting exon junctions (SEQ ID Nos. 8, 9, 12, and 13) and deletion junction (SEQ ID Nos. 17 and 18)) are listed in Table 8.
The inventor also discovered a novel splicing variant of FGFR3 (fibroblast growth factor receptor 3), which lacks exon 14 (SEQ ID No. 19, Table 10). The nucleotide sequence of FGFR3 full length cDNA sequence (SEQ ID No. 19) is shown in Table 9. Exon 14 is marked with double underline. Exemplary primer across the junction of splicing variant (SEQ ID No. 26) that is useful for detecting the presence of this variant is shown in Table 11. Exemplary siRNAs for selective knockdown of FGFR3 full length (targeting exon 14, SEQ ID NOs. 22 and 23)) and variant (targeting exon junction (SEQ ID Nos. 26 and 27) are listed in Table 12.
The inventor also discovered a novel splicing variant of TSC2 (tuberous sclerosis 2), which lacks exon 19 (SEQ ID No. 34, Table 14). The nucleotide sequence of TSC2 full length cDNA sequence (SEQ ID No. 28) is shown in Table 12. Exon 19 is marked with double underline. Exemplary primer across the junction of splicing variant (SEQ ID No. 33) that is useful for detecting the presence of this variant is shown in Table 15. Exemplary siRNAs for selective knockdown of TSC2 full length (targeting exon 19, SEQ ID NOs. 31 and 32)) and variant (targeting exon junction (SEQ ID Nos. 35 and 36) are listed in Table 16.
The inventor also discovered two novel splicing variants of RASGRP2 (RAS guanyl-releasing protein 2), which lacks exon 10 (SEQ ID No. 45, Table 18) or exon 11 (SEQ ID No. 49, Table 19). The nucleotide sequence of RASGRP2 full length cDNA sequence (SEQ ID No. 37) is shown in Table 17. Exon 10 is marked with double underline, and exon 11 is marked with wave underline. Exemplary primers across the junctions of the splicing variants (SEQ ID Nos. 44 and 48) that are useful for detecting the presence of these variants are shown in Table 20. Exemplary siRNAs for selective knockdown RASGRP2 full length (targeting exon 10, SEQ ID NOs. 40 and 41, targeting exon 11, SEQ ID NOs. 42 and 43)) and variants (targeting exon junctions (SEQ ID Nos. 46, 47, 50, and 51)) are listed in Table 21.
The inventor also discovered a novel splicing variant of ITGA4 (integrin α4), which lacks exon 23 (SEQ ID No. 58, Table 23). The nucleotide sequence of ITGA4 full length cDNA sequence (SEQ ID No. 52) is shown in Table 22. Exon 23 is marked with double underline. Exemplary primer across the junction of splicing variant (SEQ ID No. 57) that is useful for detecting the presence of this variant is shown in Table 24. Exemplary siRNAs for selective knockdown of ITGA4 full length (targeting exon 23, SEQ ID NOs. 55 and 56)) and variant (targeting exon junction (SEQ ID Nos. 59 and 60)) are listed in Table 25.
The inventor also discovered a novel splicing variant of MET (MNNG HOS Transforming gene), which include the insertion of non-coding exon 27 (SEQ ID No. 65, Table 27). The nucleotide sequence of MET full length cDNA sequence (SEQ ID No. 62) is shown in Table 26. Exon 27 is marked with double underline. Exemplary primer across junctions of full length variant (SEQ ID No. 61) is shown in Table 28. Exemplary siRNAs for selective knockdown of MET full length (targeting exon junction 26 and 28 (SEQ ID Nos. 63 and 64) and variant (targeting exon 27 (SEQ ID Nos. 68 and 69)) are listed in Table 29.
The inventor also discovered a novel splicing variant of NF1 (Neurofibromin 1), which lacks exon 8 (SEQ ID No. 76, Table 31). The nucleotide sequence of NF1 full length cDNA sequence (SEQ ID No. 70) is shown in Table 30. Exon 8 is marked with double underline. Exemplary primer across the junction of splicing variant (SEQ ID No. 75) that is useful for detecting the presence of this variant is shown in Table 32. Exemplary siRNAs for selective knockdown of NF1 full length (targeting exon 8, SEQ ID NOs. 73 and 74) and variant (targeting exon junction (SEQ ID Nos. 77 and 78)) are listed in Table 33.
The inventor also discovered a novel splicing variant of BAK1 (Bcl-2 homologous antagonist/killer), which lacks exon 2 (SEQ ID No. 85, Table 35). The nucleotide sequence of BAK1 full length cDNA sequence (SEQ ID No. 79) is shown in Table 34. Exon 2 is marked with double underline. Exemplary primer across the junction of splicing variant (SEQ ID No. 84) that is useful for detecting the presence of this variant is shown in Table 36. Exemplary siRNAs for selective knockdown of BAK1 full length (targeting exon 2, SEQ ID NOs. 82 and 83) and variant (targeting exon junction (SEQ ID Nos. 86 and 87) are listed in Table 37.
TABLE 2
PIK3CD (Full length)Nucleotide Sequence (3135 nt, SEQ ID
No. 1)
ATGCCCCCTGGGGTGGACTGCCCCATGGAATTCTGGACCAAGGAGGAGAATCAGAGCGTTGTGGTTGACT
TCCTGCTGCCCACAGGGGTCTACCTGAACTTCCCTGTGTCCCGCAATGCCAACCTCAGCACCATCAAGCA
GCTGCTGTGGCACCGCGCCCAGTATGAGCCGCTCTTCCACATGCTCAGTGGCCCCGAGGCCTATGTGTTC
ACCTGCATCAACCAGACAGCGGAGCAGCAAGAGCTGGAGGACGAGCAACGGCGTCTGTGTGACGTGCAGC
CCTTCCTGCCCGTCCTGCGCCTGGTGGCCCGTGAGGGCGACCGCGTGAAGAAGCTCATCAACTCACAGAT
CAGCCTCCTCATCGGCAAAGGCCTCCACGAGTTTGACTCCTTGTGCGACCCAGAAGTGAACGACTTTCGC
GCCAAGATGTGCCAATTCTGCGAGGAGGCGGCCGCCCGCCGGCAGCAGCTGGGCTGGGAGGCCTGGCTGC
AGTACAGTTTCCCCCTGCAGCTGGAGCCCTCGGCTCAAACCTGGGGGCCTGGTACCCTGCGGCTCCCGAA
CCGGGCCCTTCTGGTCAACGTTAAGTTTGAGGGCAGCGAGGAGAGCTTCACCTTCCAGGTGTCCACCAAG
GACGTGCCGCTGGCGCTGATGGCCTGTGCCCTGCGGAAGAAGGCCACAGTGTTCCGGCAGCCGCTGGTGG
AGCAGCCGGAAGACTACACGCTGCAGGTGAACGGCAGGCATGAGTACCTGTATGGCAGCTACCCGCTCTG
CCAGTTCCAGTACATCTGCAGCTGCCTGCACAGTGGGTTGACCCCTCACCTGACCATGGTCCATTCCTCC
TCCATCCTCGCCATGCGGGATGAGCAGAGCAACCCTGCCCCCCAGGTCCAGAAACCGCGTGCCAAACCAC
CTCCCATTCCTGCGAAGAAG CCTTCCTCTGTGTCCCTGTGGTCCCTGGAGCAGCCGTTCCGCATCGAGCT
CATCCAGGGCAGCAAAGTGAACGCCGACGAGCGGATGAAG CTGGTGGTGCAGGCCGGGCTTTTCCACGGC
AACGAGATGCTGTGCAAGACGGTGTCCAGCTCGGAGGTGAGCGTGTGCTCGGAGCCCGTGTGGAAGCAGC
GGCTGGAGTTCGACATCAACATCTGCGACCTGCCCCGCATGGCCCGTCTCTGCTTTGCGCTGTACGCCGT
GATCGAGAAAGCCAAGAAGGCTCGCTCCACCAAGAAGAAGTCCAAGAAGGCGGACTGCCCCATTGCCTGG
GCCAACCTCATGCTGTTTGACTACAAGGACCAGCTTAAGACCGGGGAACGCTGCCTCTACATGTGGCCCT
CCGTCCCAGATGAGAAGGGCGAGCTGCTGAACCCCACGGGCACTGTGCGCAGTAACCCCAACACGGATAG
CGCCGCTGCCCTGCTCATCTGCCTGCCCGAGGTGGCCCCGCACCCCGTGTACTACCCCGCCCTGGAGAAG
ATCTTGGAGCTGGGGCGACACAGCGAGTGTGTGCATGTCACCGAGGAGGAGCAGCTGCAGCTGCGGGAAA
TCCTGGAGCGGCGGGGGTCTGGGGAGCTGTATGAGCACGAGAAGGACCTGGTGTGGAAGCTGCGGCATGA
AGTCCAGGAGCACTTCCCGGAGGCGCTAGCCCGGCTGCTGCTGGTCACCAAGTGGAACAAGCATGAGGAT
GTGGCCCAGATGCTCTACCTGCTGTGCTCCTGGCCGGAGCTGCCCGTCCTGAGCGCCCTGGAGCTGCTAG
ACTTCAGCTTCCCCGATTGCCACGTAGGCTCCTTCGCCATCAAGTCGCTGCGGAAACTGACGGACGATGA
GCTGTTCCAGTACCTGCTGCAGCTGGTGCAGGTGCTCAAGTACGAGTCCTACCTGGACTGCGAGCTGACC
AAATTCCTGCTGGACCGGGCCCTGGCCAACCGCAAGATCGGCCACTTCCTTTTCTGGCACCTCCGCTCCG
AGATGCACGTGCCGTCGGTGGCCCTGCGCTTCGGCCTCATCCTGGAGGCCTACTGCAGGGGCAGCACCCA
CCACATGAAGGTGCTGATGAAGCAGGGGGAAGCACTGAG CAAACTGAAGGCCCTGAATGA CTTCGTCAAG
CTGAGCTCTCAGAAGACCCCCAAGCCCCAGACCAAGGAGCTGATGCACTTGTGCATGCGGCAGGAGGCCT
ACCTAGAGGCCCTCTCCCACCTGCAGTCCCCACTCGACCCCAGCACCCTGCTGGCTGAAGTCTGCGTGGA
GCAGTGCACCTTCATGGACTCCAAGATGAAGCCCCTGTGGATCATGTACAGCAACGAGGAGGCAGGCAGC
GGCGGCAGCGTGGGCATCATCTTTAAGAACGGGGATGACCTCCGGCAGGACATGCTGACCCTGCAGATGA
TGTGCTGGGCATTGGCGATCGGCACAG CGACAACATCATGATCCGAGA GAGTGGGCAGCTGTTCCACATT
GATTTTGGCCACTTTCTGGGGAATTTCAAGACCAAGTTTGGAATCAACCGCGAGCGTGTCCCATTCATCC
TCACCTACGACTTTGTCCATGTGATTCAGCGGGGAAGACTAATAATAGTTGAGAAATTTGAACGGTTCCG
GGGCTACTGTGAAAGGGCCTACACCATCCTGCGGCGCCACGGGCTTCTCTTCCTCCACCTCTTTGCCCTG
ATGCGGGCGGCAGGCCTGCCTGAGCTCAGCTGCTCCAAAGACATCCAGTATCTCAAGGACTCCCTGGCAC
TGGGGAAAACAGAGGAGGAGGCACTGAAGCACTTCCGAGTGAAGTTTAACGAAGCCCTCCGTGAGAGCTG
GAAAACCAAAGTGAACTGGCTGGCCCACAACGTGTCCAAAGACAACAGGCAGTAG
(Exon 10 is indicated by double underline, Exon 23 is indicated by wave underline. Primers for qRT-PCR validations of PIK3CD splice variants (-L and -S forms) are underlined)
TABLE 3
PIK3CD variant 1 (lacking exon 10) Nucleotide Sequence
(3045 nt, SEQ ID No. 7)
ATGCCCCCTGGGGTGGACTGCCCCATGGAATTCTGGACCAAGGAGGAGAATCAGAGCGTTGTGGTTGACT
TCCTGCTGCCCACAGGGGTCTACCTGAACTTCCCTGTGTCCCGCAATGCCAACCTCAGCACCATCAAGCA
GCTGCTGTGGCACCGCGCCCAGTATGAGCCGCTCTTCCACATGCTCAGTGGCCCCGAGGCCTATGTGTTC
ACCTGCATCAACCAGACAGCGGAGCAGCAAGAGCTGGAGGACGAGCAACGGCGTCTGTGTGACGTGCAGC
CCTTCCTGCCCGTCCTGCGCCTGGTGGCCCGTGAGGGCGACCGCGTGAAGAAGCTCATCAACTCACAGAT
CAGCCTCCTCATCGGCAAAGGCCTCCACGAGTTTGACTCCTTGTGCGACCCAGAAGTGAACGACTTTCGC
GCCAAGATGTGCCAATTCTGCGAGGAGGCGGCCGCCCGCCGGCAGCAGCTGGGCTGGGAGGCCTGGCTGC
AGTACAGTTTCCCCCTGCAGCTGGAGCCCTCGGCTCAAACCTGGGGGCCTGGTACCCTGCGGCTCCCGAA
CCGGGCCCTTCTGGTCAACGTTAAGTTTGAGGGCAGCGAGGAGAGCTTCACCTTCCAGGTGTCCACCAAG
GACGTGCCGCTGGCGCTGATGGCCTGTGCCCTGCGGAAGAAGGCCACAGTGTTCCGGCAGCCGCTGGTGG
AGCAGCCGGAAGACTACACGCTGCAGGTGAACGGCAGGCATGAGTACCTGTATGGCAGCTACCCGCTCTG
CCAGTTCCAGTACATCTGCAGCTGCCTGCACAGTGGGTTGACCCCTCACCTGACCATGGTCCATTCCTCC
TCCATCCTCGCCATGCGGGATGAGCAGAGCAACCCTGCCCCCCAGGTCCAGAAACCGCGTGCCAAACCAC
CTCCCATTCC TGCGAAGAA GC TGGTGGTGC AGGCCGGGCTTTTCCACGGCAACGAGATGCTGTGCAAGACGG
TGTCCAGCTCGGAGGTGAGCGTGTGCTCGGAGCCCGTGTGGAAGCAGCGGCTGGAGTTCGACATCAACATCT
GCGACCTGCCCCGCATGGCCCGTCTCTGCTTTGCGCTGTACGCCGTGATCGAGAAAGCCAAGAAGGCTCGCT
CCACCAAGAAGAAGTCCAAGAAGGCGGACTGCCCCATTGCCTGGGCCAACCTCATGCTGTTTGACTACAAGG
ACCAGCTTAAGACCGGGGAACGCTGCCTCTACATGTGGCCCTCCGTCCCAGATGAGAAGGGCGAGCTGCTGA
ACCCCACGGGCACTGTGCGCAGTAACCCCAACACGGATAGCGCCGCTGCCCTGCTCATCTGCCTGCCCGAGG
TGGCCCCGCACCCCGTGTACTACCCCGCCCTGGAGAAGATCTTGGAGCTGGGGCGACACAGCGAGTGTGTGC
ATGTCACCGAGGAGGAGCAGCTGCAGCTGCGGGAAATCCTGGAGCGGCGGGGGTCTGGGGAGCTGTATGAGC
ACGAGAAGGACCTGGTGTGGAAGCTGCGGCATGAAGTCCAGGAGCACTTCCCGGAGGCGCTAGCCCGGCTGC
TGCTGGTCACCAAGTGGAACAAGCATGAGGATGTGGCCCAGATGCTCTACCTGCTGTGCTCCTGGCCGGAGC
TGCCCGTCCTGAGCGCCCTGGAGCTGCTAGACTTCAGCTTCCCCGATTGCCACGTAGGCTCCTTCGCCATCA
AGTCGCTGCGGAAACTGACGGACGATGAGCTGTTCCAGTACCTGCTGCAGCTGGTGCAGGTGCTCAAGTACG
AGTCCTACCTGGACTGCGAGCTGACCAAATTCCTGCTGGACCGGGCCCTGGCCAACCGCAAGATCGGCCACT
TCCTTTTCTGGCACCTCCGCTCCGAGATGCACGTGCCGTCGGTGGCCCTGCGCTTCGGCCTCATCCTGGAGG
CCTACTGCAGGGGCAGCACCCACCACATGAAGGTGCTGATGAAGCAGGGGGAAGCACTGAGCAAACTGAAGG
CCCTGAATGACTTCGTCAAGCTGAGCTCTCAGAAGACCCCCAAGCCCCAGACCAAGGAGCTGATGCACTTGT
GCATGCGGCAGGAGGCCTACCTAGAGGCCCTCTCCCACCTGCAGTCCCCACTCGACCCCAGCACCCTGCTGG
CTGAAGTCTGCGTGGAGCAGTGCACCTTCATGGACTCCAAGATGAAGCCCCTGTGGATCATGTACAGCAACG
AGGAGGCAGGCAGCGGCGGCAGCGTGGGCATCATCTTTAAGAACGGGGATGACCTCCGGCAGGACATGCTGA
CCCTGCAGATGATCCAGCTCATGGACGTCCTGTGGAAGCAGGAGGGGCTGGACCTGAGGATGACCCCCTATG
GCTGCCTCCCCACCGGGGACCGCACAGGCCTCATTGAGGTGGTACTCCGTTCAGACACCATCGCCAACATCC
AACTCAACAAGAGCAACATGGCAGCCACAGCCGCCTTCAACAAGGATGCCCTGCTCAACTGGCTGAAGTCCA
AGAACCCGGGGGAGGCCCTGGATCGAGCCATTGAGGAGTTCACCCTCTCCTGTGCTGGCTATTGTGTGGCCA
CATATGTGCTGGGCATTGGCGATCGGCACAGCGACAACATCATGATCCGAGAGAGTGGGCAGCTGTTCCACA
TTGATTTTGGCCACTTTCTGGGGAATTTCAAGACCAAGTTTGGAATCAACCGCGAGCGTGTCCCATTCATCC
TCACCTACGACTTTGTCCATGTGATTCAGCAGGGGAAGACTAATAATAGTGAGAAATTTGAACGGTTCCGGG
GCTACTGTGAAAGGGCCTACACCATCCTGCGGCGCCACGGGCTTCTCTTCCTCCACCTCTTTGCCCTGATGC
GGGCGGCAGGCCTGCCTGAGCTCAGCTGCTCCAAAGACATCCAGTATCTCAAGGACTCCCTGGCACTGGGGA
AAACAGAGGAGGAGGCACTGAAGCACTTCCGAGTGAAGTTTAACGAAGCCCTCCGTGAGAGCTGGAAAACCA
AAGTGAACTGGCTGGCCCACAACGTGTCCAAAGACAACAGGCAGTAG
(Double underline indicates bases bordering the splice junction)
TABLE 4
PIK3CD variant 2 (lacking exon 23)Nucleotide Sequence
(2967 nt, SEQ ID No. 11)
ATGCCCCCTGGGGTGGACTGCCCCATGGAATTCTGGACCAAGGAGGAGAATCAGAGCGTTGTGGTTGACT
TCCTGCTGCCCACAGGGGTCTACCTGAACTTCCCTGTGTCCCGCAATGCCAACCTCAGCACCATCAAGCA
GCTGCTGTGGCACCGCGCCCAGTATGAGCCGCTCTTCCACATGCTCAGTGGCCCCGAGGCCTATGTGTTC
ACCTGCATCAACCAGACAGCGGAGCAGCAAGAGCTGGAGGACGAGCAACGGCGTCTGTGTGACGTGCAGC
CCTTCCTGCCCGTCCTGCGCCTGGTGGCCCGTGAGGGCGACCGCGTGAAGAAGCTCATCAACTCACAGAT
CAGCCTCCTCATCGGCAAAGGCCTCCACGAGTTTGACTCCTTGTGCGACCCAGAAGTGAACGACTTTCGC
GCCAAGATGTGCCAATTCTGCGAGGAGGCGGCCGCCCGCCGGCAGCAGCTGGGCTGGGAGGCCTGGCTGC
AGTACAGTTTCCCCCTGCAGCTGGAGCCCTCGGCTCAAACCTGGGGGCCTGGTACCCTGCGGCTCCCGAA
CCGGGCCCTTCTGGTCAACGTTAAGTTTGAGGGCAGCGAGGAGAGCTTCACCTTCCAGGTGTCCACCAAG
GACGTGCCGCTGGCGCTGATGGCCTGTGCCCTGCGGAAGAAGGCCACAGTGTTCCGGCAGCCGCTGGTGG
AGCAGCCGGAAGACTACACGCTGCAGGTGAACGGCAGGCATGAGTACCTGTATGGCAGCTACCCGCTCTG
CCAGTTCCAGTACATCTGCAGCTGCCTGCACAGTGGGTTGACCCCTCACCTGACCATGGTCCATTCCTCC
TCCATCCTCGCCATGCGGGATGAGCAGAGCAACCCTGCCCCCCAGGTCCAGAAACCGCGTGCCAAACCAC
CTCCCATTCCTGCGAAGAAGCCTTCCTCTGTGTCCCTGTGGTCCCTGGAGCAGCCGTTCCGCATCGAGCT
CATCCAGGGCAGCAAAGTGAACGCCGACGAGCGGATGAAGCTGGTGGTGCAGGCCGGGCTTTTCCACGGC
AACGAGATGCTGTGCAAGACGGTGTCCAGCTCGGAGGTGAGCGTGTGCTCGGAGCCCGTGTGGAAGCAGC
GGCTGGAGTTCGACATCAACATCTGCGACCTGCCCCGCATGGCCCGTCTCTGCTTTGCGCTGTACGCCGT
GATCGAGAAAGCCAAGAAGGCTCGCTCCACCAAGAAGAAGTCCAAGAAGGCGGACTGCCCCATTGCCTGG
GCCAACCTCATGCTGTTTGACTACAAGGACCAGCTTAAGACCGGGGAACGCTGCCTCTACATGTGGCCCT
CCGTCCCAGATGAGAAGGGCGAGCTGCTGAACCCCACGGGCACTGTGCGCAGTAACCCCAACACGGATAG
CGCCGCTGCCCTGCTCATCTGCCTGCCCGAGGTGGCCCCGCACCCCGTGTACTACCCCGCCCTGGAGAAG
ATCTTGGAGCTGGGGCGACACAGCGAGTGTGTGCATGTCACCGAGGAGGAGCAGCTGCAGCTGCGGGAAA
TCCTGGAGCGGCGGGGGTCTGGGGAGCTGTATGAGCACGAGAAGGACCTGGTGTGGAAGCTGCGGCATGA
AGTCCAGGAGCACTTCCCGGAGGCGCTAGCCCGGCTGCTGCTGGTCACCAAGTGGAACAAGCATGAGGAT
GTGGCCCAGATGCTCTACCTGCTGTGCTCCTGGCCGGAGCTGCCCGTCCTGAGCGCCCTGGAGCTGCTAG
ACTTCAGCTTCCCCGATTGCCACGTAGGCTCCTTCGCCATCAAGTCGCTGCGGAAACTGACGGACGATGA
GCTGTTCCAGTACCTGCTGCAGCTGGTGCAGGTGCTCAAGTACGAGTCCTACCTGGACTGCGAGCTGACC
AAATTCCTGCTGGACCGGGCCCTGGCCAACCGCAAGATCGGCCACTTCCTTTTCTGGCACCTCCGCTCCG
AGATGCACGTGCCGTCGGTGGCCCTGCGCTTCGGCCTCATCCTGGAGGCCTACTGCAGGGGCAGCACCCA
CCACATGAAGGTGCTGATGAAGCAGGGGGAAGCACTGAGCAAACTGAAGGCCCTGAATGACTTCGTCAAG
CTGAGCTCTCAGAAGACCCCCAAGCCCCAGACCAAGGAGCTGATGCACTTGTGCATGCGGCAGGAGGCCT
ACCTAGAGGCCCTCTCCCACCTGCAGTCCCCACTCGACCCCAGCACCCTGCTGGCTGAAGTCTGCGTGGA
GCAGTGCACCTTCATGGACTCCAAGATGAAGCCCCTGTGGATCATGTACAGCAACGAGGAGGCAGGCAGC
GGCGGCAGCGTGGGCATCATCTTTAAGAACGGGGATGACCTCCGGCAGGACATGCTGACCCTGCAGATGA
TCCAGCTCATGGACGTCCTGTGGAAGCAGGAGGGGC TGGACCTGA GG GAGGCCCT GGATCGAGCCATTGAGG
AGTTCACCCTCTCCTGTGCTGGCTATTGTGTGGCCACATATGTGCTGGGCATTGGCGATCGGCACAGCGACA
ACATCATGATCCGAGAGAGTGGGCAGCTGTTCCACATTGATTTTGGCCACTTTCTGGGGAATTTCAAGACCA
AGTTTGGAATCAACCGCGAGCGTGTCCCATTCATCCTCACCTACGACTTTGTCCATGTGATTCAGCAGGGGA
AGACTAATAATAGTGAGAAATTTGAACGGTTCCGGGGCTACTGTGAAAGGGCCTACACCATCCTGCGGCGCC
ACGGGCTTCTCTTCCTCCACCTCTTTGCCCTGATGCGGGCGGCAGGCCTGCCTGAGCTCAGCTGCTCCAAAG
ACATCCAGTATCTCAAGGACTCCCTGGCACTGGGGAAAACAGAGGAGGAGGCACTGAAGCACTTCCGAGTGA
AGTTTAACGAAGCCCTCCGTGAGAGCTGGAAAACCAAAGTGAACTGGCTGGCCCACAACGTGTCCAAAGACA
ACAGGCAGTAG
(Double underline indicates bases bordering the splice junction)
TABLE 5
PIK3CD variant 3 (lacking exon 10 and exon 23)
Nucleotide Sequence (2877 nt, SEQ ID No. 14):
ATGCCCCCTGGGGTGGACTGCCCCATGGAATTCTGGACCAAGGAGGAGAATCAGAGCGTTGTGGTTGACT
TCCTGCTGCCCACAGGGGTCTACCTGAACTTCCCTGTGTCCCGCAATGCCAACCTCAGCACCATCAAGCA
GCTGCTGTGGCACCGCGCCCAGTATGAGCCGCTCTTCCACATGCTCAGTGGCCCCGAGGCCTATGTGTTC
ACCTGCATCAACCAGACAGCGGAGCAGCAAGAGCTGGAGGACGAGCAACGGCGTCTGTGTGACGTGCAGC
CCTTCCTGCCCGTCCTGCGCCTGGTGGCCCGTGAGGGCGACCGCGTGAAGAAGCTCATCAACTCACAGAT
CAGCCTCCTCATCGGCAAAGGCCTCCACGAGTTTGACTCCTTGTGCGACCCAGAAGTGAACGACTTTCGC
GCCAAGATGTGCCAATTCTGCGAGGAGGCGGCCGCCCGCCGGCAGCAGCTGGGCTGGGAGGCCTGGCTGC
AGTACAGTTTCCCCCTGCAGCTGGAGCCCTCGGCTCAAACCTGGGGGCCTGGTACCCTGCGGCTCCCGAA
CCGGGCCCTTCTGGTCAACGTTAAGTTTGAGGGCAGCGAGGAGAGCTTCACCTTCCAGGTGTCCACCAAG
GACGTGCCGCTGGCGCTGATGGCCTGTGCCCTGCGGAAGAAGGCCACAGTGTTCCGGCAGCCGCTGGTGG
AGCAGCCGGAAGACTACACGCTGCAGGTGAACGGCAGGCATGAGTACCTGTATGGCAGCTACCCGCTCTG
CCAGTTCCAGTACATCTGCAGCTGCCTGCACAGTGGGTTGACCCCTCACCTGACCATGGTCCATTCCTCC
TCCATCCTCGCCATGCGGGATGAGCAGAGCAACCCTGCCCCCCAGGTCCAGAAACCGCGTGCCAAACCAC
CTCCCATTCC TGCGAAGAA GC TGGTGGTG C AGGCCGGGCTTTTCCACGGCAACGAGATGCTGTGCAAGACGG
TGTCCAGCTCGGAGGTGAGCGTGTGCTCGGAGCCCGTGTGGAAGCAGCGGCTGGAGTTCGACATCAACATCT
GCGACCTGCCCCGCATGGCCCGTCTCTGCTTTGCGCTGTACGCCGTGATCGAGAAAGCCAAGAAGGCTCGCT
CCACCAAGAAGAAGTCCAAGAAGGCGGACTGCCCCATTGCCTGGGCCAACCTCATGCTGTTTGACTACAAGG
ACCAGCTTAAGACCGGGGAACGCTGCCTCTACATGTGGCCCTCCGTCCCAGATGAGAAGGGCGAGCTGCTGA
ACCCCACGGGCACTGTGCGCAGTAACCCCAACACGGATAGCGCCGCTGCCCTGCTCATCTGCCTGCCCGAGG
TGGCCCCGCACCCCGTGTACTACCCCGCCCTGGAGAAGATCTTGGAGCTGGGGCGACACAGCGAGTGTGTGC
ATGTCACCGAGGAGGAGCAGCTGCAGCTGCGGGAAATCCTGGAGCGGCGGGGGTCTGGGGAGCTGTATGAGC
ACGAGAAGGACCTGGTGTGGAAGCTGCGGCATGAAGTCCAGGAGCACTTCCCGGAGGCGCTAGCCCGGCTGC
TGCTGGTCACCAAGTGGAACAAGCATGAGGATGTGGCCCAGATGCTCTACCTGCTGTGCTCCTGGCCGGAGC
TGCCCGTCCTGAGCGCCCTGGAGCTGCTAGACTTCAGCTTCCCCGATTGCCACGTAGGCTCCTTCGCCATCA
AGTCGCTGCGGAAACTGACGGACGATGAGCTGTTCCAGTACCTGCTGCAGCTGGTGCAGGTGCTCAAGTACG
AGTCCTACCTGGACTGCGAGCTGACCAAATTCCTGCTGGACCGGGCCCTGGCCAACCGCAAGATCGGCCACT
TCCTTTTCTGGCACCTCCGCTCCGAGATGCACGTGCCGTCGGTGGCCCTGCGCTTCGGCCTCATCCTGGAGG
CCTACTGCAGGGGCAGCACCCACCACATGAAGGTGCTGATGAAGCAGGGGGAAGCACTGAGCAAACTGAAGG
CCCTGAATGACTTCGTCAAGCTGAGCTCTCAGAAGACCCCCAAGCCCCAGACCAAGGAGCTGATGCACTTGT
GCATGCGGCAGGAGGCCTACCTAGAGGCCCTCTCCCACCTGCAGTCCCCACTCGACCCCAGCACCCTGCTGG
CTGAAGTCTGCGTGGAGCAGTGCACCTTCATGGACTCCAAGATGAAGCCCCTGTGGATCATGTACAGCAACG
AGGAGGCAGGCAGCGGCGGCAGCGTGGGCATCATCTTTAAGAACGGGGATGACCTCCGGCAGGACATGCTGA
CCCTGCAGATGATCCAGCTCATGGACGTCCTGTGGAAGCAGGAGGGGC TGGACCTGA GG GAGGCCC TGGATC
GAGCCATTGAGGAGTTCACCCTCTCCTGTGCTGGCTATTGTGTGGCCACATATGTGCTGGGCATTGGCGATC
GGCACAGCGACAACATCATGATCCGAGAGAGTGGGCAGCTGTTCCACATTGATTTTGGCCACTTTCTGGGGA
ATTTCAAGACCAAGTTTGGAATCAACCGCGAGCGTGTCCCATTCATCCTCACCTACGACTTTGTCCATGTGA
TTCAGCAGGGGAAGACTAATAATAGTGAGAAATTTGAACGGTTCCGGGGCTACTGTGAAAGGGCCTACACCA
TCCTGCGGCGCCACGGGCTTCTCTTCCTCCACCTCTTTGCCCTGATGCGGGCGGCAGGCCTGCCTGAGCTCA
GCTGCTCCAAAGACATCCAGTATCTCAAGGACTCCCTGGCACTGGGGAAAACAGAGGAGGAGGCACTGAAGC
ACTTCCGAGTGAAGTTTAACGAAGCCCTCCGTGAGAGCTGGAAAACCAAAGTGAACTGGCTGGCCCACAACG
TGTCCAAAGACAACAGGCAGTAG
(Double underline indicates bases bordering the splice junction)
TABLE 6
PIK3CD variant 4 (with large deletion) Nucleotide
Sequence (1836 nt, SEQ ID No. 16):
ATGCCCCCTGGGGTGGACTGCCCCATGGAATTCTGGACCAAGGAGGAGAATCAGAGCGTTGTGGTTGACT
TCCTGCTGCCCACAGGGGTCTACCTGAACTTCCCTGTGTCCCGCAATGCCAACCTCAGCACCATCAAGCA
GCTGCTGTGGCACCGCGCCCAGTATGAGCCGCTCTTCCACATGCTCAGTGGCCCCGAGGCCTATGTGTTC
ACCTGCATCAACCAGACAGCGGAGCAGCAAGAGCTGGAGGACGAGCAACGGCGTCTGTGTGACGTGCAGC
CCTTCCTGCCCGTCCTGCGCCTGGTGGCCCGTGAGGGCGACCGCGTGAAGAAGCTCATCAACTCACAGAT
CAGCCTCCTCATCGGCAAAGGCCTCCACGAGTTTGACTCCTTGTGCGACCCAGAAGTGAACGACTTTCGC
GCCAAGATGTGCCAATTCTGCGAGGAGGCGGCCGCCCGCCGGCAGCAGCTGGGCTGGGAGGCCTGGCTGC
AGTACAGTTTCCCCCTGCAGCTGGAGCCCTCGGCTCAAACCTGGGGGCCTGGTACCCTGCGGCTCCCGAA
CCGGGCCCTTCTGGTCAACGTTAAGTTTGAGGGCAGCGAGGAGAGCTTCACCTTCCAGGTGTCCACCAAG
GACGTGCCGCTGGCGCTGATGGCCTGTGCCCTGCGGAAGAAGGCCACAGTGTTCCGGCAGCCGCTGGTGG
AGCAGCCGGAAGACTACACGCTGCAGGTGAACGGCAGGCATGAGTACCTGTATGGCAGCTACCCGCTCTG
CCAGTTCCAGTACATCTGCAGCTGCCTGCACAGTGGGTTGACCCCTCACCTGACCATGGTCCATTCCTCC
TCCATCCTCGCCATGCGGGATGAGCAGAGCAACCCTGCCCCCCAGGTCCAGAAACCGCGTGCCAAACCAC
CTCCCATTCCTGCGAAGAAGCCTTCCTCTGTGTCCCTGTGGTCCCTGGAGCAGCCGTTCCGCATCGAGCT
CATCCAGGGCAGCAAAGTGAACGCCGACGAGCGGATGAAGCTGGTGGTGCAGGCCGGGCTTTTCCACGGC
AACGAGATGCTGTGCAAGACGGTGTCCAGCTCGGAGGTGAGCGTGTGCTCGGAGCCCGTGTGGAAGCAGC
GGCTGGAGTTCGACATCAACATCTGCGACCTGCCCCGCATGGCCCGTCTCTGCTTTGCGCTGTACGCCGT
GATCGAGAAAGCCAAGAAGGCTCGCTCCACCAAGAAGAAGTCCAAGAAGGCGGACTGCCCCATTGCCTGG
GCCAACCTCATGCTGTTTGACTACAAGGACCAGCTTAAGACCGGGGAACGCTGCCTCT ACATGTGGCC CC TC
TCCTGT GCTGGCTATTGTGTGGCCACATATGTGCTGGGCATTGGCGATCGGCACAGCGACAACATCATGATC
CGAGAGAGTGGGCAGCTGTTCCACATTGATTTTGGCCACTTTCTGGGGAATTTCAAGACCAAGTTTGGAATC
AACCGCGAGCGTGTCCCATTCATCCTCACCTACGACTTTGTCCATGTGATTCAGCAGGGGAAGACTAATAAT
AGTGAGAAATTTGAACGGTTCCGGGGCTACTGTGAAAGGGCCTACACCATCCTGCGGCGCCACGGGCTTCTC
TTCCTCCACCTCTTTGCCCTGATGCGGGCGGCAGGCCTGCCTGAGCTCAGCTGCTCCAAAGACATCCAGTAT
CTCAAGGACTCCCTGGCACTGGGGAAAACAGAGGAGGAGGCACTGAAGCACTTCCGAGTGAAGTTTAACGAA
GCCCTCCGTGAGAGCTGGAAAACCAAAGTGAACTGGCTGGCCCACAACGTGTCCAAAGACAACAGGCAGTAG
(Double underline indicates bases bordering the deletion junction)
TABLE 7
Primers for detecting PIK3CD variants
Primer across the junction
TGCGAAGAA
GC
TGGTGGTGC
between PIK3CD exon 9 and 11
(SEQ ID No. 6)
Primer sequences across the
TGGACCTGA
GG
GAGGCCCT
junct. between PIK3CD exon
22 and 24 (SEQ ID No. 10)
Primer sequences across the
ACATGTGGCC
CC
TCTCCTG
deleted region (nt1329-2627)
of PIK3CD
(SEQ ID No. 15) :
(Double underline indicates bases bordering the splice junction)
TABLE 8
siRNA for selectively knockdown PIK3CD full
length and variants expression
siRNA targeting PIK3CD exon 23 (siPIK3CD-ex23)
Sense (SEQ ID No. 4): 5′ CCAACAUCCAACUCAACAAdTdT
3′
Antisense (SEQ ID No. 5): 3′ dTdTGGUUGUAGGUUGAGUU-
GUU (5′-P)5′
siRNA targeting junction spanning between
exon 9 and exon 11
Sense (SEQ ID No. 8) 5′ CUGCGAAGAA GC UGGUGGUdTdT 3′
Antisense (SEQ ID No. 9) 3′ dTdTGACGCUUCUU CG ACCAC-
CA (5′-P)5′
siRNA targeting junction spanning between
PIK3CD exon22 and exon 24 (siPIK3CD-S)
Sense (SEQ ID No. 12) 5′ UGA GG GAGGCCCUGGAUCGAdTdT
3′
Antisense (SEQ ID No. 13) 3′ dTdTACU CC CUCCGGGACCU-
AGCU (5′-P)5′
siRNA targeting junction spanning the
deleted sequences of PIK3CD variant 4
Sense (SEQ ID No. 17) 5′ CC UCUCCUGUGCUGGCUAUdTdT
3′
Antisense (SEQ ID No. 18) 3′ dTdT GG AGAGGACACGACCG-
AUA (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 9
FGFR3 (Full length) Nucleotide Sequence
(2421 nt, SEQ ID No. 19)
ATGGGCGCCCCTGCCTGCGCCCTCGCGCTCTGCGTGGCCGTGGCCATCGT
GGCCGGCGCCTCCTCGGAGTCCTTGGGGACGGAGCAGCGCGTCGTGGGGC
GAGCGGCAGAAGTCCCGGGCCCAGAGCCCGGCCAGCAGGAGCAGTTGGTC
TTCGGCAGCGGGGATGCTGTGGAGCTGAGCTGTCCCCCGCCCGGGGGTGG
TCCCATGGGGCCCACTGTCTGGGTCAAGGATGGCACAGGGCTGGTGCCCT
CGGAGCGTGTCCTGGTGGGGCCCCAGCGGCTGCAGGTGCTGAATGCCTCC
CACGAGGACTCCGGGGCCTACAGCTGCCGGCAGCGGCTCACGCAGCGCGT
ACTGTGCCACTTCAGTGTGCGGGTGACAGACGCTCCATCCTCGGGAGATG
ACGAAGACGGGGAGGACGAGGCTGAGGACACAGGTGTGGACACAGGGGCC
CCTTACTGGACACGGCCCGAGCGGATGGACAAGAAGCTGCTGGCCGTGCC
GGCCGCCAACACCGTCCGCTTCCGCTGCCCAGCCGCTGGCAACCCCACTC
CCTCCATCTCCTGGCTGAAGAACGGCAGGGAGTTCCGCGGCGAGCACCGC
ATTGGAGGCATCAAGCTGCGGCATCAGCAGTGGAGCCTGGTCATGGAAAG
CGTGGTGCCCTCGGACCGCGGCAACTACACCTGCGTCGTGGAGAACAAGT
TTGGCAGCATCCGGCAGACGTACACGCTGGACGTGCTGGAGCGCTCCCCG
CACCGGCCCATCCTGCAGGCGGGGCTGCCGGCCAACCAGACGGCGGTGCT
GGGCAGCGACGTGGAGTTCCACTGCAAGGTGTACAGTGACGCACAGCCCC
ACATCCAGTGGCTCAAGCACGTGGAGGTGAATGGCAGCAAGGTGGGCCCG
GACGGCACACCCTACGTTACCGTGCTCAAGACGGCGGGCGCTAACACCAC
CGACAAGGAGCTAGAGGTTCTCTCCTTGCACAACGTCACCTTTGAGGACG
CCGGGGAGTACACCTGCCTGGCGGGCAATTCTATTGGGTTTTCTCATCAC
TCTGCGTGGCTGGTGGTGCTGCCAGCCGAGGAGGAGCTGGTGGAGGCTGA
CGAGGCGGGCAGTGTGTATGCAGGCATCCTCAGCTACGGGGTGGGCTTCT
TCCTGTTCATCCTGGTGGTGGCGGCTGTGACGCTCTGCCGCCTGCGCAGC
CCCCCCAAGAAAGGCCTGGGCTCCCCCACCGTGCACAAGATCTCCCGCTT
CCCGCTCAAGCGACAGGTGTCCCTGGAGTCCAACGCGTCCATGAGCTCCA
ACACACCACTGGTGCGCATCGCAAGGCTGTCCTCAGGGGAGGGCCCCACG
CTGGCCAATGTCTCCGAGCTCGAGCTGCCTGCCGACCCCAAATGGGAGCT
GTCTCGGGCCCGGCTGACCCTGGGCAAGCCCCTTGGGGAGGGCTGCTTCG
GCCAGGTGGTCATGGCGGAGGCCATCGGCATTGACAAGGACCGGGCCGCC
AAGCCTGTCACCGTAGCCGTGAAGATGCTGAAAGACGATGCCACTGACAA
GGACCTGTCGGACCTGGTGTCTGAGATGGAGATGATGAAGATGATCGGGA
AACACAAAAACATCATCAACCTGCTGGGCGCCTGCACGCAGGGCGGGCCC
CTGTACGTGCTGGTGGAGTACGCGGCCAAGGGTAACCTGCGGGAGTTTCT
GCGGGCGCGGCGGCCCCCGGGCCTGGACTACTCCTTCGACACCTGCAAGC
CGCCCGAGGAGCAGCTCACCTTCAAGGACCTGGTGTCCTGTGCCTACCAG
GTGGCCCGGGGCATGGAGTACTTGGCCTCCCAGAAG TGCATCCACAGGGA
CCTGGCTGCCCGCAATGTGCTGGTGACCGAGGACAACGTGATGAAGATCG
CAGACTTCGGGCTGGCCCGGGACGTGCACAACCTCGACTACTACAAGAAG
ACGACCAAC GGCCGGCTGCCCGTGAAGTGGATGGCGCCTGAGGCCTTGTT
TGACCGAGTCTACACTCACCAGAGTGACGTCTGGTCCTTTGGGGTCCTGC
TCTGGGAGATCTTCACGCTGGGGGGCTCCCCGTACCCCGGCATCCCTGTG
GAGGAGCTCTTCAAGCTGCTGAAGGAGGGCCACCGCATGGACAAGCCCG C
C AACTGCACACACGACCT GTACATGATCATGCGGGAGTGCTGGCATGCCG
CGCCCTCCCAGAGGCCCACCTTCAAGCAGCTGGTGGAGGACCTGGACCGT
GTCCTTACCGTGACGTCCACCGACGAGTACCTGGACCTGTCGGCGCCTTT
CGAGCAGTACTCCCCGGGTGGCCAGGACACCCCCAGCTCCAGCTCCTCAG
GGGACGACTCCGTGTTTGCCCACGACCTGCTGCCCCCGGCCCCACCCAGC
AGTGGGGGCTCGCGGACGTGA
(Exon 14 is indicated by double underline. Primers useful for detection of exon 14 splicing variants are underlined.)
TABLE 10
FGFR3 variant 1 (lacking exon 14) Nucleotide
Sequence (2298 nt, SEQ ID No. 25):
ATGGGCGCCCCTGCCTGCGCCCTCGCGCTCTGCGTGGCCGTGGCCATCGT
GGCCGGCGCCTCCTCGGAGTCCTTGGGGACGGAGCAGCGCGTCGTGGGGC
GAGCGGCAGAAGTCCCGGGCCCAGAGCCCGGCCAGCAGGAGCAGTTGGTC
TTCGGCAGCGGGGATGCTGTGGAGCTGAGCTGTCCCCCGCCCGGGGGTGG
TCCCATGGGGCCCACTGTCTGGGTCAAGGATGGCACAGGGCTGGTGCCCT
CGGAGCGTGTCCTGGTGGGGCCCCAGCGGCTGCAGGTGCTGAATGCCTCC
CACGAGGACTCCGGGGCCTACAGCTGCCGGCAGCGGCTCACGCAGCGCGT
ACTGTGCCACTTCAGTGTGCGGGTGACAGACGCTCCATCCTCGGGAGATG
ACGAAGACGGGGAGGACGAGGCTGAGGACACAGGTGTGGACACAGGGGCC
CCTTACTGGACACGGCCCGAGCGGATGGACAAGAAGCTGCTGGCCGTGCC
GGCCGCCAACACCGTCCGCTTCCGCTGCCCAGCCGCTGGCAACCCCACTC
CCTCCATCTCCTGGCTGAAGAACGGCAGGGAGTTCCGCGGCGAGCACCGC
ATTGGAGGCATCAAGCTGCGGCATCAGCAGTGGAGCCTGGTCATGGAAAG
CGTGGTGCCCTCGGACCGCGGCAACTACACCTGCGTCGTGGAGAACAAGT
TTGGCAGCATCCGGCAGACGTACACGCTGGACGTGCTGGAGCGCTCCCCG
CACCGGCCCATCCTGCAGGCGGGGCTGCCGGCCAACCAGACGGCGGTGCT
GGGCAGCGACGTGGAGTTCCACTGCAAGGTGTACAGTGACGCACAGCCCC
ACATCCAGTGGCTCAAGCACGTGGAGGTGAATGGCAGCAAGGTGGGCCCG
GACGGCACACCCTACGTTACCGTGCTCAAGACGGCGGGCGCTAACACCAC
CGACAAGGAGCTAGAGGTTCTCTCCTTGCACAACGTCACCTTTGAGGACG
CCGGGGAGTACACCTGCCTGGCGGGCAATTCTATTGGGTTTTCTCATCAC
TCTGCGTGGCTGGTGGTGCTGCCAGCCGAGGAGGAGCTGGTGGAGGCTGA
CGAGGCGGGCAGTGTGTATGCAGGCATCCTCAGCTACGGGGTGGGCTTCT
TCCTGTTCATCCTGGTGGTGGCGGCTGTGACGCTCTGCCGCCTGCGCAGC
CCCCCCAAGAAAGGCCTGGGCTCCCCCACCGTGCACAAGATCTCCCGCTT
CCCGCTCAAGCGACAGGTGTCCCTGGAGTCCAACGCGTCCATGAGCTCCA
ACACACCACTGGTGCGCATCGCAAGGCTGTCCTCAGGGGAGGGCCCCACG
CTGGCCAATGTCTCCGAGCTCGAGCTGCCTGCCGACCCCAAATGGGAGCT
GTCTCGGGCCCGGCTGACCCTGGGCAAGCCCCTTGGGGAGGGCTGCTTCG
GCCAGGTGGTCATGGCGGAGGCCATCGGCATTGACAAGGACCGGGCCGCC
AAGCCTGTCACCGTAGCCGTGAAGATGCTGAAAGACGATGCCACTGACAA
GGACCTGTCGGACCTGGTGTCTGAGATGGAGATGATGAAGATGATCGGGA
AACACAAAAACATCATCAACCTGCTGGGCGCCTGCACGCAGGGCGGGCCC
CTGTACGTGCTGGTGGAGTACGCGGCCAAGGGTAACCTGCGGGAGTTTCT
GCGGGCGCGGCGGCCCCCGGGCCTGGACTACTCCTTCGACACCTGCAAGC
CGCCCGAGGAGCAGCTCACCTTCAAGGACCTGGTGTCCTGTGCCTACCAG
GTGGCCCGGGGCATGGAGTAC TTGGCCTCCCAGAA GG GCCGGCT GCCCGT
GAAGTGGATGGCGCCTGAGGCCTTGTTTGACCGAGTCTACACTCACCAGA
GTGACGTCTGGTCCTTTGGGGTCCTGCTCTGGGAGATCTTCACGCTGGGG
GGCTCCCCGTACCCCGGCATCCCTGTGGAGGAGCTCTTCAAGCTGCTGAA
GGAGGGCCACCGCATGGACAAGCCCGCCAACTGCACACACGACCTGTACA
TGATCATGCGGGAGTGCTGGCATGCCGCGCCCTCCCAGAGGCCCACCTTC
AAGCAGCTGGTGGAGGACCTGGACCGTGTCCTTACCGTGACGTCCACCGA
CGAGTACCTGGACCTGTCGGCGCCTTTCGAGCAGTACTCCCCGGGTGGCC
AGGACACCCCCAGCTCCAGCTCCTCAGGGGACGACTCCGTGTTTGCCCAC
GACCTGCTGCCCCCGGCCCCACCCAGCAGTGGGGGCTCGCGGACGTGA
(Double underline indicates bases bordering the splice junction)
TABLE 11
Primer across the junction between
FGFR3 exon 13 and 15
Primer across the
TTGGCCTCCCAGAA
GG
GCCGGCT
junction between FGFR3
exon 13 and 15
(SEQ ID No. 24)
(Double underline indicates bases bordering the splice junction)
TABLE 12
siRNA for selectively knockdown FGFR3
full length and variants expression
siRNA targeting FGFR3 exon 14:
Sense (SEQ ID No. 22) 5′ CUCGACUACUACAAGAAGAdTdT
3′
Antisense (SEQ ID No. 23) 3′ dTdTGAGCUGAUGAUGUUCU-
UCU (5′-P)5′
siRNA targeting splice junction
between FGFR3 exon 13 and 15
Sense (SEQ ID No. 26) 5′ CCUCCCAGAA GG GCCGGCU dTdT
3′
Antisense (SEQ ID No. 27) 3′ dTdTGGAGGGUCUU CC CGGC-
CGA (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 13
TSC2 (full length)Nucleotide Sequence (5424 nt, SEQ ID No. 28)
ATGGCCAAACCAACAAGCAAAGATTCAGGCTTGAAGGAGAAGTTTAAGATTCTGTTGGGACTGGGAACACCG
AGGCCAAATCCCAGGTCTGCAGAGGGTAAACAGACGGAGTTTATCATCACCGCGGAAATACTGAGAGAACTG
AGCATGGAATGTGGCCTCAACAATCGCATCCGGATGATAGGGCAGATTTGTGAAGTCGCAAAAACCAAGAAA
TTTGAAGAGCACGCAGTGGAAGCACTCTGGAAGGCGGTCGCGGATCTGTTGCAGCCGGAGCGGCCGCTGGAG
GCCCGGCACGCGGTGCTGGCTCTGCTGAAGGCCATCGTGCAGGGGCAGGGCGAGCGTTTGGGGGTCCTCAGA
GCCCTCTTCTTTAAGGTCATCAAGGATTACCCTTCCAACGAAGACCTTCACGAAAGGCTGGAGGTTTTCAAG
GCCCTCACAGACAATGGGAGACACATCACCTACTTGGAGGAAGAGCTGGCTGACTTTGTCCTGCAGTGGATG
GATGTTGGCTTGTCCTCGGAATTCCTTCTGGTGCTGGTGAACTTGGTCAAATTCAATAGCTGTTACCTCGAC
GAGTACATCGCAAGGATGGTTCAGATGATCTGTCTGCTGTGCGTCCGGACCGCGTCCTCTGTGGACATAGAG
GTCTCCCTGCAGGTGCTGGACGCCGTGGTCTGCTACAACTGCCTGCCGGCTGAGAGCCTCCCGCTGTTCATC
GTTACCCTCTGTCGCACCATCAACGTCAAGGAGCTCTGCGAGCCTTGCTGGAAGCTGATGCGGAACCTCCTT
GGCACCCACCTGGGCCACAGCGCCATCTACAACATGTGCCACCTCATGGAGGACAGAGCCTACATGGAGGAC
GCGCCCCTGCTGAGAGGAGCCGTGTTTTTTGTGGGCATGGCTCTCTGGGGAGCCCACCGGCTCTATTCTCTC
AGGAACTCGCCGACATCTGTGTTGCCATCATTTTACCAGGCCATGGCATGTCCGAACGAGGTGGTGTCCTAT
GAGATCGTCCTGTCCATCACCAGGCTCATCAAGAAGTATAGGAAGGAGCTCCAGGTGGTGGCGTGGGACATT
CTGCTGAACATCATCGAACGGCTCCTTCAGCAGCTCCAGACCTTGGACAGCCCGGAGCTCAGGACCATCGTC
CATGACCTGTTGACCACGGTGGAGGAGCTGTGTGACCAGAACGAGTTCCACGGGTCTCAGGAGAGATACTTT
GAACTGGTGGAGAGATGTGCGGACCAGAGGCCTGAGTCCTCCCTCCTGAACCTGATCTCCTATAGAGCGCAG
TCCATCCACCCGGCCAAGGACGGCTGGATTCAGAACCTGCAGGCGCTGATGGAGAGATTCTTCAGGAGCGAG
TCCCGAGGCGCCGTGCGCATCAAGGTGCTGGACGTGCTGTCCTTTGTGCTGCTCATCAACAGGCAGTTCTAT
GAGGAGGAGCTGATTAACTCAGTGGTCATCTCGCAGCTCTCCCACATCCCCGAGGATAAAGACCACCAGGTC
CGAAAGCTGGCCACCCAGTTGCTGGTGGACCTGGCAGAGGGCTGCCACACACACCACTTCAACAGCCTGCTG
GACATCATCGAGAAGGTGATGGCCCGCTCCCTCTCCCCACCCCCGGAGCTGGAAGAAAGGGATGTGGCCGCA
TACTCGGCCTCCTTGGAGGATGTGAAGACAGCCGTCCTGGGGCTTCTGGTCATCCTTCAGACCAAGCTGTAC
ACCCTGCCTGCAAGCCACGCCACGCGTGTGTATGAGATGCTGGTCAGCCACATTCAGCTCCACTACAAGCAC
AGCTACACCCTGCCAATCGCGAGCAGCATCCGGCTGCAGGCC TTTGACTTCCTGTTGCTGCT GCGGGCCGAC
TCACTGCACCGCCTGGGCCTGCCCAACAAGGATGGAGTCGTGCGGTTCAGCCCCTACTGCGTCTGCGACTAC
ATGGAGCCAGAGAGAGGCTCTGAGAAGAAGACCAGCGGCCCCCTTTCTCCTCCCACAGGGCCTCCTGGCCCG
GCGCCTGCAGGCCCCGCCGTGCGGCTGGGGTCCGTGCCCTACTCCCTGCTCTTCCGCGTCCTGCTGCAGTGC
TTGAAGCAG GAGTCTGACTGGAAGGTGCTGAAGCTGGTTCTGGGCAGGCTGCCTGAGTCCCTGCGCTATAAA
GTGCTCATCTTTACTTCCCCTTGCAGTGTGGACCAGCTGTGCTCTGCTCTCTGCTCCATG CTTTCAGGCCCA
AAGACACTGGAGCGGCTCCGAGGCGCCCCAGAAGGCTTCTCCAGAACTGACTTGCACCTGGCCGTGGTTCCA
GTGCTGACAGCATTAATCTCTTACCATAACTACCTGGACAAAACCAAACAGCGCGAGATGGTCTACTGCCTG
GAGCAGGGCCTCATCCACCGCTGTGCCAGCCAGTGCGTCGTGGCCTTGTCCATCTGCAGCGTGGAGATGCCT
GACATCATCATCAAGGCGCTGCCTGTTCTGGTGGTGAAGCTCACGCACATCTCAGCCACAGCCAGCATGGCC
GTCCCACTGCTGGAGTTCCTGTCCACTCTGGCCAGGCTGCCGCACCTCTACAGGAACTTTGCCGCGGAGCAG
TATGCCAGTGTGTTCGCCATCTCCCTGCCGTACACCAACCCCTCCAAGTTTAATCAGTACATCGTGTGTCTG
GCCCATCACGTCATAGCCATGTGGTTCATCAGGTGCCGCCTGCCCTTCCGGAAGGATTTTGTCCCTTTCATC
ACTAAGGGCCTGCGGTCCAATGTCCTCTTGTCTTTTGATGACACCCCCGAGAAGGACAGCTTCAGGGCCCGG
AGTACTAGTCTCAACGAGAGACCCAAGAGTCTGAGGATAGCCAGACCCCCCAAACAAGGCTTGAATAACTCT
CCACCCGTGAAAGAATTCAAGGAGAGCTCTGCAGCCGAGGCCTTCCGGTGCCGCAGCATCAGTGTGTCTGAA
CATGTGGTCCGCAGCAGGATACAGACGTCCCTCACCAGTGCCAGCTTGGGGTCTGCAGATGAGAACTCCGTG
GCCCAGGCTGACGATAGCCTGAAAAACCTCCACCTGGAGCTCACGGAAACCTGTCTGGACATGATGGCTCGA
TACGTCTTCTCCAACTTCACGGCTGTCCCGAAGAGGTCTCCTGTGGGCGAGTTCCTCCTAGCGGGTGGCAGG
ACCAAAACCTGGCTGGTTGGGAACAAGCTTGTCACTGTGACGACAAGCGTGGGAACCGGGACCCGGTCGTTA
CTAGGCCTGGACTCGGGGGAGCTGCAGTCCGGCCCGGAGTCGAGCTCCAGCCCCGGGGTGCATGTGAGACAG
ACCAAGGAGGCGCCGGCCAAGCTGGAGTCCCAGGCTGGGCAGCAGGTGTCCCGTGGGGCCCGGGATCGGGTC
CGTTCCATGTCGGGGGGCCATGGTCTTCGAGTTGGCGCCCTGGACGTGCCGGCCTCCCAGTTCCTGGGCAGT
GCCACTTCTCCAGGACCACGGACTGCACCAGCCGCGAAACCTGAGAAGGCCTCAGCTGGCACCCGGGTTCCT
GTGCAGGAGAAGACGAACCTGGCGGCCTATGTGCCCCTGCTGACCCAGGGCTGGGCGGAGATCCTGGTCCGG
AGGCCCACAGGGAACACCAGCTGGCTGATGAGCCTGGAGAACCCGCTCAGCCCTTTCTCCTCGGACATCAAC
AACATGCCCCTGCAGGAGCTGTCTAACGCCCTCATGGCGGCTGAGCGCTTCAAGGAGCACCGGGACACAGCC
CTGTACAAGTCACTGTCGGTGCCGGCAGCCAGCACGGCCAAACCCCCTCCTCTGCCTCGCTCCAACACAGTG
GCCTCTTTCTCCTCCCTGTACCAGTCCAGCTGCCAAGGACAGCTGCACAGGAGCGTTTCCTGGGCAGACTCC
GCCGTGGTCATGGAGGAGGGAAGTCCGGGCGAGGTTCCTGTGCTGGTGGAGCCCCCAGGGTTGGAGGACGTT
GAGGCAGCGCTAGGCATGGACAGGCGCACGGATGCCTACAGCAGGTCGTCCTCAGTCTCCAGCCAGGAGGAG
AAGTCGCTCCACGCGGAGGAGCTGGTTGGCAGGGGCATCCCCATCGAGCGAGTCGTCTCCTCGGAGGGTGGC
CGGCCCTCTGTGGACCTCTCCTTCCAGCCCTCGCAGCCCCTGAGCAAGTCCAGCTCCTCTCCCGAGCTGCAG
ACTCTGCAGGACATCCTCGGGGACCCTGGGGACAAGGCCGACGTGGGCCGGCTGAGCCCTGAGGTTAAGGCC
CGGTCACAGTCAGGGACCCTGGACGGGGAAAGTGCTGCCTGGTCGGCCTCGGGCGAAGACAGTCGGGGCCAG
CCCGAGGGTCCCTTGCCTTCCAGCTCCCCCCGCTCGCCCAGTGGCCTCCGGCCCCGAGGTTACACCATCTCC
GACTCGGCCCCATCACGCAGGGGCAAGAGAGTAGAGAGGGACGCCTTAAAGAGCAGAGCCACAGCCTCCAAT
GCAGAGAAAGTGCCAGGCATCAACCCCAGTTTCGTGTTCCTGCAGCTCTACCATTCCCCCTTCTTTGGCGAC
GAGTCAAACAAGCCAATCCTGCTGCCCAATGAGTCACAGTCCTTTGAGCGGTCGGTGCAGCTCCTCGACCAG
ATCCCATCATACGACACCCACAAGATCGCCGTCCTGTATGTTGGAGAAGGCCAGAGCAACAGCGAGCTCGCC
ATCCTGTCCAATGAGCATGGCTCCTACAGGTACACGGAGTTCCTGACGGGCCTGGGCCGGCTCATCGAGCTG
AAGGACTGCCAGCCGGACAAGGTGTACCTGGGAGGCCTGGACGTGTGTGGTGAGGACGGCCAGTTCACCTAC
TGCTGGCACGATGACATCATGCAAGCCGTCTTCCACATCGCCACCCTGATGCCCACCAAGGACGTGGACAAG
CACCGCTGCGACAAGAAGCGCCACCTGGGCAACGACTTTGTGTCCATTGTCTACAATGACTCCGGTGAGGAC
TTCAAGCTTGGCACCATCAAGGGCCAGTTCAACTTTGTCCACGTGATCGTCACCCCGCTGGACTACGAGTGC
AACCTGGTGTCCCTGCAGTGCAGGAAAGACATGGAGGGCCTTGTGGACACCAGCGTGGCCAAGATCGTGTCT
GACCGCAACCTGCCCTTCGTGGCCCGCCAGATGGCCCTGCACGCAAATATGGCCTCACAGGTGCATCATAGC
CGCTCCAACCCCACCGATATCTACCCCTCCAAGTGGATTGCCCGGCTCCGCCACATCAAGCGGCTCCGCCAG
CGGATCTGCGAGGAAGCCGCCTACTCCAACCCCAGCCTACCTCTGGTGCACCCTCCGTCCCATAGCAAAGCC
CCTGCACAGACTCCAGCCGAGCCCACACCTGGCTATGAGGTGGGCCAGCGGAAGCGCCTCATCTCCTCGGTG
GAGGACTTCACCGAGTTTGTGTGA
(Exon 19 is indicated by double underline. Primers useful for detection of exon 19 splicing variants are underlined.)
TABLE 14
TSC2 variant 1 (lacking exon 19) Nucleotide Sequence
(5301 nt, SEQ ID No. 34)
ATGGCCAAACCAACAAGCAAAGATTCAGGCTTGAAGGAGAAGTTTAAGATTCTGTTGGGACTGGGAACACCG
AGGCCAAATCCCAGGTCTGCAGAGGGTAAACAGACGGAGTTTATCATCACCGCGGAAATACTGAGAGAACTG
AGCATGGAATGTGGCCTCAACAATCGCATCCGGATGATAGGGCAGATTTGTGAAGTCGCAAAAACCAAGAAA
TTTGAAGAGCACGCAGTGGAAGCACTCTGGAAGGCGGTCGCGGATCTGTTGCAGCCGGAGCGGCCGCTGGAG
GCCCGGCACGCGGTGCTGGCTCTGCTGAAGGCCATCGTGCAGGGGCAGGGCGAGCGTTTGGGGGTCCTCAGA
GCCCTCTTCTTTAAGGTCATCAAGGATTACCCTTCCAACGAAGACCTTCACGAAAGGCTGGAGGTTTTCAAG
GCCCTCACAGACAATGGGAGACACATCACCTACTTGGAGGAAGAGCTGGCTGACTTTGTCCTGCAGTGGATG
GATGTTGGCTTGTCCTCGGAATTCCTTCTGGTGCTGGTGAACTTGGTCAAATTCAATAGCTGTTACCTCGAC
GAGTACATCGCAAGGATGGTTCAGATGATCTGTCTGCTGTGCGTCCGGACCGCGTCCTCTGTGGACATAGAG
GTCTCCCTGCAGGTGCTGGACGCCGTGGTCTGCTACAACTGCCTGCCGGCTGAGAGCCTCCCGCTGTTCATC
GTTACCCTCTGTCGCACCATCAACGTCAAGGAGCTCTGCGAGCCTTGCTGGAAGCTGATGCGGAACCTCCTT
GGCACCCACCTGGGCCACAGCGCCATCTACAACATGTGCCACCTCATGGAGGACAGAGCCTACATGGAGGAC
GCGCCCCTGCTGAGAGGAGCCGTGTTTTTTGTGGGCATGGCTCTCTGGGGAGCCCACCGGCTCTATTCTCTC
AGGAACTCGCCGACATCTGTGTTGCCATCATTTTACCAGGCCATGGCATGTCCGAACGAGGTGGTGTCCTAT
GAGATCGTCCTGTCCATCACCAGGCTCATCAAGAAGTATAGGAAGGAGCTCCAGGTGGTGGCGTGGGACATT
CTGCTGAACATCATCGAACGGCTCCTTCAGCAGCTCCAGACCTTGGACAGCCCGGAGCTCAGGACCATCGTC
CATGACCTGTTGACCACGGTGGAGGAGCTGTGTGACCAGAACGAGTTCCACGGGTCTCAGGAGAGATACTTT
GAACTGGTGGAGAGATGTGCGGACCAGAGGCCTGAGTCCTCCCTCCTGAACCTGATCTCCTATAGAGCGCAG
TCCATCCACCCGGCCAAGGACGGCTGGATTCAGAACCTGCAGGCGCTGATGGAGAGATTCTTCAGGAGCGAG
TCCCGAGGCGCCGTGCGCATCAAGGTGCTGGACGTGCTGTCCTTTGTGCTGCTCATCAACAGGCAGTTCTAT
GAGGAGGAGCTGATTAACTCAGTGGTCATCTCGCAGCTCTCCCACATCCCCGAGGATAAAGACCACCAGGTC
CGAAAGCTGGCCACCCAGTTGCTGGTGGACCTGGCAGAGGGCTGCCACACACACCACTTCAACAGCCTGCTG
GACATCATCGAGAAGGTGATGGCCCGCTCCCTCTCCCCACCCCCGGAGCTGGAAGAAAGGGATGTGGCCGCA
TACTCGGCCTCCTTGGAGGATGTGAAGACAGCCGTCCTGGGGCTTCTGGTCATCCTTCAGACCAAGCTGTAC
ACCCTGCCTGCAAGCCACGCCACGCGTGTGTATGAGATGCTGGTCAGCCACATTCAGCTCCACTACAAGCAC
AGCTACACCCTGCCAATCGCGAGCAGCATCCGGCTGCAGGCCTTTGACTTCCTGTTGCTGCTGCGGGCCGAC
TCACTGCACCGCCTGGGCCTGCCCAACAAGGATGGAGTCGTGCGGTTCAGCCCCTACTGCGTCTGCGACTAC
ATGGAGCCAGAGAGAGGCTCTGAGAAGAAGACCAGCGGCCCCCTTTCTCCTCCCACAGGGCCTCCTGGCCCG
GCGCCTGCAGGCCCCGCCGTGCGGCTGGGGTCCGTGCCCTACTCCCTGCTCTTCCGCGTCCTGCTGCAGTGC
TTGAAGCA GC TTTCAGGCC CAAAGACACTGGAGCGGCTCCGAGGCGCCCCAGAAGGCTTCTCCAGAACTGAC
TTGCACCTGGCCGTGGTTCCAGTGCTGACAGCATTAATCTCTTACCATAACTACCTGGACAAAACCAAACAG
CGCGAGATGGTCTACTGCCTGGAGCAGGGCCTCATCCACCGCTGTGCCAGCCAGTGCGTCGTGGCCTTGTCC
ATCTGCAGCGTGGAGATGCCTGACATCATCATCAAGGCGCTGCCTGTTCTGGTGGTGAAGCTCACGCACATC
TCAGCCACAGCCAGCATGGCCGTCCCACTGCTGGAGTTCCTGTCCACTCTGGCCAGGCTGCCGCACCTCTAC
AGGAACTTTGCCGCGGAGCAGTATGCCAGTGTGTTCGCCATCTCCCTGCCGTACACCAACCCCTCCAAGTTT
AATCAGTACATCGTGTGTCTGGCCCATCACGTCATAGCCATGTGGTTCATCAGGTGCCGCCTGCCCTTCCGG
AAGGATTTTGTCCCTTTCATCACTAAGGGCCTGCGGTCCAATGTCCTCTTGTCTTTTGATGACACCCCCGAG
AAGGACAGCTTCAGGGCCCGGAGTACTAGTCTCAACGAGAGACCCAAGAGTCTGAGGATAGCCAGACCCCCC
AAACAAGGCTTGAATAACTCTCCACCCGTGAAAGAATTCAAGGAGAGCTCTGCAGCCGAGGCCTTCCGGTGC
CGCAGCATCAGTGTGTCTGAACATGTGGTCCGCAGCAGGATACAGACGTCCCTCACCAGTGCCAGCTTGGGG
TCTGCAGATGAGAACTCCGTGGCCCAGGCTGACGATAGCCTGAAAAACCTCCACCTGGAGCTCACGGAAACC
TGTCTGGACATGATGGCTCGATACGTCTTCTCCAACTTCACGGCTGTCCCGAAGAGGTCTCCTGTGGGCGAG
TTCCTCCTAGCGGGTGGCAGGACCAAAACCTGGCTGGTTGGGAACAAGCTTGTCACTGTGACGACAAGCGTG
GGAACCGGGACCCGGTCGTTACTAGGCCTGGACTCGGGGGAGCTGCAGTCCGGCCCGGAGTCGAGCTCCAGC
CCCGGGGTGCATGTGAGACAGACCAAGGAGGCGCCGGCCAAGCTGGAGTCCCAGGCTGGGCAGCAGGTGTCC
CGTGGGGCCCGGGATCGGGTCCGTTCCATGTCGGGGGGCCATGGTCTTCGAGTTGGCGCCCTGGACGTGCCG
GCCTCCCAGTTCCTGGGCAGTGCCACTTCTCCAGGACCACGGACTGCACCAGCCGCGAAACCTGAGAAGGCC
TCAGCTGGCACCCGGGTTCCTGTGCAGGAGAAGACGAACCTGGCGGCCTATGTGCCCCTGCTGACCCAGGGC
TGGGCGGAGATCCTGGTCCGGAGGCCCACAGGGAACACCAGCTGGCTGATGAGCCTGGAGAACCCGCTCAGC
CCTTTCTCCTCGGACATCAACAACATGCCCCTGCAGGAGCTGTCTAACGCCCTCATGGCGGCTGAGCGCTTC
AAGGAGCACCGGGACACAGCCCTGTACAAGTCACTGTCGGTGCCGGCAGCCAGCACGGCCAAACCCCCTCCT
CTGCCTCGCTCCAACACAGTGGCCTCTTTCTCCTCCCTGTACCAGTCCAGCTGCCAAGGACAGCTGCACAGG
AGCGTTTCCTGGGCAGACTCCGCCGTGGTCATGGAGGAGGGAAGTCCGGGCGAGGTTCCTGTGCTGGTGGAG
CCCCCAGGGTTGGAGGACGTTGAGGCAGCGCTAGGCATGGACAGGCGCACGGATGCCTACAGCAGGTCGTCC
TCAGTCTCCAGCCAGGAGGAGAAGTCGCTCCACGCGGAGGAGCTGGTTGGCAGGGGCATCCCCATCGAGCGA
GTCGTCTCCTCGGAGGGTGGCCGGCCCTCTGTGGACCTCTCCTTCCAGCCCTCGCAGCCCCTGAGCAAGTCC
AGCTCCTCTCCCGAGCTGCAGACTCTGCAGGACATCCTCGGGGACCCTGGGGACAAGGCCGACGTGGGCCGG
CTGAGCCCTGAGGTTAAGGCCCGGTCACAGTCAGGGACCCTGGACGGGGAAAGTGCTGCCTGGTCGGCCTCG
GGCGAAGACAGTCGGGGCCAGCCCGAGGGTCCCTTGCCTTCCAGCTCCCCCCGCTCGCCCAGTGGCCTCCGG
CCCCGAGGTTACACCATCTCCGACTCGGCCCCATCACGCAGGGGCAAGAGAGTAGAGAGGGACGCCTTAAAG
AGCAGAGCCACAGCCTCCAATGCAGAGAAAGTGCCAGGCATCAACCCCAGTTTCGTGTTCCTGCAGCTCTAC
CATTCCCCCTTCTTTGGCGACGAGTCAAACAAGCCAATCCTGCTGCCCAATGAGTCACAGTCCTTTGAGCGG
TCGGTGCAGCTCCTCGACCAGATCCCATCATACGACACCCACAAGATCGCCGTCCTGTATGTTGGAGAAGGC
CAGAGCAACAGCGAGCTCGCCATCCTGTCCAATGAGCATGGCTCCTACAGGTACACGGAGTTCCTGACGGGC
CTGGGCCGGCTCATCGAGCTGAAGGACTGCCAGCCGGACAAGGTGTACCTGGGAGGCCTGGACGTGTGTGGT
GAGGACGGCCAGTTCACCTACTGCTGGCACGATGACATCATGCAAGCCGTCTTCCACATCGCCACCCTGATG
CCCACCAAGGACGTGGACAAGCACCGCTGCGACAAGAAGCGCCACCTGGGCAACGACTTTGTGTCCATTGTC
TACAATGACTCCGGTGAGGACTTCAAGCTTGGCACCATCAAGGGCCAGTTCAACTTTGTCCACGTGATCGTC
ACCCCGCTGGACTACGAGTGCAACCTGGTGTCCCTGCAGTGCAGGAAAGACATGGAGGGCCTTGTGGACACC
AGCGTGGCCAAGATCGTGTCTGACCGCAACCTGCCCTTCGTGGCCCGCCAGATGGCCCTGCACGCAAATATG
GCCTCACAGGTGCATCATAGCCGCTCCAACCCCACCGATATCTACCCCTCCAAGTGGATTGCCCGGCTCCGC
CACATCAAGCGGCTCCGCCAGCGGATCTGCGAGGAAGCCGCCTACTCCAACCCCAGCCTACCTCTGGTGCAC
CCTCCGTCCCATAGCAAAGCCCCTGCACAGACTCCAGCCGAGCCCACACCTGGCTATGAGGTGGGCCAGCGG
AAGCGCCTCATCTCCTCGGTGGAGGACTTCACCGAGTTTGTGTGA
(Double underline indicates bases bordering the splice junction)
TABLE 15
Primer across the junction between
TSC2 exon 18 and 20
Table 23. Primer sequences
CTTGAAGCA
GC
TTTCAGGCC
across the junction between
TSC2 exon 18 and 20
(SEQ ID No. 33)
(Double underline indicates bases bordering the splice junction)
TABLE 16
siRNA for selectively knockdown TSC2 full
length and variant expression
siRNA targeting TSC2 exon 19
Sense (SEQ ID No. 31) 5′ CUGCGCUAUAAAGUGCUCA dTdT
3′
Antisense (SEQ ID No. 32) 3′ dTdT GACGCGAUAUUUCACG-
AGU (5′-P)5′
siRNA targeting the junction between
TSC2 exon 18 and exon 20
Sense (SEQ ID No. 35) 5′ GAAGCA GC UUUCAGGCCCAdTdT
3′
Antisense (SEQ ID No. 36) 3′ dTdTCUUCGU CG AAAGUCCG-
GGU (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 17
RASGRP2 (full length) Nucleotide Sequence (1830 nt, SEQ ID No. 37)
ATGGCAGGCACCCTGGACCTGGACAAGGGCTGCACGGTGGAGGAGCTGCTCCGCGGGTGCATCGAAGCCTTC
GATGACTCCGGGAAGGTGCGGGACCCGCAGCTGGTGCGCATGTTCCTCATGATGCACCCCTGGTACATCCCC
TCCTCTCAGCTGGCGGCCAAGCTGCTCCACATCTACCAACAATCCCGGAAGGACAACTCCAATTCCCTGCAG
GTGAAAACGTGCCACCTGGTCAGGTACTGGATCTCCGCCTTCCCAGCGGAGTTTGACTTGAACCCGGAGTTG
GCTGAGCAGATCAAGGAGCTGAAGGCTCTGCTAGACCAAGAAGGGAACCGACGGCACAGCAGCCTAATCGAC
ATAGACAGCGTCCCTACCTACAAGTGGAAGCGGCAGGTGACTCAGCGGAACCCTGTGGGACAGAAAAAGCGC
AAGATGTCCCTGTTGTTTGACCACCTGGAGCCCATGGAGCTGGCGGAGCATCTCACCTACTTGGAGTATCGC
TCCTTCTGCAAGATCCTGTTTCAGGACTATCACAGTTTCGTGACTCATGGCTGCACTGTGGACAACCCCGTC
CTGGAGCGGTTCATCTCCCTCTTCAACAGCGTCTCACAGTGGGTGCAGCTCATGATCCTCAGCAAACCCACA
GCCCCGCAGCGGGCCCTGGTCATCACACACTTTGTCCACGTGGCGGAGAAGCTGCTACAGCTGCAGAACTTC
AACACGCTGATGGCAGTGGTCGGGGGCCTGAGCCACAGCTCCATCTCCCGCCTCAAGGAGACCCACAGCCAC
GTTAGCCCTGAGACCATCAAGCTCTGGGAGGGTCTCACGGAACTAGTGACGGCGACAGGCAACTATGGCAAC
TACCGGCGTCGGCTGGCAGCCTGTGTGGGCTTCCGCTTCCCGATCCTGGGTGTGCACCTCAAGGACCTGGTG
GCCCTGCAGCTGGCACTGCCTGACTGGCTGGACCCAGCCCGGACCCGGCTCAACGGGGCCAAGATGAAGCAG
CTCTTTAGCATCCTGGAGGAGCTGGCCATGGTGACCAGCCTGCGGCCACCAGTACAGGCCAACCCCGACCTG
CTGAGCCTGC TCACGGTGTCTCTGGATCAGT ATCAGACGGAGGATGAGCTGTACCAGCTGTCCCTGCAGCGG
GTTTCCTATTTCCTGCGCTCCAGCTCTGTGTTGGGGGGGCGCATGGGCTTCGTACACAACTTCCAGGAGAGC
AACTCCTTGCGCCCCGTCGCCTGCCGCCACTGCAAAGCCCTGATCCTGGGCATCTACAAGCAGGGCCTCAAA
TGCCGAGCCTGTGGAGTGAACTGCCACAAGCAGTGCAAGGATCGCCTGTCAGTTGAGTGTCGGCGCAGGGCC
CAGAGTGTGAGCCTGGAGGGGTCTGCACCCTCACCCTCACCCATGCACAGCCACCATCACCGCGCCTTCAGC
TTCTCTCTGCCCCGCCCTGGCAGGCGAGGCTCCAGGCCTCCAGAGATCCGTGAGGAGGAGGTACAGACGGTG
GAGGATGGGGTGTTTGACATCCACTTGTAA
(Exon 10 is indicated by double underline. Exon 11 is indicated by wave underline.)
TABLE 18
RASGRP2 variant 1 (lacking exon 10)
Nucleotide Sequence (1707 nt,
SEQ ID No. 45)
ATGGCAGGCACCCTGGACCTGGACAAGGGCTGCACGGTGGAGGAGCTGCT
CCGCGGGTGCATCGAAGCCTTCGATGACTCCGGGAAGGTGCGGGACCCGC
AGCTGGTGCGCATGTTCCTCATGATGCACCCCTGGTACATCCCCTCCTCT
CAGCTGGCGGCCAAGCTGCTCCACATCTACCAACAATCCCGGAAGGACAA
CTCCAATTCCCTGCAGGTGAAAACGTGCCACCTGGTCAGGTACTGGATCT
CCGCCTTCCCAGCGGAGTTTGACTTGAACCCGGAGTTGGCTGAGCAGATC
AAGGAGCTGAAGGCTCTGCTAGACCAAGAAGGGAACCGACGGCACAGCAG
CCTAATCGACATAGACAGCGTCCCTACCTACAAGTGGAAGCGGCAGGTGA
CTCAGCGGAACCCTGTGGGACAGAAAAAGCGCAAGATGTCCCTGTTGTTT
GACCACCTGGAGCCCATGGAGCTGGCGGAGCATCTCACCTACTTGGAGTA
TCGCTCCTTCTGCAAGATCCTGTTTCAGGACTATCACAGTTTCGTGACTC
ATGGCTGCACTGTGGACAACCCCGTCCTGGAGCGGTTCATCTCCCTCTTC
AACAGCGTCTCACAGTGGGTGCAGCTCATGATCCTCAGCAAACCCACAGC
CCCGCAGCGGGCCCTGGTCATCACACACTTTGTCCACGTGGCGGAGAAGC
TGCTACAGCTGCAGAACTTCAACACGCTGATGGCAGTGGTCGGGGGCCTG
AGCCACAGCTCCATCTCCCGCCTCAAGGAGACCCACAGCCACGTTAGCCC
TGAGACCATCAAGCTCTGGGAGGGTCTCACGGAACTAGTGACGGCGACAG
GCAACTATGGCAACTACCGGCGTCGGCTGGCAGCCTGTGTGGGCTTCCGC
TTCCCGATCCTGGGTGTGCACCTCAAGGACCTGGTGGCCCTGCAGCTGGC
ACTGCCTGACTGGCTGGACCCAGCCCGGACCCGGCTCAACGGGGCCAAGA
TGAAGCAGCTCTTTAGCATCCTGGAGGAGCTGGCCATGGTGACCAGCCTG
CGGCCACCAGTACAGGCCAACCCCGACCTGCTGAGCCTGCTCACGGTGTC
TCTGGATCAGTATCAGACGGAGGATGAGCTGTACCAGCTGTCCCTGCAGC
GGGAGCCGCGCTC CAAGTCCTC GT CTGTGTTCC GGAACTTTGACGTCGAT
GGGGATGGCCACATCTCACAGGAAGAATTCCAGATCATCCGTGGGAACTT
CCCTTACCTCAGCGCCTTTGGGGACCTCGACCAGAACCAGGATGGCTGCA
TCAGCAGGGAGGAGATGGTTTCCTATTTCCTGCGCTCCAGCTCTGTGTTG
GGGGGGCGCATGGGCTTCGTACACAACTTCCAGGAGAGCAACTCCTTGCG
CCCCGTCGCCTGCCGCCACTGCAAAGCCCTGATCCTGGGCATCTACAAGC
AGGGCCTCAAATGCCGAGCCTGTGGAGTGAACTGCCACAAGCAGTGCAAG
GATCGCCTGTCAGTTGAGTGTCGGCGCAGGGCCCAGAGTGTGAGCCTGGA
GGGGTCTGCACCCTCACCCTCACCCATGCACAGCCACCATCACCGCGCCT
TCAGCTTCTCTCTGCCCCGCCCTGGCAGGCGAGGCTCCAGGCCTCCAGAG
ATCCGTGAGGAGGAGGTACAGACGGTGGAGGATGGGGTGTTTGACATCCA
CTTGTAA
(Double underline indicates bases bordering the splice junction)
TABLE 19
RASGRP2 variant 2 (lacking exon 11)
Nucleotide Sequence (1714 nt,
SEQ ID No. 49)
ATGGCAGGCACCCTGGACCTGGACAAGGGCTGCACGGTGGAGGAGCTGCT
CCGCGGGTGCATCGAAGCCTTCGATGACTCCGGGAAGGTGCGGGACCCGC
AGCTGGTGCGCATGTTCCTCATGATGCACCCCTGGTACATCCCCTCCTCT
CAGCTGGCGGCCAAGCTGCTCCACATCTACCAACAATCCCGGAAGGACAA
CTCCAATTCCCTGCAGGTGAAAACGTGCCACCTGGTCAGGTACTGGATCT
CCGCCTTCCCAGCGGAGTTTGACTTGAACCCGGAGTTGGCTGAGCAGATC
AAGGAGCTGAAGGCTCTGCTAGACCAAGAAGGGAACCGACGGCACAGCAG
CCTAATCGACATAGACAGCGTCCCTACCTACAAGTGGAAGCGGCAGGTGA
CTCAGCGGAACCCTGTGGGACAGAAAAAGCGCAAGATGTCCCTGTTGTTT
GACCACCTGGAGCCCATGGAGCTGGCGGAGCATCTCACCTACTTGGAGTA
TCGCTCCTTCTGCAAGATCCTGTTTCAGGACTATCACAGTTTCGTGACTC
ATGGCTGCACTGTGGACAACCCCGTCCTGGAGCGGTTCATCTCCCTCTTC
AACAGCGTCTCACAGTGGGTGCAGCTCATGATCCTCAGCAAACCCACAGC
CCCGCAGCGGGCCCTGGTCATCACACACTTTGTCCACGTGGCGGAGAAGC
TGCTACAGCTGCAGAACTTCAACACGCTGATGGCAGTGGTCGGGGGCCTG
AGCCACAGCTCCATCTCCCGCCTCAAGGAGACCCACAGCCACGTTAGCCC
TGAGACCATCAAGCTCTGGGAGGGTCTCACGGAACTAGTGACGGCGACAG
GCAACTATGGCAACTACCGGCGTCGGCTGGCAGCCTGTGTGGGCTTCCGC
TTCCCGATCCTGGGTGTGCACCTCAAGGACCTGGTGGCCCTGCAGCTGGC
ACTGCCTGACTGGCTGGACCCAGCCCGGACCCGGCTCAACGGGGCCAAGA
TGAAGCAGCTCTTTAGCATCCTGGAGGAGCTGGCCATGGTGACCAGCCTG
CGGCCACCAGTACAGGCCAACCCCGACCTGCTGAGCCTGCTCACGGTGTC
TCTGGATCAGTATCAGACGGAGGATGAGCTGTACCAGCTGTCCCTGCAGC
GGGAGCCGCGCTCCAAGTCCTCGCCAACCAGCCCCACGAGTTGCACCCCA
CCACCCCGGCCCCCGGTACTGGAGGAGTGGACCTCGGCTGCCAAACCCAA
GCTGGATCAGGCCCTCGTGGTGGAGCACATCGAGAA GATGGTGGA GG GAT
GGCTGC ATCAGCAGGGAGGAGATGGTTTCCTATTTCCTGCGCTCCAGCTC
TGTGTTGGGGGGGCGCATGGGCTTCGTACACAACTTCCAGGAGAGCAACT
CCTTGCGCCCCGTCGCCTGCCGCCACTGCAAAGCCCTGATCCTGGGCATC
TACAAGCAGGGCCTCAAATGCCGAGCCTGTGGAGTGAACTGCCACAAGCA
GTGCAAGGATCGCCTGTCAGTTGAGTGTCGGCGCAGGGCCCAGAGTGTGA
GCCTGGAGGGGTCTGCACCCTCACCCTCACCCATGCACAGCCACCATCAC
CGCGCCTTCAGCTTCTCTCTGCCCCGCCCTGGCAGGCGAGGCTCCAGGCC
TCCAGAGATCCGTGAGGAGGAGGTACAGACGGTGGAGGATGGGGTGTTTG
ACATCCACTTGTAA
(Double underline indicates bases bordering the splice junction)
TABLE 20
Primer across the junction between
RASGRP2 variants
Primer across junction
CAAGTCCTC
GT
CTGTGTTCC
between RASGRP2 exon
9 and exon 11
(SEQ ID No. 44)
Primer across junction
GATGGTGGA
GG
GATGGCTGC
between RASGRP2 exon
10 and exon 12
(SEQ ID No. 48)
(Double underline indicates bases bordering the splice junction)
TABLE 21
siRNA for selectively knockdown
RASGRP2 full length and variants
expression
siRNA targeting RASGRP2 exon 10
Sense (SEQ ID No. 40): 5′ GUGGAGCACAUCGAGAAGAdTdT
3′
Antisense (SEQ ID No. 41): 3′ dTdTCACCUCGUGUAGCUC-
UUCU (5′-P)5′
siRNA targeting RASGRP2 exon 11
Sense (SEQ ID No. 42): 5′ CCACAUCUCACAGGAAGAAdTdT
3′
Antisense (SEQ ID No. 43): 3′ dTdTGGUGUAGAGUGUCCU-
UCUU (5′-P)5
siRNA targeting junction between
RASGRP2 exon 9 and 11:
Sense (SEQ ID No. 46): 5′ CCUC GU CUGUGUUCCGGAAdTdT
3′
Antisense (SEQ ID No. 47): 3′ dTdTGGAG CA GACACAAGG-
CCUU (5′-P)5′
siRNA targeting junction between
RASGRP2 exon 10 and 12
Sense (SEQ ID No. 50): 5′ GGUGGA GG GAUGGCUGCAUdTdT
3′
Antisense (SEQ ID No. 51): 3′ dTdTCCACCU CC CUACCGA-
CGUA (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 22
ITGA4 (full length) Nucleotide Sequence
(3099 nt, SEQ ID No. 52)
ATGGCTTGGGAAGCGAGGCGCGAACCCGGCCCCCGAAGGGCCGCCGTCCG
GGAGACGGTGATGCTGTTGCTGTGCCTGGGGGTCCCGACCGGCCGCCCCT
ACAACGTGGACACTGAGAGCGCGCTGCTTTACCAGGGCCCCCACAACACG
CTGTTCGGCTACTCGGTCGTGCTGCACAGCCACGGGGCGAACCGATGGCT
CCTAGTGGGTGCGCCCACTGCCAACTGGCTCGCCAACGCTTCAGTGATCA
ATCCCGGGGCGATTTACAGATGCAGGATCGGAAAGAATCCCGGCCAGACG
TGCGAACAGCTCCAGCTGGGTAGCCCTAATGGAGAACCTTGTGGAAAGAC
TTGTTTGGAAGAGAGAGACAATCAGTGGTTGGGGGTCACACTTTCCAGAC
AGCCAGGAGAAAATGGATCCATCGTGACTTGTGGGCATAGATGGAAAAAT
ATATTTTACATAAAGAATGAAAATAAGCTCCCCACTGGTGGTTGCTATGG
AGTGCCCCCTGATTTACGAACAGAACTGAGTAAAAGAATAGCTCCGTGTT
ATCAAGATTATGTGAAAAAATTTGGAGAAAATTTTGCATCATGTCAAGCT
GGAATATCCAGTTTTTACACAAAGGATTTAATTGTGATGGGGGCCCCAGG
ATCATCTTACTGGACTGGCTCTCTTTTTGTCTACAATATAACTACAAATA
AATACAAGGCTTTTTTAGACAAACAAAATCAAGTAAAATTTGGAAGTTAT
TTAGGATATTCAGTCGGAGCTGGTCATTTTCGGAGCCAGCATACTACCGA
AGTAGTCGGAGGAGCTCCTCAACATGAGCAGATTGGTAAGGCATATATAT
TCAGCATTGATGAAAAAGAACTAAATATCTTACATGAAATGAAAGGTAAA
AAGCTTGGATCGTACTTTGGAGCTTCTGTCTGTGCTGTGGACCTCAATGC
AGATGGCTTCTCAGATCTGCTCGTGGGAGCACCCATGCAGAGCACCATCA
GAGAGGAAGGAAGAGTGTTTGTGTACATCAACTCTGGCTCGGGAGCAGTA
ATGAATGCAATGGAAACAAACCTCGTTGGAAGTGACAAATATGCTGCAAG
ATTTGGGGAATCTATAGTTAATCTTGGCGACATTGACAATGATGGCTTTG
AAGATGTTGCTATCGGAGCTCCACAAGAAGATGACTTGCAAGGTGCTATT
TATATTTACAATGGCCGTGCAGATGGGATCTCGTCAACCTTCTCACAGAG
AATTGAAGGACTTCAGATCAGCAAATCGTTAAGTATGTTTGGACAGTCTA
TATCAGGACAAATTGATGCAGATAATAATGGCTATGTAGATGTAGCAGTT
GGTGCTTTTCGGTCTGATTCTGCTGTCTTGCTAAGGACAAGACCTGTAGT
AATTGTTGACGCTTCTTTAAGCCACCCTGAGTCAGTAAATAGAACGAAAT
TTGACTGTGTTGAAAATGGATGGCCTTCTGTGTGCATAGATCTAACACTT
TGTTTCTCATATAAGGGCAAGGAAGTTCCAGGTTACATTGTTTTGTTTTA
TAACATGAGTTTGGATGTGAACAGAAAGGCAGAGTCTCCACCAAGATTCT
ATTTCTCTTCTAATGGAACTTCTGACGTGATTACAGGAAGCATACAGGTG
TCCAGCAGAGAAGCTAACTGTAGAACACATCAAGCATTTATGCGGAAAGA
TGTGCGGGACATCCTCACCCCAATTCAGATTGAAGCTGCTTACCACCTTG
GTCCTCATGTCATCAGTAAACGAAGTACAGAGGAATTCCCACCACTTCAG
CCAATTCTTCAGCAGAAGAAAGAAAAAGACATAATGAAAAAAACAATAAA
CTTTGCAAGGTTTTGTGCCCATGAAAATTGTTCTGCTGATTTACAGGTTT
CTGCAAAGATTGGGTTTTTGAA GCCCCATGAAAATAAAACATA TCTTGCT
GTTGGGAGTATGAA GACATTGATGTTGAATGTGTCCTTGTTTAATGCTGG
AGATGATGCATATGAAACGACTCTACATGTCAAACTACCCGTGGGTCTTT
ATTTCATTAAGATTTTAGAGCTG GAAGAGAAGCAAATAAACTGTGAAGTC
ACAGATAACTCTGGCGTGGTACAACTTGACTGCAGTATTGGCTATATATA
TGTAGATCATCTCTCAAGGATAGATATTAGCTTTCTCCTGGATGTGAGCT
CACTCAGCAGAG CGGAAGAGGACCTCAGTATCA CAGTGCATGCTACCTGT
GAAAATGAAGAGGAAATGGACAATCTAAAGCACAGCAGAGTGACTGTAGC
AATACCTTTAAAATATGAGGTTAAGCTGACTGTTCATGGGTTTGTAAACC
CAACTTCATTTGTGTATGGATCAAATGATGAAAATGAGCCTGAAACGTGC
ATGGTGGAGAAAATGAACTTAACTTTCCATGTTATCAACACTGGCAATAG
TATGGCTCCCAATGTTAGTGTGGAAATAATGGTACCAAATTCTTTTAGCC
CCCAAACTGATAAGCTGTTCAACATTTTGGATGTCCAGACTACTACTGGA
GAATGCCACTTTGAAAATTATCAAAGAGTGTGTGCATTAGAGCAGCAAAA
GAGTGCAATGCAGACCTTGAAAGGCATAGTCCGGTTCTTGTCCAAGACTG
ATAAGAGGCTATTGTACTGCATAAAAGCTGATCCACATTGTTTAAATTTC
TTGTGTAATTTTGGGAAAATGGAAAGTGGAAAAGAAGCCAGTGTTCATAT
CCAACTGGAAGGCCGGCCATCCATTTTAGAAATGGATGAGACTTCAGCAC
TCAAGTTTGAAATAAGAGCAACAGGTTTTCCAGAGCCAAATCCAAGAGTA
ATTGAACTAAACAAGGATGAGAATGTTGCGCATGTTCTACTGGAAGGACT
ACATCATCAAAGACCCAAACGTTATTTCACCATAGTGATTATTTCAAGTA
GCTTGCTACTTGGACTTATTGTACTTCTATTGATCTCATATGTTATGTGG
AAGGCTGGCTTCTTTAAAAGACAATACAAATCTATCCTACAAGAAGAAAA
CAGAAGAGACAGTTGGAGTTATATCAACAGTAAAAGCAATGATGATTAA
(Exon 23 is indicated by double underline.)
TABLE 23
ITGA4 variant (lacking exon 23) Nucleotide
Sequence (2948 nt, SEQ ID No. 58)
ATGGCTTGGGAAGCGAGGCGCGAACCCGGCCCCCGAAGGGCCGCCGTCCG
GGAGACGGTGATGCTGTTGCTGTGCCTGGGGGTCCCGACCGGCCGCCCCT
ACAACGTGGACACTGAGAGCGCGCTGCTTTACCAGGGCCCCCACAACACG
CTGTTCGGCTACTCGGTCGTGCTGCACAGCCACGGGGCGAACCGATGGCT
CCTAGTGGGTGCGCCCACTGCCAACTGGCTCGCCAACGCTTCAGTGATCA
ATCCCGGGGCGATTTACAGATGCAGGATCGGAAAGAATCCCGGCCAGACG
TGCGAACAGCTCCAGCTGGGTAGCCCTAATGGAGAACCTTGTGGAAAGAC
TTGTTTGGAAGAGAGAGACAATCAGTGGTTGGGGGTCACACTTTCCAGAC
AGCCAGGAGAAAATGGATCCATCGTGACTTGTGGGCATAGATGGAAAAAT
ATATTTTACATAAAGAATGAAAATAAGCTCCCCACTGGTGGTTGCTATGG
AGTGCCCCCTGATTTACGAACAGAACTGAGTAAAAGAATAGCTCCGTGTT
ATCAAGATTATGTGAAAAAATTTGGAGAAAATTTTGCATCATGTCAAGCT
GGAATATCCAGTTTTTACACAAAGGATTTAATTGTGATGGGGGCCCCAGG
ATCATCTTACTGGACTGGCTCTCTTTTTGTCTACAATATAACTACAAATA
AATACAAGGCTTTTTTAGACAAACAAAATCAAGTAAAATTTGGAAGTTAT
TTAGGATATTCAGTCGGAGCTGGTCATTTTCGGAGCCAGCATACTACCGA
AGTAGTCGGAGGAGCTCCTCAACATGAGCAGATTGGTAAGGCATATATAT
TCAGCATTGATGAAAAAGAACTAAATATCTTACATGAAATGAAAGGTAAA
AAGCTTGGATCGTACTTTGGAGCTTCTGTCTGTGCTGTGGACCTCAATGC
AGATGGCTTCTCAGATCTGCTCGTGGGAGCACCCATGCAGAGCACCATCA
GAGAGGAAGGAAGAGTGTTTGTGTACATCAACTCTGGCTCGGGAGCAGTA
ATGAATGCAATGGAAACAAACCTCGTTGGAAGTGACAAATATGCTGCAAG
ATTTGGGGAATCTATAGTTAATCTTGGCGACATTGACAATGATGGCTTTG
AAGATGTTGCTATCGGAGCTCCACAAGAAGATGACTTGCAAGGTGCTATT
TATATTTACAATGGCCGTGCAGATGGGATCTCGTCAACCTTCTCACAGAG
AATTGAAGGACTTCAGATCAGCAAATCGTTAAGTATGTTTGGACAGTCTA
TATCAGGACAAATTGATGCAGATAATAATGGCTATGTAGATGTAGCAGTT
GGTGCTTTTCGGTCTGATTCTGCTGTCTTGCTAAGGACAAGACCTGTAGT
AATTGTTGACGCTTCTTTAAGCCACCCTGAGTCAGTAAATAGAACGAAAT
TTGACTGTGTTGAAAATGGATGGCCTTCTGTGTGCATAGATCTAACACTT
TGTTTCTCATATAAGGGCAAGGAAGTTCCAGGTTACATTGTTTTGTTTTA
TAACATGAGTTTGGATGTGAACAGAAAGGCAGAGTCTCCACCAAGATTCT
ATTTCTCTTCTAATGGAACTTCTGACGTGATTACAGGAAGCATACAGGTG
TCCAGCAGAGAAGCTAACTGTAGAACACATCAAGCATTTATGCGGAAAGA
TGTGCGGGACATCCTCACCCCAATTCAGATTGAAGCTGCTTACCACCTTG
GTCCTCATGTCATCAGTAAACGAAGTACAGAGGAATTCCCACCACTTCAG
CCAATTCTTCAGCAGAAGAAAGAAAAAGACATAATGAAAAAAACAATAAA
CTTTGCAAGGTTTTGTGCCCATGAAAATTGTTCTGCTGATTTACAGGTTT
CTGCAAAGATT GGGTTTTTGA AG AAGAGAAGC AAATAAACTGTGAAGTCA
CAGATAACTCTGGCGTGGTACAACTTGACTGCAGTATTGGCTATATATAT
GTAGATCATCTCTCAAGGATAGATATTAGCTTTCTCCTGGATGTGAGCTC
ACTCAGCAGAGCGGAAGAGGACCTCAGTATCACAGTGCATGCTACCTGTG
AAAATGAAGAGGAAATGGACAATCTAAAGCACAGCAGAGTGACTGTAGCA
ATACCTTTAAAATATGAGGTTAAGCTGACTGTTCATGGGTTTGTAAACCC
AACTTCATTTGTGTATGGATCAAATGATGAAAATGAGCCTGAAACGTGCA
TGGTGGAGAAAATGAACTTAACTTTCCATGTTATCAACACTGGCAATAGT
ATGGCTCCCAATGTTAGTGTGGAAATAATGGTACCAAATTCTTTTAGCCC
CCAAACTGATAAGCTGTTCAACATTTTGGATGTCCAGACTACTACTGGAG
AATGCCACTTTGAAAATTATCAAAGAGTGTGTGCATTAGAGCAGCAAAAG
AGTGCAATGCAGACCTTGAAAGGCATAGTCCGGTTCTTGTCCAAGACTGA
TAAGAGGCTATTGTACTGCATAAAAGCTGATCCACATTGTTTAAATTTCT
TGTGTAATTTTGGGAAAATGGAAAGTGGAAAAGAAGCCAGTGTTCATATC
CAACTGGAAGGCCGGCCATCCATTTTAGAAATGGATGAGACTTCAGCACT
CAAGTTTGAAATAAGAGCAACAGGTTTTCCAGAGCCAAATCCAAGAGTAA
TTGAACTAAACAAGGATGAGAATGTTGCGCATGTTCTACTGGAAGGACTA
CATCATCAAAGACCCAAACGTTATTTCACCATAGTGATTATTTCAAGTAG
CTTGCTACTTGGACTTATTGTACTTCTATTGATCTCATATGTTATGTGGA
AGGCTGGCTTCTTTAAAAGACAATACAAATCTATCCTACAAGAAGAAAAC
AGAAGAGACAGTTGGAGTTATATCAACAGTAAAAGCAATGATGATTAA
(Double underline indicates bases bordering the splice junction)
TABLE 24
Primer across the junction between ITGA4
exon 22 and 24
Primer across the junction
GGGTTTTTGA
AG
AAGAGAAGC
between ITGA4 exon 22 and
24 (SEQ ID No. 57)
(Double underline indicates bases bordering the splice junction)
TABLE 25
siRNA for selectively knockdown ITGA4
full length and variants expression
siRNA targeting ITGA4 exon 23
Sense (SEQ ID No. 55) 5′ GGGAGUAUGAAGACAUUGA dTdT
3′
Antisense (SEQ ID No. 56) 3′ dTdTCCCUCAUACUUCUGUA-
ACU (5′-P)5′
siRNA targeting splice junction between
ITGA4 exon 22 and exon 24
Sense (SEQ ID No. 59) 5′ GA AG AAGAGAAGCAAAUAA dTdT
3′
Antisense (SEQ ID No. 60) 3′ dTdTCU UC UUCUCUUCGUUU-
AUU (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 26
MET (Full length)Nucleotide Sequence (4226 nt, SEQ ID No. 62)
ATGAAGGCCCCCGCTGTGCTTGCACCTGGCATCCTCGTGCTCCTGTTTACCTTGGTGCAGAGGAGCAATGGG
AGTGTAAAGAGGCACTAGCAAAGTCCGAGATGAATGTGAATATGAAGTATCAGCTTCCCAACTTCACCGCGG
AAACACCCATCCAGAATGTCATTCTACATGAGCATCACATTTTCCTTGGTGCCACTAACTACATTTATGTTT
TAAATGAGGAAGACCTTCAGAAGGTTGCTGAGTACAAGACTGGGCCTGTGCTGGAACACCCAGATTGTTTCC
CATGTCAGGACTGCAGCAGCAAAGCCAATTTATCAGGAGGTGTTTGGAAAGATAACATCAACATGGCTCTAG
TTGTCGACACCTACTATGATGATCAACTCATTAGCTGTGGCAGCGTCAACAGAGGGACCTGCCAGCGACATG
TCTTTCCCCACAATCATACTGCTGACATACAGTCGGAGGTTCACTGCATATTCTCCCCACAGATAGAAGAGC
CCAGCCAGTGTCCTGACTGTGTGGTGAGCGCCCTGGGAGCCAAAGTCCTTTCATCTGTAAAGGACCGGTTCA
TCAACTTCTTTGTAGGCAATACCATAAATTCTTCTTATTTCCCAGATCATCCATTGCATTCGATATCAGTGA
GAAGGCTAAAGGAAACGAAAGATGGTTTTATGTTTTTGACGGACCAGTCCTACATTGATGTTTTACCTGAGT
TCAGAGATTCTTACCCCATTAAGTATGTCCATGCCTTTGAAAGCAACAATTTTATTTACTTCTTGACGGTCC
AAAGGGAAACTCTAGATGCTCAGACTTTTCACACAAGAATAATCAGGTTCTGTTCCATAAACTCTGGATTGC
ATTCCTACATGGAAATGCCTCTGGAGTGTATTCTCACAGAAAAGAGAAAAAAGAGATCCACAAAGAAGGAAG
TGTTTAATATACTTCAGGCTGCGTATGTCAGCAAGCCTGGGGCCCAGCTTGCTAGACAAATAGGAGCCAGCC
TGAATGATGACATTCTTTTCGGGGTGTTCGCACAAAGCAAGCCAGATTCTGCCGAACCAATGGATCGATCTG
CCATGTGTGCATTCCCTATCAAATATGTCAACGACTTCTTCAACAAGATCGTCAACAAAAACAATGTGAGAT
GTCTCCAGCATTTTTACGGACCCAATCATGAGCACTGCTTTAATAGGACACTTCTGAGAAATTCATCAGGCT
GTGAAGCGCGCCGTGATGAATATCGAACAGAGTTTACCACAGCTTTGCAGCGCGTTGACTTATTCATGGGTC
AATTCAGCGAAGTCCTCTTAACATCTATATCCACCTTCATTAAAGGAGACCTCACCATAGCTAATCTTGGGA
CATCAGAGGGTCGCTTCATGCAGGTTGTGGTTTCTCGATCAGGACCATCAACCCCTCATGTGAATTTTCTCC
TGGACTCCCATCCAGTGTCTCCAGAAGTGATTGTGGAGCATACATTAAACCAAAATGGCTACACACTGGTTA
TCACTGGGAAGAAGATCACGAAGATCCCATTGAATGGCTTGGGCTGCAGACATTTCCAGTCCTGCAGTCAAT
GCCTCTCTGCCCCACCCTTTGTTCAGTGTGGCTGGTGCCACGACAAATGTGTGCGATCGGAGGAATGCCTGA
GCGGGACATGGACTCAACAGATCTGTCTGCCTGCAATCTACAAGGTTTTCCCAAATAGTGCACCCCTTGAAG
GAGGGACAAGGCTGACCATATGTGGCTGGGACTTTGGATTTCGGAGGAATAATAAATTTGATTTAAAGAAAA
CTAGAGTTCTCCTTGGAAATGAGAGCTGCACCTTGACTTTAAGTGAGAGCACGATGAATACATTGAAATGCA
CAGTTGGTCCTGCCATGAATAAGCATTTCAATATGTCCATAATTATTTCAAATGGCCACGGGACAACACAAT
ACAGTACATTCTCCTATGTGGATCCTGTAATAACAAGTATTTCGCCGAAATACGGTCCTATGGCTGGTGGCA
CTTTACTTACTTTAACTGGAAATTACCTAAACAGTGGGAATTCTAGACACATTTCAATTGGTGGAAAAACAT
GTACTTTAAAAAGTGTGTCAAACAGTATTCTTGAATGTTATACCCCAGCCCAAACCATTTCAACTGAGTTTG
CTGTTAAATTGAAAATTGACTTAGCCAACCGAGAGACAAGCATCTTCAGTTACCGTGAAGATCCCATTGTCT
ATGAAATTCATCCAACCAAATCTTTTATTAGTACTTGGTGGAAAGAACCTCTCAACATTGTCAGTTTTCTAT
TTTGCTTTGCCAGTGGTGGGAGCACAATAACAGGTGTTGGGAAAAACCTGAATTCAGTTAGTGTCCCGAGAA
TGGTCATAAATGTGCATGAAGCAGGAAGGAACTTTACAGTGGCATGTCAACATCGCTCTAATTCAGAGATAA
TCTGTTGTACCACTCCTTCCCTGCAACAGCTGAATCTGCAACTCCCCCTGAAAACCAAAGCCTTTTTCATGT
TAGATGGGATCCTTTCCAAATACTTTGATCTCATTTATGTACATAATCCTGTGTTTAAGCCTTTTGAAAAGC
CAGTGATGATCTCAATGGGCAATGAAAATGTA CTGGAAATTAA GG GAAATG ATATTGACCCTGAAGCAGTTA
AAGGTGAAGTGTTAAAAGTTGGAAATAAGAGCTGTGAGAATATACACTTACATTCTGAAGCCGTTTTATGCA
CGGTCCCCAATGACCTGCTGAAATTGAACAGCGAGCTAAATATAGAGTGGAAGCAAGCAATTTCTTCAACCG
TCCTTGGAAAAGTAATAGTTCAACCAGATCAGAATTTCACAGGATTGATTGCTGGTGTTGTCTCAATATCAA
CAGCACTGTTATTACTACTTGGGTTTTTCCTGTGGCTGAAAAAGAGAAAGCAAATTAAAGATCTGGGCAGTG
AATTAGTTCGCTACGATGCAAGAGTACACACTCCTCATTTGGATAGGCTTGTAAGTGCCCGAAGTGTAAGCC
CAACTACAGAAATGGTTTCAAATGAATCTGTAGACTACCGAGCTACTTTTCCAGAAGATCAGTTTCCTAATT
CATCTCAGAACGGTTCATGCCGACAAGTGCAGTATCCTCTGACAGACATGTCCCCCATCCTAACTAGTGGGG
ACTCTGATATATCCAGTCCATTACTGCAAAATACTGTCCACATTGACCTCAGTGCTCTAAATCCAGAGCTGG
TCCAGGCAGTGCAGCATGTAGTGATTGGGCCCAGTAGCCTGATTGTGCATTTCAATGAAGTCATAGGAAGAG
GGCATTTTGGTTGTGTATATCATGGGACTTTGTTGGACAATGATGGCAAGAAAATTCACTGTGCTGTGAAAT
CCTTGAACAGAATCACTGACATAGGAGAAGTTTCCCAATTTCTGACCGAGGGAATCATCATGAAAGATTTTA
GTCATCCCAATGTCCTCTCGCTCCTGGGAATCTGCCTGCGAAGTGAAGGGTCTCCGCTGGTGGTCCTACCAT
ACATGAAACATGGAGATCTTCGAAATTTCATTCGAAATGAGACTCATAATCCAACTGTAAAAGATCTTATTG
GCTTTGGTCTTCAAGTAGCCAAAGGCATGAAATATCTTGCAAGCAAAAAGTTTGTCCACAGAGACTTGGCTG
CAAGAAACTGTATGCTGGATGAAAAATTCACAGTCAAGGTTGCTGATTTTGGTCTTGCCAGAGACATGTATG
ATAAAGAATACTATAGTGTACACAACAAAACAGGTGCAAAGCTGCCAGTGAAGTGGATGGCTTTGGAAAGTC
TGCAAACTCAAAAGTTTACCACCAAGTCAGATGTGTGGTCCTTTGGCGTGCTCCTCTGGGAGCTGATGACAA
GAGGAGCCCCACCTTATCCTGACGTAAACACCTTTGATATAACTGTTTACTTGTTGCAAGGGAGAAGACTCC
TACAACCCGAATACTGCCCAGACCCCTTATATGAAGTAATGCTAAAATGCTGGCACCCTAAAGCCGAAATGC
GCCCATCCTTTTCTGAACTGGTGTCCCGGATATCAGCGATCTTCTCTACTTTCATTGGGGAGCACTATGTCC
ATGTGAACGCTACTTATGTGAACGTAAAATGTGTCGCTCCGTATCCTTCTCTGTTGTCATCAGAAGATAACG
CTGATGATGAGGTGGACACACGACCAGCCTCCTTCTGGGAGACATCATAG
(Double underline indicates bases bordering the splice junction between exon 26 and 28)
TABLE 27
MET variant (with non-coding exon 27) Nucleotide
Sequence (4651 nt, SEQ ID No. 65)
ATGAAGGCCCCCGCTGTGCTTGCACCTGGCATCCTCGTGCTCCTGTTTACCTTGGTGCAGAGGAGCAATGGG
AGTGTAAAGAGGCACTAGCAAAGTCCGAGATGAATGTGAATATGAAGTATCAGCTTCCCAACTTCACCGCGG
AAACACCCATCCAGAATGTCATTCTACATGAGCATCACATTTTCCTTGGTGCCACTAACTACATTTATGTTT
TAAATGAGGAAGACCTTCAGAAGGTTGCTGAGTACAAGACTGGGCCTGTGCTGGAACACCCAGATTGTTTCC
CATGTCAGGACTGCAGCAGCAAAGCCAATTTATCAGGAGGTGTTTGGAAAGATAACATCAACATGGCTCTAG
TTGTCGACACCTACTATGATGATCAACTCATTAGCTGTGGCAGCGTCAACAGAGGGACCTGCCAGCGACATG
TCTTTCCCCACAATCATACTGCTGACATACAGTCGGAGGTTCACTGCATATTCTCCCCACAGATAGAAGAGC
CCAGCCAGTGTCCTGACTGTGTGGTGAGCGCCCTGGGAGCCAAAGTCCTTTCATCTGTAAAGGACCGGTTCA
TCAACTTCTTTGTAGGCAATACCATAAATTCTTCTTATTTCCCAGATCATCCATTGCATTCGATATCAGTGA
GAAGGCTAAAGGAAACGAAAGATGGTTTTATGTTTTTGACGGACCAGTCCTACATTGATGTTTTACCTGAGT
TCAGAGATTCTTACCCCATTAAGTATGTCCATGCCTTTGAAAGCAACAATTTTATTTACTTCTTGACGGTCC
AAAGGGAAACTCTAGATGCTCAGACTTTTCACACAAGAATAATCAGGTTCTGTTCCATAAACTCTGGATTGC
ATTCCTACATGGAAATGCCTCTGGAGTGTATTCTCACAGAAAAGAGAAAAAAGAGATCCACAAAGAAGGAAG
TGTTTAATATACTTCAGGCTGCGTATGTCAGCAAGCCTGGGGCCCAGCTTGCTAGACAAATAGGAGCCAGCC
TGAATGATGACATTCTTTTCGGGGTGTTCGCACAAAGCAAGCCAGATTCTGCCGAACCAATGGATCGATCTG
CCATGTGTGCATTCCCTATCAAATATGTCAACGACTTCTTCAACAAGATCGTCAACAAAAACAATGTGAGAT
GTCTCCAGCATTTTTACGGACCCAATCATGAGCACTGCTTTAATAGGACACTTCTGAGAAATTCATCAGGCT
GTGAAGCGCGCCGTGATGAATATCGAACAGAGTTTACCACAGCTTTGCAGCGCGTTGACTTATTCATGGGTC
AATTCAGCGAAGTCCTCTTAACATCTATATCCACCTTCATTAAAGGAGACCTCACCATAGCTAATCTTGGGA
CATCAGAGGGTCGCTTCATGCAGGTTGTGGTTTCTCGATCAGGACCATCAACCCCTCATGTGAATTTTCTCC
TGGACTCCCATCCAGTGTCTCCAGAAGTGATTGTGGAGCATACATTAAACCAAAATGGCTACACACTGGTTA
TCACTGGGAAGAAGATCACGAAGATCCCATTGAATGGCTTGGGCTGCAGACATTTCCAGTCCTGCAGTCAAT
GCCTCTCTGCCCCACCCTTTGTTCAGTGTGGCTGGTGCCACGACAAATGTGTGCGATCGGAGGAATGCCTGA
GCGGGACATGGACTCAACAGATCTGTCTGCCTGCAATCTACAAGGTTTTCCCAAATAGTGCACCCCTTGAAG
GAGGGACAAGGCTGACCATATGTGGCTGGGACTTTGGATTTCGGAGGAATAATAAATTTGATTTAAAGAAAA
CTAGAGTTCTCCTTGGAAATGAGAGCTGCACCTTGACTTTAAGTGAGAGCACGATGAATACATTGAAATGCA
CAGTTGGTCCTGCCATGAATAAGCATTTCAATATGTCCATAATTATTTCAAATGGCCACGGGACAACACAAT
ACAGTACATTCTCCTATGTGGATCCTGTAATAACAAGTATTTCGCCGAAATACGGTCCTATGGCTGGTGGCA
CTTTACTTACTTTAACTGGAAATTACCTAAACAGTGGGAATTCTAGACACATTTCAATTGGTGGAAAAACAT
GTACTTTAAAAAGTGTGTCAAACAGTATTCTTGAATGTTATACCCCAGCCCAAACCATTTCAACTGAGTTTG
CTGTTAAATTGAAAATTGACTTAGCCAACCGAGAGACAAGCATCTTCAGTTACCGTGAAGATCCCATTGTCT
ATGAAATTCATCCAACCAAATCTTTTATTAGTACT TGGTGGAAAGAACCTCTCAA CATTGTCAGTTTTCTAT
TTTGCTTTGCCAGTGGTGGGAGCACAATAACAGGTGTTGGGAAAAACCTGAATTCAGTTAGTGTCCCGAGAA
TGGTCATAAATGTGCATGAAGCAGGAAGGAACTTTACAGTGGCATGTCAACATCGCTCTAATTCAGAGATAA
TCTGTTGTACCACTCCTTCCCTGCAACAGCTGAATCTGCAACTCCCCCTGAAAACCAAAGCCTTTTTCATGT
TAGATGGGATCCTTTCCAAATACTTTGATCTCATTTATGTACATAATCCTGTGTTTAAGCCTTTTGAAAAGC
CAGTGATGATCTCAATGGGCAATGAAAATGTACTGGAAATTAAG gtgggagcagtggcaattcagggag
attattttagtatcatggttcaatattttttcatacttcatttttcttatgtatgagaggaaagc
aaaggcataagagaatatttgttgtgtcagcaatctaactctttatcaatacgttaagttgatca
cattaaaacttctacctotcagccaggcacggtagctcatacctgtaatcccagcactttgggag
gccaaggcgggtgaatcacttgagatcaggagttcaagaccagcctggccaaaatggtgaaaccc
catctccactaaaaatacaaaaattagctgggcatggtggtgggtgcctgtaatcccagctactc
aggaggctgagggacggaggtgacctgagtcctgaaggcgg aggttgcagtgagccaaga tggca
ccactgcact GGAAATGATATTGACCCTGAAGCAGTTAAAGGTGAAGTGTTAAAAGTTGGAAATAAGAGC
TGTGAGAATATACACTTACATTCTGAAGCCGTTTTATGCACGGTCCCCAATGACCTGCTGAAATTGAACAGC
GAGCTAAATATAGAGTGGAAGCAAGCAATTTCTTCAACCGTCCTTGGAAAAGTAATAGTTCAACCAGATCAG
AATTTCACAGGATTGATTGCTGGTGTTGTCTCAATATCAACAGCACTGTTATTACTACTTGGGTTTTTCCTG
TGGCTGAAAAAGAGAAAGCAAATTAAAGATCTGGGCAGTGAATTAGTTCGCTACGATGCAAGAGTACACACT
CCTCATTTGGATAGGCTTGTAAGTGCCCGAAGTGTAAGCCCAACTACAGAAATGGTTTCAAATGAATCTGTA
GACTACCGAGCTACTTTTCCAGAAGATCAGTTTCCTAATTCATCTCAGAACGGTTCATGCCGACAAGTGCAG
TATCCTCTGACAGACATGTCCCCCATCCTAACTAGTGGGGACTCTGATATATCCAGTCCATTACTGCAAAAT
ACTGTCCACATTGACCTCAGTGCTCTAAATCCAGAGCTGGTCCAGGCAGTGCAGCATGTAGTGATTGGGCCC
AGTAGCCTGATTGTGCATTTCAATGAAGTCATAGGAAGAGGGCATTTTGGTTGTGTATATCATGGGACTTTG
TTGGACAATGATGGCAAGAAAATTCACTGTGCTGTGAAATCCTTGAACAGAATCACTGACATAGGAGAAGTT
TCCCAATTTCTGACCGAGGGAATCATCATGAAAGATTTTAGTCATCCCAATGTCCTCTCGCTCCTGGGAATC
TGCCTGCGAAGTGAAGGGTCTCCGCTGGTGGTCCTACCATACATGAAACATGGAGATCTTCGAAATTTCATT
CGAAATGAGACTCATAATCCAACTGTAAAAGATCTTATTGGCTTTGGTCTTCAAGTAGCCAAAGGCATGAAA
TATCTTGCAAGCAAAAAGTTTGTCCACAGAGACTTGGCTGCAAGAAACTGTATGCTGGATGAAAAATTCACA
GTCAAGGTTGCTGATTTTGGTCTTGCCAGAGACATGTATGATAAAGAATACTATAGTGTACACAACAAAACA
GGTGCAAAGCTGCCAGTGAAGTGGATGGCTTTGGAAAGTCTGCAAACTCAAAAGTTTACCACCAAGTCAGAT
GTGTGGTCCTTTGGCGTGCTCCTCTGGGAGCTGATGACAAGAGGAGCCCCACCTTATCCTGACGTAAACACC
TTTGATATAACTGTTTACTTGTTGCAAGGGAGAAGACTCCTACAACCCGAATACTGCCCAGACCCCTTATAT
GAAGTAATGCTAAAATGCTGGCACCCTAAAGCCGAAATGCGCCCATCCTTTTCTGAACTGGTGTCCCGGATA
TCAGCGATCTTCTCTACTTTCATTGGGGAGCACTATGTCCATGTGAACGCTACTTATGTGAACGTAAAATGT
GTCGCTCCGTATCCTTCTCTGTTGTCATCAGAAGATAACGCTGATGATGAGGTGGACACACGACCAGCCTCC
TTCTGGGAGACATCATAG
(Exon 27 is indicated as double underline.)
TABLE 28
Primer across the junction between MET
exon 26 and 28
Primer across the junction
CTGGAAATTAA
GG
GAAATG
between MET exon 26 and
28 (SEQ ID No. 61):
(Double underline indicates bases bordering the splice junction)
TABLE 29
siRNA for selectively knockdown MET full
length and variants expression
siRNA targeting splice junction between
MET exon 26 and exon 28
Sense (SEQ ID No. 63) 5′ GUACUGGAAAUUAA GG GAAdTdT
3′
Antisense (SEQ ID No. 64) 3′ dTdTCAUGACCUUUAAUU CC -
CUU (5′-P)5′
siRNA targeting non-coding MET exon 27
Sense (SEQ ID No. 68) 5′ CAGCAAUCUAACUCUUUAUdTdT
3′
Antisense (SEQ ID No. 69) 3′ dTdTGUCGUUAGAUUGAGAA-
AUA (5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 30
NF1 (full length)Nucleotide Sequence (8520 nt, SEQ ID No. 70)
ATGGCCGCGCACAGGCCGGTGGAATGGGTCCAGGCCGTGGTCAGCCGCTTCGACGAGCAGCTTCCAATAA
AAACAGGACAGCAGAACACACATACCAAAGTCAGTACTGAGCACAACAAGGAATGTCTAATCAATATTTC
CAAATACAAGTTTTCTTTGGTTATAAGCGGCCTCACTACTATTTTAAAGAATGTTAACAATATGAGAATA
TTTGGAGAAGCTGCTGAAAAAAATTTATATCTCTCTCAGTTGATTATATTGGATACACTGGAAAAATGTC
TTGCTGGGCAACCAAAGGACACAATGAGATTAGATGAAACGATGCTGGTCAAACAGTTGCTGCCAGAAAT
CTGCCATTTTCTTCACACCTGTCGTGAAGGAAACCAGCATGCAGCTGAACTTCGGAATTCTGCCTCTGGG
GTTTTATTTTCTCTCAGCTGCAACAACTTCAATGCAGTCTTTAGTCGCATTTCTACCAGGTTACAGGAAT
TAACTGTTTGTTCAGAAGACAATGTTGATGTTCATGATATAGAATTGTTACAGTATATCAATGTGGATTG
TGCAAAATTAAAACGACTCCTGAAGGAAACAGCATTTAAATTTAAAGCCCTAAAGAAGGTTGCGCAGTTA
GCAGTTATAAATAGCCTGGAAAAG GCATTTTGGAACTGGGTAGAA AATTATCCAGATGAATTTACAAAAC
TGTACCAGATCCCACAGACTGATATGGCTG AATGTGCAGAAAAGCTATTTGACTTGGTGGATGGTTTTGC
TGAAAGCACCAAACGTAAAGCAGCAGTTTGGCCACTACAAATCATTCTCCTTATCTTGTGTCCAGAAATA
ATCCAGGATATATCCAAAGACGTGGTTGATGAAAACAACATGAATAAGAAGTTATTTCTGGACAGTCTAC
GAAAAGCTCTTGCTGGCCATGGAGGAAGTAGGCAGCTGACAGAAAGTGCTGCAATTGCCTGTGTCAAACT
GTGTAAAGCAAGTACTTACATCAATTGGGAAGATAACTCTGTCATTTTCCTAC TTGTTCAGTCCATGGTG
GTT GATCTTAAGAACCTGCTTTTTAATCCAAGTAAGCCATTCTCAAGAGGCAGTCAGCCTGCAGATGTGG
ATCTAATGATTGACTGCCTTGTTTCTTGCTTTCGTATAAGCCCTCACAACAACCAACACTTTAAGATCTG
CCTGGCTCAGAATTCACCTTCTACATTTCACTATGTGCTGGTAAATTCACTCCATCGAATCATCACCAAT
TCCGCATTGGATTGGTGGCCTAAGATTGATGCTGTGTATTGTCACTCGGTTGAACTTCGAAATATGTTTG
GTGAAACACTTCATAAAGCAGTGCAAGGTTGTGGAGCACACCCAGCAATACGAATGGCACCGAGTCTTAC
ATTTAAAGAAAAAGTAACAAGCCTTAAATTTAAAGAAAAACCTACAGACCTGGAGACAAGAAGCTATAAG
TATCTTCTCTTGTCCATGGTGAAACTAATTCATGCAGATCCAAAGCTCTTGCTTTGTAATCCAAGAAAAC
AGGGGCCCGAAACCCAAGGCAGTACAGCAGAATTAATTACAGGGCTCGTCCAACTGGTCCCTCAGTCACA
CATGCCAGAGATTGCTCAGGAAGCAATGGAGGCTCTGCTGGTTCTTCATCAGTTAGATAGCATTGATTTG
TGGAATCCTGATGCTCCTGTAGAAACATTTTGGGAGATTAGCTCACAAATGCTTTTTTACATCTGCAAGA
AATTAACTAGTCATCAAATGCTTAGTAGCACAGAAATTCTCAAGTGGTTGCGGGAAATATTGATCTGCAG
GAATAAATTTCTTCTTAAAAATAAGCAGGCAGATAGAAGTTCCTGTCACTTTCTCCTTTTTTACGGGGTA
GGATGTGATATTCCTTCTAGTGGAAATACCAGTCAAATGTCCATGGATCATGAAGAATTACTACGTACTC
CTGGAGCCTCTCTCCGGAAGGGAAAAGGGAACTCCTCTATGGATAGTGCAGCAGGATGCAGCGGAACCCC
CCCGATTTGCCGACAAGCCCAGACCAAACTAGAAGTGGCCCTGTACATGTTTCTGTGGAACCCTGACACT
GAAGCTGTTCTGGTTGCCATGTCCTGTTTCCGCCACCTCTGTGAGGAAGCAGATATCCGGTGTGGGGTGG
ATGAAGTGTCAGTGCATAACCTCTTGCCCAACTATAACACATTCATGGAGTTTGCCTCTGTCAGCAATAT
GATGTCAACAGGAAGAGCAGCACTTCAGAAAAGAGTGATGGCACTGCTGAGGCGCATTGAGCATCCCACT
GCAGGAAACACTGAGGCTTGGGAAGATACACATGCAAAATGGGAACAAGCAACAAAGCTAATCCTTAACT
ATCCAAAAGCCAAAATGGAAGATGGCCAGGCTGCTGAAAGCCTTCACAAGACCATTGTTAAGAGGCGAAT
GTCCCATGTGAGTGGAGGAGGATCCATAGATTTGTCTGACACAGACTCCCTACAGGAATGGATCAACATG
ACTGGCTTCCTTTGTGCCCTTGGGGGAGTGTGCCTCCAGCAGAGAAGCAATTCTGGCCTGGCAACCTATA
GCCCACCCATGGGTCCAGTCAGTGAACGTAAGGGTTCTATGATTTCAGTGATGTCTTCAGAGGGAAACGC
AGATACACCTGTCAGCAAATTTATGGATCGGCTGTTGTCCTTAATGGTGTGTAACCATGAGAAAGTGGGA
CTTCAAATACGGACCAATGTTAAGGATCTGGTGGGTCTAGAATTGAGTCCTGCTCTGTATCCAATGCTAT
TTAACAAATTGAAGAATACCATCAGCAAGTTTTTTGACTCCCAAGGACAGGTTTTATTGACTGATACCAA
TACTCAATTTGTAGAACAAACCATAGCTATAATGAAGAACTTGCTAGATAATCATACTGAAGGCAGCTCT
GAACATCTAGGGCAAGCTAGCATTGAAACAATGATGTTAAATCTGGTCAGGTATGTTCGTGTGCTTGGGA
ATATGGTCCATGCAATTCAAATAAAAACGAAACTGTGTCAATTAGTTGAAGTAATGATGGCAAGGAGAGA
TGACCTCTCATTTTGCCAAGAGATGAAATTTAGGAATAAGATGGTAGAATACCTGACAGACTGGGTTATG
GGAACATCAAACCAAGCAGCAGATGATGATGTAAAATGTCTTACAAGAGATTTGGACCAGGCAAGCATGG
AAGCAGTAGTTTCACTTCTAGCTGGTCTCCCTCTGCAGCCTGAAGAAGGAGATGGTGTGGAATTGATGGA
AGCCAAATCACAGTTATTTCTTAAATACTTCACATTATTTATGAACCTTTTGAATGACTGCAGTGAAGTT
GAAGATGAAAGTGCGCAAACAGGTGGCAGGAAACGTGGCATGTCTCGGAGGCTGGCATCACTGAGGCACT
GTACGGTCCTTGCAATGTCAAACTTACTCAATGCCAACGTAGACAGTGGTCTCATGCACTCCATAGGCTT
AGGTTACCACAAGGATCTCCAGACAAGAGCTACATTTATGGAAGTTCTGACAAAAATCCTTCAACAAGGC
ACAGAATTTGACACACTTGCAGAAACAGTATTGGCTGATCGGTTTGAGAGATTGGTGGAACTGGTCACAA
TGATGGGTGATCAAGGAGAACTCCCTATAGCGATGGCTCTGGCCAATGTGGTTCCTTGTTCTCAGTGGGA
TGAACTAGCTCGAGTTCTGGTTACTCTGTTTGATTCTCGGCATTTACTCTACCAACTGCTCTGGAACATG
TTTTCTAAAGAAGTAGAATTGGCAGACTCCATGCAGACTCTCTTCCGAGGCAACAGCTTGGCCAGTAAAA
TAATGACATTCTGTTTCAAGGTATATGGTGCTACCTATCTACAAAAACTCCTGGATCCTTTATTACGAAT
TGTGATCACATCCTCTGATTGGCAACATGTTAGCTTTGAAGTGGATCCTACCAGGTTAGAACCATCAGAG
AGCCTTGAGGAAAACCAGCGGAACCTCCTTCAGATGACTGAAAAGTTCTTCCATGCCATCATCAGTTCCT
CCTCAGAATTCCCCCCTCAACTTCGAAGTGTGTGCCACTGTTTATACCAGGCAACTTGCCACTCCCTACT
GAATAAAGCTACAGTAAAAGAAAAAAAGGAAAACAAAAAATCAGTGGTTAGCCAGCGTTTCCCTCAGAAC
AGCATCGGTGCAGTAGGAAGTGCCATGTTCCTCAGATTTATCAATCCTGCCATTGTCTCACCGTATGAAG
CAGGGATTTTAGATAAAAAGCCACCACCTAGAATCGAAAGGGGCTTGAAGTTAATGTCAAAGATACTTCA
GAGTATTGCCAATCATGTTCTCTTCACAAAAGAAGAACATATGCGGCCTTTCAATGATTTTGTGAAAAGC
AACTTTGATGCAGCACGCAGGTTTTTCCTTGATATAGCATCTGATTGTCCTACAAGTGATGCAGTAAATC
ATAGTCTTTCCTTCATAAGTGACGGCAATGTGCTTGCTTTACATCGTCTACTCTGGAACAATCAGGAGAA
AATTGGGCAGTATCTTTCCAGCAACAGGGATCATAAAGCTGTTGGAAGACGACCTTTTGATAAGATGGCA
ACACTTCTTGCATACCTGGGTCCTCCAGAGCACAAACCTGTGGCAGATACACACTGGTCCAGCCTTAACC
TTACCAGTTCAAAGTTTGAGGAATTTATGACTAGGCATCAGGTACATGAAAAAGAAGAATTCAAGGCTTT
GAAAACGTTAAGTATTTTCTACCAAGCTGGGACTTCCAAAGCTGGGAATCCTATTTTTTATTATGTTGCA
CGGAGGTTCAAAACTGGTCAAATCAATGGTGATTTGCTGATATACCATGTCTTACTGACTTTAAAGCCAT
ATTATGCAAAGCCATATGAAATTGTAGTGGACCTTACCCATACCGGGCCTAGCAATCGCTTTAAAACAGA
CTTTCTCTCTAAGTGGTTTGTTGTTTTTCCTGGCTTTGCTTACGACAACGTCTCCGCAGTCTATATCTAT
AACTGTAACTCCTGGGTCAGGGAGTACACCAAGTATCATGAGCGGCTGCTGACTGGCCTCAAAGGTAGCA
AAAGGCTTGTTTTCATAGACTGTCCTGGGAAACTGGCTGAGCACATAGAGCATGAACAACAGAAACTACC
TGCTGCCACCTTGGCTTTAGAAGAGGACCTGAAGGTATTCCACAATGCTCTCAAGCTAGCTCACAAAGAC
ACCAAAGTTTCTATTAAAGTTGGTTCTACTGCTGTCCAAGTAACTTCAGCAGAGCGAACAAAAGTCCTAG
GGCAATCAGTCTTTCTAAATGACATTTATTATGCTTCGGAAATTGAAGAAATCTGCCTAGTAGATGAGAA
CCAGTTCACCTTAACCATTGCAAACCAGGGCACGCCGCTCACCTTCATGCACCAGGAGTGTGAAGCCATT
GTCCAGTCTATCATTCATATCCGGACCCGCTGGGAACTGTCACAGCCCGACTCTATCCCCCAACACACCA
AGATTCGGCCAAAAGATGTCCCTGGGACACTGCTCAATATCGCATTACTTAATTTAGGCAGTTCTGACCC
GAGTTTACGGTCAGCTGCCTATAATCTTCTGTGTGCCTTAACTTGTACCTTTAATTTAAAAATCGAGGGC
CAGTTACTAGAGACATCAGGTTTATGTATCCCTGCCAACAACACCCTCTTTATTGTCTCTATTAGTAAGA
CACTGGCAGCCAATGAGCCACACCTCACGTTAGAATTTTTGGAAGAGTGTATTTCTGGATTTAGCAAATC
TAGTATTGAATTGAAACACCTTTGTTTGGAATACATGACTCCATGGCTGTCAAATCTAGTTCGTTTTTGC
AAGCATAATGATGATGCCAAACGACAAAGAGTTACTGCTATTCTTGACAAGCTGATAACAATGACCATCA
ATGAAAAACAGATGTACCCATCTATTCAAGCAAAAATATGGGGAAGCCTTGGGCAGATTACAGATCTGCT
TGATGTTGTACTAGACAGTTTCATCAAAACCAGTGCAACAGGTGGCTTGGGATCAATAAAAGCTGAGGTG
ATGGCAGATACTGCTGTAGCTTTGGCTTCTGGAAATGTGAAATTGGTTTCAAGCAAGGTTATTGGAAGGA
TGTGCAAAATAATTGACAAGACATGCTTATCTCCAACTCCTACTTTAGAACAACATCTTATGTGGGATGA
TATTGCTATTTTAGCACGCTACATGCTGATGCTGTCCTTCAACAATTCCCTTGATGTGGCAGCTCATCTT
CCCTACCTCTTCCACGTTGTTACTTTCTTAGTAGCCACAGGTCCGCTCTCCCTTAGAGCTTCCACACATG
GACTGGTCATTAATATCATTCACTCTCTGTGTACTTGTTCACAGCTTCATTTTAGTGAAGAGACCAAGCA
AGTTTTGAGACTCAGTCTGACAGAGTTCTCATTACCCAAATTTTACTTGCTGTTTGGCATTAGCAAAGTC
AAGTCAGCTGCTGTCATTGCCTTCCGTTCCAGTTACCGGGACAGGTCATTCTCTCCTGGCTCCTATGAGA
GAGAGACTTTTGCTTTGACATCCTTGGAAACAGTCACAGAAGCTTTGTTGGAGATCATGGAGGCATGCAT
GAGAGATATTCCAACGTGCAAGTGGCTGGACCAGTGGACAGAACTAGCTCAAAGATTTGCATTCCAATAT
AATCCATCCCTGCAACCAAGAGCTCTTGTTGTCTTTGGGTGTATTAGCAAACGAGTGTCTCATGGGCAGA
TAAAGCAGATAATCCGTATTCTTAGCAAGGCACTTGAGAGTTGCTTAAAAGGACCTGACACTTACAACAG
TCAAGTTCTGATAGAAGCTACAGTAATAGCACTAACCAAATTACAGCCACTTCTTAATAAGGACTCGCCT
CTGCACAAAGCCCTCTTTTGGGTAGCTGTGGCTGTGCTGCAGCTTGATGAGGTCAACTTGTATTCAGCAG
GTACCGCACTTCTTGAACAAAACCTGCATACTTTAGATAGTCTCCGTATATTCAATGACAAGAGTCCAGA
GGAAGTATTTATGGCAATCCGGAATCCTCTGGAGTGGCACTGCAAGCAAATGGATCATTTTGTTGGACTC
AATTTCAACTCTAACTTTAACTTTGCATTGGTTGGACACCTTTTAAAAGGGTACAGGCATCCTTCACCTG
CTATTGTTGCAAGAACAGTCAGAATTTTACATACACTACTAACTCTGGTTAACAAACACAGAAATTGTGA
CAAATTTGAAGTGAATACACAGAGCGTGGCCTACTTAGCAGCTTTACTTACAGTGTCTGAAGAAGTTCGA
AGTCGCTGCAGCCTAAAACATAGAAAGTCACTTCTTCTTACTGATATTTCAATGGAAAATGTTCCTATGG
ATACATATCCCATTCATCATGGTGACCCTTCCTATAGGACACTAAAGGAGACTCAGCCATGGTCCTCTCC
CAAAGGTTCTGAAGGATACCTTGCAGCCACCTATCCAACTGTCGGCCAGACCAGTCCCCGAGCCAGGAAA
TCCATGAGCCTGGACATGGGGCAACCTTCTCAGGCCAACACTAAGAAGTTGCTTGGAACAAGGAAAAGTT
TTGATCACTTGATATCAGACACAAAGGCTCCTAAAAGGCAAGAAATGGAATCAGGGATCACAACACCCCC
CAAAATGAGGAGAGTAGCAGAAACTGATTATGAAATGGAAACTCAGAGGATTTCCTCATCACAACAGCAC
CCACATTTACGTAAAGTTTCAGTGTCTGAATCAAATGTTCTCTTGGATGAAGAAGTACTTACTGATCCGA
AGATCCAGGCGCTGCTTCTTACTGTTCTAGCTACACTGGTAAAATATACCACAGATGAGTTTGATCAACG
AATTCTTTATGAATACTTAGCAGAGGCCAGTGTTGTGTTTCCCAAAGTCTTTCCTGTTGTGCATAATTTG
TTGGACTCTAAGATCAACACCCTGTTATCATTGTGCCAAGATCCAAATTTGTTAAATCCAATCCATGGAA
TTGTGCAGAGTGTGGTGTACCATGAAGAATCCCCACCACAATACCAAACATCTTACCTGCAAAGTTTTGG
TTTTAATGGCTTGTGGCGGTTTGCAGGACCGTTTTCAAAGCAAACACAAATTCCAGACTATGCTGAGCTT
ATTGTTAAGTTTCTTGATGCCTTGATTGACACGTACCTGCCTGGAATTGATGAAGAAACCAGTGAAGAAT
CCCTCCTGACTCCCACATCTCCTTACCCTCCTGCACTGCAGAGCCAGCTTAGTATCACTGCCAACCTTAA
CCTTTCTAATTCCATGACCTCACTTGCAACTTCCCAGCATTCCCCAGGAATCGACAAGGAGAACGTTGAA
CTCTCCCCTACCACTGGCCACTGTAACAGTGGACGAACTCGCCACGGATCCGCAAGCCAAGTGCAGAAGC
AAAGAAGCGCTGGCAGTTTCAAACGTAATAGCATTAAGAAGATCGTGTGA
(Exon 8 is indicated as double underline.)
TABLE 31
NF1 variant (lacking exon 8) Nucleotide Sequence
(8444 nt, SEQ ID No. 76)
ATGGCCGCGCACAGGCCGGTGGAATGGGTCCAGGCCGTGGTCAGCCGCTTCGACGAGCAGCTTCCAATAA
AAACAGGACAGCAGAACACACATACCAAAGTCAGTACTGAGCACAACAAGGAATGTCTAATCAATATTTC
CAAATACAAGTTTTCTTTGGTTATAAGCGGCCTCACTACTATTTTAAAGAATGTTAACAATATGAGAATA
TTTGGAGAAGCTGCTGAAAAAAATTTATATCTCTCTCAGTTGATTATATTGGATACACTGGAAAAATGTC
TTGCTGGGCAACCAAAGGACACAATGAGATTAGATGAAACGATGCTGGTCAAACAGTTGCTGCCAGAAAT
CTGCCATTTTCTTCACACCTGTCGTGAAGGAAACCAGCATGCAGCTGAACTTCGGAATTCTGCCTCTGGG
GTTTTATTTTCTCTCAGCTGCAACAACTTCAATGCAGTCTTTAGTCGCATTTCTACCAGGTTACAGGAAT
TAACTGTTTGTTCAGAAGACAATGTTGATGTTCATGATATAGAATTGTTACAGTATATCAATGTGGATTG
TGCAAAATTAAAACGACTCCTGAAGGAAACAGCATTTAAATTTAAAGCCCTAAAGAAGGTTGCGCAGTTA
GCAGTTATAAATA GCCTGGAAAA GA ATGTGCAGA AAAGCTATTTGACTTGGTGGATGGTTTTGCTGAAAG
CACCAAACGTAAAGCAGCAGTTTGGCCACTACAAATCATTCTCCTTATCTTGTGTCCAGAAATAATCCAG
GATATATCCAAAGACGTGGTTGATGAAAACAACATGAATAAGAAGTTATTTCTGGACAGTCTACGAAAAG
CTCTTGCTGGCCATGGAGGAAGTAGGCAGCTGACAGAAAGTGCTGCAATTGCCTGTGTCAAACTGTGTAA
AGCAAGTACTTACATCAATTGGGAAGATAACTCTGTCATTTTCCTACTTGTTCAGTCCATGGTGGTTGAT
CTTAAGAACCTGCTTTTTAATCCAAGTAAGCCATTCTCAAGAGGCAGTCAGCCTGCAGATGTGGATCTAA
TGATTGACTGCCTTGTTTCTTGCTTTCGTATAAGCCCTCACAACAACCAACACTTTAAGATCTGCCTGGC
TCAGAATTCACCTTCTACATTTCACTATGTGCTGGTAAATTCACTCCATCGAATCATCACCAATTCCGCA
TTGGATTGGTGGCCTAAGATTGATGCTGTGTATTGTCACTCGGTTGAACTTCGAAATATGTTTGGTGAAA
CACTTCATAAAGCAGTGCAAGGTTGTGGAGCACACCCAGCAATACGAATGGCACCGAGTCTTACATTTAA
AGAAAAAGTAACAAGCCTTAAATTTAAAGAAAAACCTACAGACCTGGAGACAAGAAGCTATAAGTATCTT
CTCTTGTCCATGGTGAAACTAATTCATGCAGATCCAAAGCTCTTGCTTTGTAATCCAAGAAAACAGGGGC
CCGAAACCCAAGGCAGTACAGCAGAATTAATTACAGGGCTCGTCCAACTGGTCCCTCAGTCACACATGCC
AGAGATTGCTCAGGAAGCAATGGAGGCTCTGCTGGTTCTTCATCAGTTAGATAGCATTGATTTGTGGAAT
CCTGATGCTCCTGTAGAAACATTTTGGGAGATTAGCTCACAAATGCTTTTTTACATCTGCAAGAAATTAA
CTAGTCATCAAATGCTTAGTAGCACAGAAATTCTCAAGTGGTTGCGGGAAATATTGATCTGCAGGAATAA
ATTTCTTCTTAAAAATAAGCAGGCAGATAGAAGTTCCTGTCACTTTCTCCTTTTTTACGGGGTAGGATGT
GATATTCCTTCTAGTGGAAATACCAGTCAAATGTCCATGGATCATGAAGAATTACTACGTACTCCTGGAG
CCTCTCTCCGGAAGGGAAAAGGGAACTCCTCTATGGATAGTGCAGCAGGATGCAGCGGAACCCCCCCGAT
TTGCCGACAAGCCCAGACCAAACTAGAAGTGGCCCTGTACATGTTTCTGTGGAACCCTGACACTGAAGCT
GTTCTGGTTGCCATGTCCTGTTTCCGCCACCTCTGTGAGGAAGCAGATATCCGGTGTGGGGTGGATGAAG
TGTCAGTGCATAACCTCTTGCCCAACTATAACACATTCATGGAGTTTGCCTCTGTCAGCAATATGATGTC
AACAGGAAGAGCAGCACTTCAGAAAAGAGTGATGGCACTGCTGAGGCGCATTGAGCATCCCACTGCAGGA
AACACTGAGGCTTGGGAAGATACACATGCAAAATGGGAACAAGCAACAAAGCTAATCCTTAACTATCCAA
AAGCCAAAATGGAAGATGGCCAGGCTGCTGAAAGCCTTCACAAGACCATTGTTAAGAGGCGAATGTCCCA
TGTGAGTGGAGGAGGATCCATAGATTTGTCTGACACAGACTCCCTACAGGAATGGATCAACATGACTGGC
TTCCTTTGTGCCCTTGGGGGAGTGTGCCTCCAGCAGAGAAGCAATTCTGGCCTGGCAACCTATAGCCCAC
CCATGGGTCCAGTCAGTGAACGTAAGGGTTCTATGATTTCAGTGATGTCTTCAGAGGGAAACGCAGATAC
ACCTGTCAGCAAATTTATGGATCGGCTGTTGTCCTTAATGGTGTGTAACCATGAGAAAGTGGGACTTCAA
ATACGGACCAATGTTAAGGATCTGGTGGGTCTAGAATTGAGTCCTGCTCTGTATCCAATGCTATTTAACA
AATTGAAGAATACCATCAGCAAGTTTTTTGACTCCCAAGGACAGGTTTTATTGACTGATACCAATACTCA
ATTTGTAGAACAAACCATAGCTATAATGAAGAACTTGCTAGATAATCATACTGAAGGCAGCTCTGAACAT
CTAGGGCAAGCTAGCATTGAAACAATGATGTTAAATCTGGTCAGGTATGTTCGTGTGCTTGGGAATATGG
TCCATGCAATTCAAATAAAAACGAAACTGTGTCAATTAGTTGAAGTAATGATGGCAAGGAGAGATGACCT
CTCATTTTGCCAAGAGATGAAATTTAGGAATAAGATGGTAGAATACCTGACAGACTGGGTTATGGGAACA
TCAAACCAAGCAGCAGATGATGATGTAAAATGTCTTACAAGAGATTTGGACCAGGCAAGCATGGAAGCAG
TAGTTTCACTTCTAGCTGGTCTCCCTCTGCAGCCTGAAGAAGGAGATGGTGTGGAATTGATGGAAGCCAA
ATCACAGTTATTTCTTAAATACTTCACATTATTTATGAACCTTTTGAATGACTGCAGTGAAGTTGAAGAT
GAAAGTGCGCAAACAGGTGGCAGGAAACGTGGCATGTCTCGGAGGCTGGCATCACTGAGGCACTGTACGG
TCCTTGCAATGTCAAACTTACTCAATGCCAACGTAGACAGTGGTCTCATGCACTCCATAGGCTTAGGTTA
CCACAAGGATCTCCAGACAAGAGCTACATTTATGGAAGTTCTGACAAAAATCCTTCAACAAGGCACAGAA
TTTGACACACTTGCAGAAACAGTATTGGCTGATCGGTTTGAGAGATTGGTGGAACTGGTCACAATGATGG
GTGATCAAGGAGAACTCCCTATAGCGATGGCTCTGGCCAATGTGGTTCCTTGTTCTCAGTGGGATGAACT
AGCTCGAGTTCTGGTTACTCTGTTTGATTCTCGGCATTTACTCTACCAACTGCTCTGGAACATGTTTTCT
AAAGAAGTAGAATTGGCAGACTCCATGCAGACTCTCTTCCGAGGCAACAGCTTGGCCAGTAAAATAATGA
CATTCTGTTTCAAGGTATATGGTGCTACCTATCTACAAAAACTCCTGGATCCTTTATTACGAATTGTGAT
CACATCCTCTGATTGGCAACATGTTAGCTTTGAAGTGGATCCTACCAGGTTAGAACCATCAGAGAGCCTT
GAGGAAAACCAGCGGAACCTCCTTCAGATGACTGAAAAGTTCTTCCATGCCATCATCAGTTCCTCCTCAG
AATTCCCCCCTCAACTTCGAAGTGTGTGCCACTGTTTATACCAGGCAACTTGCCACTCCCTACTGAATAA
AGCTACAGTAAAAGAAAAAAAGGAAAACAAAAAATCAGTGGTTAGCCAGCGTTTCCCTCAGAACAGCATC
GGTGCAGTAGGAAGTGCCATGTTCCTCAGATTTATCAATCCTGCCATTGTCTCACCGTATGAAGCAGGGA
TTTTAGATAAAAAGCCACCACCTAGAATCGAAAGGGGCTTGAAGTTAATGTCAAAGATACTTCAGAGTAT
TGCCAATCATGTTCTCTTCACAAAAGAAGAACATATGCGGCCTTTCAATGATTTTGTGAAAAGCAACTTT
GATGCAGCACGCAGGTTTTTCCTTGATATAGCATCTGATTGTCCTACAAGTGATGCAGTAAATCATAGTC
TTTCCTTCATAAGTGACGGCAATGTGCTTGCTTTACATCGTCTACTCTGGAACAATCAGGAGAAAATTGG
GCAGTATCTTTCCAGCAACAGGGATCATAAAGCTGTTGGAAGACGACCTTTTGATAAGATGGCAACACTT
CTTGCATACCTGGGTCCTCCAGAGCACAAACCTGTGGCAGATACACACTGGTCCAGCCTTAACCTTACCA
GTTCAAAGTTTGAGGAATTTATGACTAGGCATCAGGTACATGAAAAAGAAGAATTCAAGGCTTTGAAAAC
GTTAAGTATTTTCTACCAAGCTGGGACTTCCAAAGCTGGGAATCCTATTTTTTATTATGTTGCACGGAGG
TTCAAAACTGGTCAAATCAATGGTGATTTGCTGATATACCATGTCTTACTGACTTTAAAGCCATATTATG
CAAAGCCATATGAAATTGTAGTGGACCTTACCCATACCGGGCCTAGCAATCGCTTTAAAACAGACTTTCT
CTCTAAGTGGTTTGTTGTTTTTCCTGGCTTTGCTTACGACAACGTCTCCGCAGTCTATATCTATAACTGT
AACTCCTGGGTCAGGGAGTACACCAAGTATCATGAGCGGCTGCTGACTGGCCTCAAAGGTAGCAAAAGGC
TTGTTTTCATAGACTGTCCTGGGAAACTGGCTGAGCACATAGAGCATGAACAACAGAAACTACCTGCTGC
CACCTTGGCTTTAGAAGAGGACCTGAAGGTATTCCACAATGCTCTCAAGCTAGCTCACAAAGACACCAAA
GTTTCTATTAAAGTTGGTTCTACTGCTGTCCAAGTAACTTCAGCAGAGCGAACAAAAGTCCTAGGGCAAT
CAGTCTTTCTAAATGACATTTATTATGCTTCGGAAATTGAAGAAATCTGCCTAGTAGATGAGAACCAGTT
CACCTTAACCATTGCAAACCAGGGCACGCCGCTCACCTTCATGCACCAGGAGTGTGAAGCCATTGTCCAG
TCTATCATTCATATCCGGACCCGCTGGGAACTGTCACAGCCCGACTCTATCCCCCAACACACCAAGATTC
GGCCAAAAGATGTCCCTGGGACACTGCTCAATATCGCATTACTTAATTTAGGCAGTTCTGACCCGAGTTT
ACGGTCAGCTGCCTATAATCTTCTGTGTGCCTTAACTTGTACCTTTAATTTAAAAATCGAGGGCCAGTTA
CTAGAGACATCAGGTTTATGTATCCCTGCCAACAACACCCTCTTTATTGTCTCTATTAGTAAGACACTGG
CAGCCAATGAGCCACACCTCACGTTAGAATTTTTGGAAGAGTGTATTTCTGGATTTAGCAAATCTAGTAT
TGAATTGAAACACCTTTGTTTGGAATACATGACTCCATGGCTGTCAAATCTAGTTCGTTTTTGCAAGCAT
AATGATGATGCCAAACGACAAAGAGTTACTGCTATTCTTGACAAGCTGATAACAATGACCATCAATGAAA
AACAGATGTACCCATCTATTCAAGCAAAAATATGGGGAAGCCTTGGGCAGATTACAGATCTGCTTGATGT
TGTACTAGACAGTTTCATCAAAACCAGTGCAACAGGTGGCTTGGGATCAATAAAAGCTGAGGTGATGGCA
GATACTGCTGTAGCTTTGGCTTCTGGAAATGTGAAATTGGTTTCAAGCAAGGTTATTGGAAGGATGTGCA
AAATAATTGACAAGACATGCTTATCTCCAACTCCTACTTTAGAACAACATCTTATGTGGGATGATATTGC
TATTTTAGCACGCTACATGCTGATGCTGTCCTTCAACAATTCCCTTGATGTGGCAGCTCATCTTCCCTAC
CTCTTCCACGTTGTTACTTTCTTAGTAGCCACAGGTCCGCTCTCCCTTAGAGCTTCCACACATGGACTGG
TCATTAATATCATTCACTCTCTGTGTACTTGTTCACAGCTTCATTTTAGTGAAGAGACCAAGCAAGTTTT
GAGACTCAGTCTGACAGAGTTCTCATTACCCAAATTTTACTTGCTGTTTGGCATTAGCAAAGTCAAGTCA
GCTGCTGTCATTGCCTTCCGTTCCAGTTACCGGGACAGGTCATTCTCTCCTGGCTCCTATGAGAGAGAGA
CTTTTGCTTTGACATCCTTGGAAACAGTCACAGAAGCTTTGTTGGAGATCATGGAGGCATGCATGAGAGA
TATTCCAACGTGCAAGTGGCTGGACCAGTGGACAGAACTAGCTCAAAGATTTGCATTCCAATATAATCCA
TCCCTGCAACCAAGAGCTCTTGTTGTCTTTGGGTGTATTAGCAAACGAGTGTCTCATGGGCAGATAAAGC
AGATAATCCGTATTCTTAGCAAGGCACTTGAGAGTTGCTTAAAAGGACCTGACACTTACAACAGTCAAGT
TCTGATAGAAGCTACAGTAATAGCACTAACCAAATTACAGCCACTTCTTAATAAGGACTCGCCTCTGCAC
AAAGCCCTCTTTTGGGTAGCTGTGGCTGTGCTGCAGCTTGATGAGGTCAACTTGTATTCAGCAGGTACCG
CACTTCTTGAACAAAACCTGCATACTTTAGATAGTCTCCGTATATTCAATGACAAGAGTCCAGAGGAAGT
ATTTATGGCAATCCGGAATCCTCTGGAGTGGCACTGCAAGCAAATGGATCATTTTGTTGGACTCAATTTC
AACTCTAACTTTAACTTTGCATTGGTTGGACACCTTTTAAAAGGGTACAGGCATCCTTCACCTGCTATTG
TTGCAAGAACAGTCAGAATTTTACATACACTACTAACTCTGGTTAACAAACACAGAAATTGTGACAAATT
TGAAGTGAATACACAGAGCGTGGCCTACTTAGCAGCTTTACTTACAGTGTCTGAAGAAGTTCGAAGTCGC
TGCAGCCTAAAACATAGAAAGTCACTTCTTCTTACTGATATTTCAATGGAAAATGTTCCTATGGATACAT
ATCCCATTCATCATGGTGACCCTTCCTATAGGACACTAAAGGAGACTCAGCCATGGTCCTCTCCCAAAGG
TTCTGAAGGATACCTTGCAGCCACCTATCCAACTGTCGGCCAGACCAGTCCCCGAGCCAGGAAATCCATG
AGCCTGGACATGGGGCAACCTTCTCAGGCCAACACTAAGAAGTTGCTTGGAACAAGGAAAAGTTTTGATC
ACTTGATATCAGACACAAAGGCTCCTAAAAGGCAAGAAATGGAATCAGGGATCACAACACCCCCCAAAAT
GAGGAGAGTAGCAGAAACTGATTATGAAATGGAAACTCAGAGGATTTCCTCATCACAACAGCACCCACAT
TTACGTAAAGTTTCAGTGTCTGAATCAAATGTTCTCTTGGATGAAGAAGTACTTACTGATCCGAAGATCC
AGGCGCTGCTTCTTACTGTTCTAGCTACACTGGTAAAATATACCACAGATGAGTTTGATCAACGAATTCT
TTATGAATACTTAGCAGAGGCCAGTGTTGTGTTTCCCAAAGTCTTTCCTGTTGTGCATAATTTGTTGGAC
TCTAAGATCAACACCCTGTTATCATTGTGCCAAGATCCAAATTTGTTAAATCCAATCCATGGAATTGTGC
AGAGTGTGGTGTACCATGAAGAATCCCCACCACAATACCAAACATCTTACCTGCAAAGTTTTGGTTTTAA
TGGCTTGTGGCGGTTTGCAGGACCGTTTTCAAAGCAAACACAAATTCCAGACTATGCTGAGCTTATTGTT
AAGTTTCTTGATGCCTTGATTGACACGTACCTGCCTGGAATTGATGAAGAAACCAGTGAAGAATCCCTCC
TGACTCCCACATCTCCTTACCCTCCTGCACTGCAGAGCCAGCTTAGTATCACTGCCAACCTTAACCTTTC
TAATTCCATGACCTCACTTGCAACTTCCCAGCATTCCCCAGGAATCGACAAGGAGAACGTTGAACTCTCC
CCTACCACTGGCCACTGTAACAGTGGACGAACTCGCCACGGATCCGCAAGCCAAGTGCAGAAGCAAAGAA
GCGCTGGCAGTTTCAAACGTAATAGCATTAAGAAGATCGTGTGA
(Double underline indicates bases bordering the splice junction)
TABLE 32
Primer across the junction between NF1
exon 7 and 9
Primer across the junction
GCCTGGAAAA
GA
ATGTGCAGA
between NF1 exon 7 and 9
(SEQ ID No. 75)
(Double underline indicates bases bordering the splice junction)
TABLE 33
siRNA for selectively knockdown NF1
full length and variants expression
siRNA targeting NF1 exon 8
Sense (SEQ ID No. 73) 5′ CCAGAUCCCACAGACUGAUdTdT
3′
Antisense (SEQ ID No. 74) 3′ dTdTGGUCUAGGGUGUCUGA-
CUA (5′-P)5′
siRNA targeting splice junction between
NF1 exon 7 and exon 9
Sense (SEQ ID No. 77) 5′ GGAAAA GA AUGUGCAGAAAdTdT
3′
Antisense (SEQ ID No. 78) 3′ dTdTCCUUUU CU UACACGUC-
UUU(5′-P)5′
(Double underline indicates bases bordering the splice junction)
TABLE 34
BAK1 (full length)Nucleotide Sequence
(636 nt, SEQ ID No. 79)
ATGGCTTCGGGGCAAGGCCCAGGTCCTCCCAGGCAGGAGTGCGGAGAGCC
TGCCCTGCCCTCTGCTTCTG AGGAGCAGGTAGCCCAGGACACAGAGGAGG
TTTTCCGCAGCTACGTTTTTTACCGCCATCAGCAGGAACAGGAGGCTGAA
GGGGTGGCTGCCCCTGCCGACCCAGAG ATGGTCACCTTACCTCTGCAA CC
TAGCA GCACCATGGGGCAGGTGGGACGGCAGCTCGCCATCATCGGGGACG
ACATCAACCGACGCTATGACTCAGAGTTCCAGACCATGTTGCAGCACCTG
CAGCCCACGGCAGAGAATGCCTATGAGTACTTCACCAAGATTGCCACCAG
CCTGTTTGAGAGTGGCATCAA TTGGGGCCGTGTGGTGGCTCTTCTGGGCT
TCGGCTACCGTCTGGCCCTACACGTCTACCAGCATGGCCTGACTGGCTTC
CTAGGCCAGGTGACCCGCTTCGTGGTCGACTTCATGCTGCATCACTGCAT
TGCCCGGTGGATTGCACAGAGGGGTGGCTGGGTGGCAGCCCTGAACTTGG
GCAATGGTCCCATCCTGAACGTGCTGGTGGTTCTGGGTGTGGTTCTGTTG
GGCCAGTTTGTGGTACGAAGATTCTTCAAATCATGA
(Exon 2 is indicated as double underline.)
TABLE 35
BAK1 variant (lacking exon 2) Nucleotide
Sequence (501 nt, SEQ ID No. 85).
ATGGCTTCGGGGCAAGGCCCAGGTCCTCCCAGGCAGGAGTGCGGAGAGCC
TGCCCTGCCC TCTGCTTCT GG CACCATGGG GCAGGTGGGACGGCAGCTCG
CCATCATCGGGGACGACATCAACCGACGCTATGACTCAGAGTTCCAGACC
ATGTTGCAGCACCTGCAGCCCACGGCAGAGAATGCCTATGAGTACTTCAC
CAAGATTGCCACCAGCCTGTTTGAGAGTGGCATCAATTGGGGCCGTGTGG
TGGCTCTTCTGGGCTTCGGCTACCGTCTGGCCCTACACGTCTACCAGCAT
GGCCTGACTGGCTTCCTAGGCCAGGTGACCCGCTTCGTGGTCGACTTCAT
GCTGCATCACTGCATTGCCCGGTGGATTGCACAGAGGGGTGGCTGGGTGG
CAGCCCTGAACTTGGGCAATGGTCCCATCCTGAACGTGCTGGTGGTTCTG
GGTGTGGTTCTGTTGGGCCAGTTTGTGGTACGAAGATTCTTCAAATCATG
A
(Double underline indicates bases bordering the splice junction)
TABLE 36
Primer across the junction between BAK1
exon 7 and 9
Primer across the junction
TCTGCTTCT
GG
CACCATGGG
between BAK1 exon 1 and 3
(SEQ ID No. 84)
(Double underline indicates bases bordering the splice junction)
TABLE 37 siRNA for selectively knockdown BAK1 full length and variants expression siRNA targeting exon 2 Sense (SEQ ID No. 82) 5′ GGUCACCUUACCUCUGCAAdTdT 3′ Antisense (SEQ ID No. 83) 3′ dTdTCCAGUGGAAUGGAGAC- GUU(5′-P)5′ siRNA targeting splice junction between exon 1 and exon 3 Sense (SEQ ID No. 86) 5′ CCCUCUGCUUCUGGCACCAdTdT 3′ Antisense (SEQ ID No. 87) 3′ dTdTGGGAGACGAAGACCGU- GGU (5′-P)5′ (Double underline indicates bases bordering the splice junction)
Methods of Detection
The present invention provides a method of identifying splicing variants of genes associated with prostate cancer risk and survival. The method generally comprises detecting the splicing variants in a nucleic acid sample from an individual, such as a prostate biopsy specimen. Typically, total RNA is extracted from the specimen, cDNA is synthesized from the extracted RNA and subject to further analysis. Nucleic acid samples used in the methods and assays of the present invention may be prepared by any available method or process.
Detection of splicing variants may be accomplished by amplifying specific fragments directly from a cDNA preparation from the tumor tissue using PCR. Presence of certain PCR product can be indicative of the presence of certain splicing variants, when the primers for the PCR are designed in such way that PCR products are only available when certain variants are present in the sample. Alternatively, primers may be designed to produce easily differentiable products for different variants. The sequence composition of the variants may also be determined from the amplified product.
The PCR reaction is well known in the art (See, e.g., U.S. Pat. No. 4,683,203; and U.S. Pat. No. 4,683,195). In general, the PCR procedure describes a method of gene amplification which is comprised of (i) sequence-specific hybridization of primers to specific genes within a DNA sample (or library), (ii) subsequent amplification involving multiple rounds of annealing, elongation, and denaturation using a DNA polymerase, and (iii) screening the PCR products for a band of the correct size. The primers used are oligonucleotides of sufficient length and appropriate sequence to provide initiation of polymerization, i.e. each primer is specifically designed to be complementary to each strand of the genomic locus to be amplified. The primers are prepared using any suitable method, such as conventional phosphotriester or phosphodiester methods or automated embodiments thereof (Beaucage, Tet. Lett. 22:1859-1862, 1981).
For the detection of splicing variants, primers may be designed to flank a certain exon that may be alternatively spliced, i.e., one primer is complementary to the 5′ side of the exon, and the other primer is complementary to the 3′ side of the exon. The PCR amplification products thus would show different sizes. When the exon is present, a larger amplification product is obtained. When the exon is absent, a smaller amplification product is obtained. Alternatively, a primer may be designed to be complementary to a nucleotide sequence within the exon. This way, PCR amplification product is only available when the exon is present in the specimen. Additionally, a primer may be designed to be partially complementary to the 3′ end of an exon 5′ to the alternatively spliced exon, and partially complementary to the 5′ end of an exon 3′ to the alternatively spliced exon. PCR amplification product can only be obtained when the alternatively spliced exon is present in the sample.
The polymerization agent can be any compound or system (including enzymes) which will facilitate combination of the nucleotides in the proper manner to form the primer extension products which are complementary to each nucleic acid strand. Other fundamental conditions to allow amplification include the presence of nucleoside triphosphates and suitable temperature and pH (Thigpen et al., J. Clin. Invest. 90: 799-809, 1992; Saiki et al., Science 239: 487-491, 1988).
DNA sequences of the specified gene which have been amplified by use of polymerase chain reaction may also be screened using exon oligonucleotide probes. These probes are nucleic acid oligomers, each of which are complementary to a corresponding segment of the investigated gene and may or may not contain a known variant. The assay is performed by detecting the presence or absence of a hybridization signal for the specific sequence.
Oligonucleotide Probes
Another aspect of the subject invention is to provide for variant specific nucleic acid hybridization probes capable of detecting splicing variants of genes which predispose an individual to prostate cancer. The hybridization probes of the subject invention may be derived from the disclosed nucleotide sequences of the identified variants and form stable hybrids with the target sequences, under stringent to moderately stringent hybridization and wash conditions. Stringent conditions will be used in the case of perfect complementation with the target sequence, less stringent hybridization conditions will be used if mismatches are expected among the variants. Conditions will always be chosen such that nonspecific/adventitious bindings are eliminated or minimized. The probes may be of any suitable length, which span all or a portion of the specified gene region, and which allow specific hybridization.
Nucleic acid hybridization simply involves contacting a probe and target nucleic acid (from a nucleic acid sample) under conditions where the probe and its complementary target can form stable hybrid duplexes through complementary base pairing (see U.S. Pat. No. 6,333,155). Methods of nucleic acid hybridization are well known in the art. In a preferred embodiment, the probes are immobilized on solid supports such as beads, microarrays, or gene chips.
The probes include an isolated polynucleotide, preferably attached to a label or reporter molecule, may be used to isolate other polynucleotide sequences, having sequence similarity by standard methods. Techniques for preparing and labeling probes are known in the art and disclosed in Sambrook et al. (Molecular Cloning: A Laboratory Manual, Ed. 2; Cold Spring Harbor, N.Y.: Cold Spring Harbor Laboratory, 1989) or Ausubel et al. (Current Protocols in Molecular Biology, Wiley & Sons, New York, N.Y., 1995). The labels may be incorporated by any of a number of means well known to those of skill in the art (see U.S. Pat. No. 6,333,155). Commonly employed labels include, but are not limited to, biotin, fluorescent molecules, radioactive molecules, chromogenic substrates, chemiluminescent labels, enzymes, and the like. The methods for biotinylating nucleic acids are well known in the art, as are methods for introducing fluorescent molecules and radioactive molecules into oligonucleotides and nucleotides.
Other similar polynucleotides may be selected by using homologous polynucleotides. Alternatively, polynucleotides encoding these or similar polypeptides may be synthesized or selected by use of the redundancy in the genetic code. Various codon substitutions may be introduced, e.g., by silent changes (thereby producing various restriction sites) or to optimize expression for a particular system. Mutations may be introduced to modify the properties of the polypeptide, perhaps to change ligand-binding affinities, interchain affinities, or the polypeptide degradation or turnover rate.
Probes comprising synthetic oligonucleotides or other polynucleotides of the present invention may be derived from naturally occurring or recombinant single- or double-stranded polynucleotides, or be chemically synthesized. Probes may also be labeled by nick translation, Klenow fill-in reaction, or other methods known in the art.
Other means for producing specific hybridization probes for nucleic acids include the cloning of nucleic acid sequences into vectors for the production of mRNA probes. Such vectors are known in the art and are commercially available and may be used to synthesize RNA probes in vitro by means of the addition of the appropriate RNA polymerase as T7 or SP6 RNA polymerase and the appropriate radioactively labeled nucleotides.
The nucleotide sequences may be used to construct hybridization probes for mapping their respective genomic sequences. The nucleotide sequence provided herein may be mapped to a chromosome or specific regions of a chromosome using well known genetic and/or chromosomal mapping techniques. These techniques include in situ hybridization, linkage analysis against known chromosomal markers, hybridization screening with libraries or flow-sorted chromosomal preparations specific to known chromosomes, and the like (Verma et al., Human Chromosomes: A Manual of Basic Techniques, Pergamon Press, New York N.Y., 1988).
To detect the presence of the splicing variants of genes predisposing an individual to prostate cancer, a test sample is prepared and analyzed for the presence or absence of such susceptibility alleles. Thus, the present invention provides methods to identify the expression of one of the nucleic acids of the present invention, or homolog thereof, in a test sample, using a nucleic acid probe or antibodies of the present invention. In particular, such methods comprise incubating a test sample with one or more of oligonucleotide probes of the present invention (as described above) and assaying for binding of the nucleic acid probes or antibodies to components within the test sample.
Conditions for incubating a nucleic acid probe or antibody with a test sample depend on the format employed in the assay, the detection methods used, and the type and nature of the probe used in the assay. One skilled in the art will recognize that any one of the commonly available hybridization or amplification formats can readily be adapted to employ the nucleic acid probes or antibodies of the present invention. Examples of such assays can be found in Chard, An Introduction to Radioimmunoassay and Related Techniques, Elsevier Science Publishers, Amsterdam, Netherlands, 1986; Bullock et al., Techniques in Immunocytochemistry, Academic Press, Orlando, Fla. Vol. 1, 1982, Vol. 2, 1983, Vol. 3, 1985; Tijssen, Practice and Theory of Immunoassays: Laboratory Techniques in Biochemistry and Molecular Biology, Elsevier Science Publishers, Amsterdam, Netherlands, 1985.
The test samples of the present invention include cells, protein or membrane extracts of cells, or biological fluids such as sputum, blood, serum, plasma, or urine. The test sample used in the above-described method will vary based on the assay format, nature of the detection method and the tissues, cells or extracts used as the sample to be assayed. Methods for preparing DNA extracts from any of the above samples are well known in the art and can be readily be adapted in order to obtain a sample which is compatible with the system utilized.
Gene Silencing
The phrase “gene silencing” refers to a process by which the expression of a specific gene product is lessened or attenuated. It is also used interchangeably with the term “gene knockdown.” Gene silencing can take place by a variety of pathways. Unless specified otherwise, as used herein, gene silencing refers to decreases in gene product expression that results from RNA interference (RNAi), a defined, though partially characterized pathway whereby small inhibitory RNA (siRNA) act in concert with host proteins (e.g. the RNA induced silencing complex, RISC) to degrade messenger RNA (mRNA) in a sequence-dependent fashion. The level of gene silencing can be measured by a variety of means, including, but not limited to, measurement of transcript levels by Northern Blot Analysis, B-DNA techniques, transcription-sensitive reporter constructs, expression profiling (e.g. DNA chips), and related technologies. Alternatively, the level of silencing can be measured by assessing the level of the protein encoded by a specific gene. This can be accomplished by performing a number of studies including Western Analysis, measuring the levels of expression of a reporter protein that has e.g. fluorescent properties (e.g. GFP) or enzymatic activity (e.g. alkaline phosphatases), or several other procedures.
The term “siRNA” refers to small inhibitory RNA duplexes that induce the RNA interference (RNAi) pathway. These molecules can vary in length (generally between 18-30 basepairs) and contain varying degrees of complementation to their target mRNA in the antisense strand. Some, but not all, siRNAs have unpaired overhanging bases on the 5′ or 3′ end of the sense strand and/or the antisense strand. The term “siRNA” includes duplexes of two separate strands, as well as single strands that can form hairpin structures comprising a duplex region. Designing a siRNA molecule that can specifically silence a certain gene is well known in the art, and can be routinely carried out using methods similar to what is disclosed in U.S. Pat. No. 8,008,474, which is incorporated herein by reference. siRNA can be routinely introduced to cells through conventional means such as transfection.
For targeted silencing of certain splicing variant, siRNA can be designed to target a specific exon that is only present in one variant. The mRNA of the variant that include this exon will be selectively silenced. Alternatively, siRNA can be designed to target a specific exon junction, which will only exist when certain splicing event occurs. In other words, siRNA can be designed to target the junction sequence of an exon immediately 5′ to the alternatively spliced exon and an exon that is immediately 3′ to the alternatively spliced exon. This particular junction sequence would only exist in a continuous polynucleotide sequence within an mRNA when the alternatively spliced exon is lacking. | Disclosed are novel splicing variants of the genes associated with prostate cancer risk and survival, particularly splicing variants of PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1. The disclosure also relates risk assessment, detection, diagnosis, or prognosis of prostate cancer. More specifically, this disclosure relates to the detection of certain splicing variants of PIK3CD, FGFR3, TSC2, RASGRP2, ITGA4, MET, NF1 and BAK1. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation of PCT Application No. PCT/DE02/02071, filed Jun. 7, 2002, and claims priority to German Patent Application 101 28 692.1 filed Jun. 13, 2001. Both of these applications are hereby incorporated by reference herein.
BACKGROUND INFORMATION
[0002] The present invention relates to a method and a system for controlling the creep behavior of a vehicle equipped with an automated clutch.
[0003] Automated clutches are being increasingly used not only because of the added convenience they provide, but also because of the possible reduction in wear in motor vehicles.
[0004] [0004]FIG. 2 shows a schematic diagram of a power train of a motor vehicle equipped with an automated clutch as an example. The power train includes an internal combustion engine 2 , a clutch 4 , and a transmission 6 , which is connected to driven wheels (not shown) via a drive shaft 8 . Transmission 6 is an automated manual shift transmission, for example, a taper disk belt transmission having a continuously variable transmission ratio, or a conventional automatic transmission having planetary gears. A shifting device 9 , which is controllable from a selector device 10 using a selector lever 12 via a control unit 14 in a known manner, is used to actuate or shift transmission 6 . It is understood that the selector device may also have a different design, for example, as a conventional shift stick (H gate) or as a lever having jog positions for shifting up and down. Clutch 4 is a friction disk clutch, for example, of a design which is known per se, having an actuating device 16 , which may have a hydraulic, electric, electrohydraulic, or other known design.
[0005] The sensors contained in the power train, such as a pressure sensor 18 for detecting the intake pressure of engine 2 , a rotational speed sensor 20 for detecting rotational speed n M of the engine crankshaft, a sensor 22 for detecting position α of an accelerator pedal 24 , a sensor 26 for detecting the position of selector lever 12 , and an additional rotational speed sensor 28 for detecting the rotational speed of drive shaft 8 , are connected to the inputs of control unit 14 .
[0006] Control unit 14 , having a microprocessor with respective memories 29 , contains characteristic maps and programs in an essentially known manner, which control actuators, such as a load adjustment element 30 for adjusting the load of engine 2 , actuating device 16 , clutch 4 , and shifting device 9 of transmission 6 , and other consumers 31 driven directly or indirectly by the engine such as a generator, a pump, or a heating element, etc. The individual actuators may be designed in such a way that their position is immediately known in control unit 14 , for example, as stepping motors, or additional position transducers, such as position transducer 32 for detecting a parameter relevant to position s K of clutch 4 , may be provided.
[0007] A brake pedal 34 is connected, via a hydraulic line 35 , to a braking pressure control unit 36 , which is connected to vehicle brakes 38 via additional hydraulic lines. An additional electronic control unit 40 , which is connected to control unit 14 via a data line 42 , is provided for controlling brake pressure control unit 36 . The pressure in hydraulic line 35 generated by the actuation of brake pedal 34 is detected by a pressure sensor 44 connected to control unit 14 . Control unit 40 controls the brakes, for example, in an essentially known manner, in such a way that locking of a wheel is prevented (ABS system) and/or that the vehicle does not skid unintentionally (vehicle stability system). For this purpose, additional sensors (not shown) are provided, whose signals are analyzed in control unit 40 , possibly together with signals delivered by control unit 14 , so that the individual vehicle brakes and, if present, load adjustment element 30 , may be triggered as needed. The distribution of hardware and software between devices 14 and 34 , as well as the connections of the sensors and actuators are adapted to the particular conditions.
[0008] The design and function of the above-described system are essentially known and will therefore not be described in detail. Depending on the driver's intent communicated via accelerator pedal 24 and the intent of selecting a driving program or a driving direction communicated via selector lever 12 , load adjustment element 30 , actuating device 16 , and shifting device 9 are actuated in a mutually coordinated manner as a function of the signals delivered by the sensors in such a way that comfortable and/or economical driving results.
[0009] A characteristic curve, for example, which determines a setpoint position of clutch 4 set by actuating device 16 as a function of the torque to be transmitted by clutch 4 is stored in the memory of control unit 14 to actuate clutch 4 . For reasons of control quality, clutch wear, and power consumption of the actuating device, the clutch torque to be transmitted at a given time should not exceed the absolutely necessary value. The required torque to be transmitted results from the driver's intent, i.e., the position of accelerator pedal 24 and, for example, from the load on internal combustion engine 2 , detected by sensor 18 , and possibly from additional operating parameters such as the rotational speed of engine 2 , etc.
[0010] The characteristic curve stored in control unit 14 , which provides the desired path of the clutch's final control element moved by actuating device 16 as a function of the calculated torque to be transmitted, has a decisive influence on comfortable start and comfortable shifting. The characteristic curve changes in the short-term due to temperature changes, for example, and in the long-term over the lifetime of the clutch due to wear, for example. It is, therefore, constantly updated, i.e., readjusted, according to a wide variety of strategies, to the prevailing operating conditions.
[0011] One important function which is made possible by an automated clutch is the vehicle creep, which makes it possible for the vehicle to move slowly when a forward or reverse gear is selected and the engine is running, without actuating the accelerator pedal. The driver is thus able to maneuver the vehicle more easily by operating only the brake pedal to stop the creeping vehicle. In creeping, the clutch is controlled in general in such a way that it is engaged as long as it transmits a certain creep torque, for example, 10 Nm. This creep torque is controlled, for example, by control unit 14 slowly engaging clutch 4 using actuating device 16 with the transmission in gear and the gas pedal not actuated, while engine 2 is controlled via load adjustment element 30 of engine 2 at, as far as possible, a constant speed of engine 2 in such a way that it generates the predefined torque on the clutch. It is understood that the power consumption of any additional consumers driven by the engine is taken into consideration.
[0012] One peculiar feature of the known creep behavior of vehicles is that the driver is not able to directly influence the creep, which impairs comfort and requires a high degree of skill from the driver when, for example, he must maneuver on a sloping roadway.
BRIEF SUMMARY OF THE INVENTION
[0013] An object of the present invention is to provide a method and a system for controlling the creep behavior of a vehicle equipped with an automated clutch, in which it is possible to further enhance comfort in creep operation.
[0014] The present invention provides a method for controlling the creep behavior of a vehicle equipped with an automated clutch, wherein the actuation of a brake actuating element is detected and a creep parameter influencing the creep, whose magnitude influences the actuating position of the clutch, is modified when the brake actuating element is increasingly actuated in such a way that the extent of creep is reduced.
[0015] Using the method according to the present invention, it is achieved that the driver is able to directly influence the position of the clutch and thus the creep behavior by actuating the brake, so that the creep torque transmitted by the clutch during creep states may vary within broad limits. Furthermore, the clutch is spared, because the creep torque is weakened with increasing actuation of the brake, and the clutch, i.e., the engine, does not work entirely against the actuated brakes.
[0016] The present invention also provides a system for controlling the creep behavior of a vehicle equipped with an automated clutch, containing sensors for detecting operating parameters of a vehicle engine, a sensor for detecting an operating state of a vehicle braking device, a power adjustment actuator for controlling the power output of the engine, a clutch actuator for controlling the clutch, a brake actuating element, and an electronic control device having memory devices and a microprocessor, connected to the sensors and actuators, the control device controlling the actuators according to the analysis of the sensor signals for carrying out the method according to the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The present invention is elucidated below on the basis of the schematic drawing used as an example and further details.
[0018] [0018]FIG. 1 represents a flow chart for elucidating a creep strategy, and
[0019] [0019]FIG. 2 represents a schematic drawing, described previously, of a prior art vehicle power train having a controller.
DETAILED DESCRIPTION
[0020] As an example, the present invention is elucidated below using a power train designed as in FIG. 2 described previously.
[0021] A characteristic curve which provides the setpoint value of a creep parameter KP S as a function of a brake actuation parameter B, i.e., KP S =f(B), is stored in control unit 14 . Creep parameter KP is a variable which defines the “extent of creep” of the vehicle. Function f is such that KP S decreases as brake actuation B increases, i.e., when the brake is not being actuated, the vehicle creeps strongly by itself, and the extent of creep diminishes with increased brake actuation in that, for example, the clutch is gradually disengaged or the engine is controlled in such a way that its torque is reduced.
[0022] The measure of brake actuation B may be given, for example, by pressure p detected by sensor 44 or by a force with which the brake pedal is actuated or the path by which the brake pedal is displaced (the corresponding sensors are not shown in the drawing). Taking the force on the brake pedal or the path of actuation of the brake pedal as the variable describing the brake actuation is advantageous in electronic or electric brake systems where, like in electronic gas pedals, actuation of the brake itself is separated from the operation of the brake pedal. The actuation of a hand brake lever, not shown, may also be used as a variable describing the brake actuation.
[0023] The creep parameter describing the creep behavior of the vehicle may be of different types. For example, the creep torque transmitted by clutch 4 may be used as the creep parameter, the engine then being kept at a constant speed using, for example, an idling control device (not shown), and the clutch being controlled by actuating device 16 in such a way that it transmits the torque predefined by the brake actuation. The torque that is transmitted when the brake is not actuated may be defined by a value such that the vehicle creeps forward even if it is standing on an upward slope.
[0024] It is particularly advantageous if the vehicle speed is used as the creep parameter, which, to be measurable with sufficient accuracy even at very low speeds, is advantageously detected by a sensor which detects the rotation of an input shaft of transmission 6 . This rotation is convertible directly into the vehicle speed if the transmission ratio of the transmission is known. Rotational speed sensor 28 , which in FIG. 2 detects the rotational speed of output shaft 8 of the transmission, may then be omitted and is replaced by a corresponding sensor which detects the rotational speed of the input shaft of transmission 6 . Because of the higher speed of the transmission input shaft compared to the rotational speed of the vehicle's wheels, it is advantageous to detect the speed of the transmission input shaft rather than using the wheel speed sensors usually present in vehicles equipped with ABS systems.
[0025] An example of the creep control by the driver is elucidated on the basis of FIG. 1.
[0026] Initially, it is determined in step 50 whether the vehicle is in the creep mode. The creep mode is defined, for example, by the fact that the engine is running, gas pedal 24 is not being actuated, and the forward gear having the highest transmission ratio or the reverse gear is engaged.
[0027] If the vehicle is in the creep mode, it is determined in step 52 whether clutch 4 , i.e., engine 2 , is controlled in such a way that instantaneous creep parameter KP i is greater than, for example, setpoint creep parameter KP S dependent on the actuation of brake pedal 34 (the pressure detected by sensor 44 , for example) plus a value Δ which is advantageous for the control, i.e., whether the condition
KP i >KP s +Δ
[0028] is met. If this is the case, in step 54 the clutch is gradually disengaged and/or the engine torque is reduced, so that KP i is reduced by a predefined value, for example. The system then jumps back to step 50 .
[0029] If it is determined in step 52 that the condition is not met, it is determined, in step 54 , whether the condition KP i <KP s −Δ is met. If this is the case, KP i is increased in step 56 , and the system jumps to step 50 . If it is determined in step 54 that the condition checked there is not met, engine and/or clutch control is maintained in step 58 , whereupon the system jumps to step 50 . If it is determined in step 50 that the creep mode is no longer present, for example, due to the fact that the accelerator pedal has been actuated, the neutral gear has been selected, or, for example, the brake pedal has been actuated using a force greater than the threshold value, the system jumps to end step 60 , where the creep mode is terminated.
[0030] A simple function KP i =f(B) reads, for example:
v setpoint =(( B max −B )/ B max )× v max for B<B max and
v setpoint =0 for B>B max .
[0031] Here, v max is the maximum creep speed (the brakes not being actuated). If brake actuation B exceeds the value B max , the creep speed should be reduced to zero. The torque transmitted via the clutch is controlled by control unit 14 in such a way that the desired speed dependent on the brake actuation is quickly set without control vibrations. In this way, the vehicle exhibits a creep behavior which allows it to maneuver very comfortably under a great variety of conditions.
[0032] The above-mentioned method in which the creep speed is taken as the creep parameter has the following advantages:
[0033] The engine torque available at the clutch, which is difficult to measure accurately, does not need to be determined directly.
[0034] Displacements of the clutch measuring point, which always occur, do not need to be taken into account directly.
[0035] The strategy is easily usable even on an upward slope, as long as the engine is capable of delivering sufficient torque within the controlled range, e.g., at its idling speed. Otherwise, the control range of the engine may be extended by activating not only the idling control system, but also the setting of a load adjustment element.
[0036] The above-described method according to the present invention may be modified in many ways. For example, different characteristic curves, setpoint values, and limiting values may be used for a forward and a reverse gear. | A method and system for controlling the creeping behavior of a vehicle equipped with an automated clutch ( 4 ). According to the method for controlling the creeping behavior of a vehicle equipped with an automated clutch ( 4 ), the actuation of a brake actuation element ( 34 ) is detected. In addition, a creep parameter, which influences creeping and whose magnitude influences the actuation position of the clutch ( 4 ), is modified with an increasing actuation of the brake actuation element ( 34 ) to reduce the creeping behavior. | 5 |
TECHNICAL FIELD
[0001] This disclosure generally relates to systems and methods for storing and managing nuclear spent fuel.
BACKGROUND
[0002] Spent fuel pools provide long term decay heat removal from fuel that has been recently discharged from a nuclear reactor. A recently discharged nuclear core typically represents the largest source of heat generation in a spent fuel pool. In the event of a complete loss of power to the nuclear power plant, cooling systems for the spent fuel pool may not be available to remove the fuel's decay heat. For prolonged nuclear plant station blackout conditions with recently discharged fuel, the potential exists to boil off all of the water in the spent fuel pool thereby overheating and subsequently damaging the spent fuel bundles. This may result in a radioactive release to the environment.
SUMMARY
[0003] This disclosure describes technologies related to systems, apparatus, and methods for handling, storing, and otherwise managing spent fuel rods from a nuclear reactor. In one general implementation, a spent nuclear fuel rod canister includes a submersible pressure vessel including a casing that defines an interior cavity, the casing including a corrosion resistant and heat conductive material with a thermal conductivity of above about 7.0 watts per meter per kelvin; and a rack enclosed within the interior cavity and configured to support one or more spent nuclear fuel rods.
[0004] A first aspect combinable with the general implementation further includes a first hemispherical enclosure coupled to the casing at a top end of the casing.
[0005] In a second aspect combinable with any of the previous aspects, the first hemispherical enclosure includes a radiussed interior surface that defines a top portion of the interior cavity.
[0006] A third aspect combinable with any of the previous aspects further includes a second hemispherical enclosure coupled to the casing at a bottom end of the casing,
[0007] In a fourth aspect combinable with any of the previous aspects, the second hemispherical enclosure includes a radiussed interior surface that defines a bottom portion of the interior cavity.
[0008] A fifth aspect combinable with any of the previous aspects further includes a riser that defines a fluid pathway through the riser between a top portion of the interior cavity and a bottom portion of the interior cavity.
[0009] A sixth aspect combinable with any of the previous aspects further includes an annulus defined between the riser and the casing.
[0010] A seventh aspect combinable with any of the previous aspects further includes a fuel basket positioned in the interior cavity between the riser and the bottom portion of the interior cavity.
[0011] In an eighth aspect combinable with any of the previous aspects, the fuel basket includes a spent nuclear fuel rod rack.
[0012] In a ninth aspect combinable with any of the previous aspects, the fuel basket includes a perforated support plate adjacent a bottom surface of the rack, the fluid pathway fluidly coupled to the bottom portion of the interior cavity through the perforated support plate.
[0013] A tenth aspect combinable with any of the previous aspects further includes a heat exchanger attached to the casing of the pressure vessel.
[0014] In an eleventh aspect combinable with any of the previous aspects, the heat exchanger includes at least one conduit that is at least partially disposed exterior to the casing and is in fluid communication with the interior cavity.
[0015] In a twelfth aspect combinable with any of the previous aspects, the corrosion resistant material includes a high radioactivity conduction material.
[0016] In a thirteenth aspect combinable with any of the previous aspects, the vessel is free of any radiation shielding material.
[0017] In another general implementation, a spent nuclear fuel rod management system includes a spent fuel pool containing a heat transfer liquid; and a plurality of spent fuel canisters, where each of the canisters includes a submersible pressure vessel including a casing defining an interior cavity at least partially tilled with a liquid coolant; a rack enclosed within the interior cavity; and one or more spent nuclear fuel rods supported in the rack.
[0018] In a first aspect combinable with the general implementation, the liquid coolant includes water.
[0019] In a second aspect combinable with any of the previous aspects, the heat transfer fluid includes at least one of water or ambient air.
[0020] In a third aspect combinable with any of the previous aspects, the heat removal rate of each canister is between about 0.3 MW and 0.8 MW.
[0021] In another general implementation, a method of dissipating decay heat generated by a spent nuclear fuel rod includes loading at least one spent nuclear fuel rod in a spent fuel canister that includes an inner cavity, the interior cavity at least partially filled with a fluid coolant; submerging the spent fuel canister in a heat transfer fluid contained in a spent fuel pool; transferring decay heat from the spent nuclear fuel rod to the fluid coolant; and transferring the decay heat from the fluid coolant to the heat transfer fluid in the spent fuel pool.
[0022] In a first aspect combinable with the general implementation, a rate at which heat is transferred from the spent fuel rod is at Past as great as a rate at which the spent nuclear fuel rod produces decay heat.
[0023] A second aspect combinable with any of the previous aspects further includes circulating the fluid coolant within the interior cavity of the spent fuel canister via natural circulation.
[0024] A third aspect combinable with any of the previous aspects further includes exposing an exterior surface of the spent fuel the canister to ambient air.
[0025] A fourth aspect combinable with any of the previous aspects further includes based on the exposure to ambient air, phase changing a portion of the fluid coolant from a liquid to a gas in the spent fuel canister; and phase changing the gas hack to a liquid condensate on an interior surface of the spent fuel canister based at least in part on heat transfer between the gas and the ambient air.
[0026] A fifth aspect combinable with any of the previous aspects further includes circulating at least a portion of the liquid condensate on the interior surface to a pool of the fluid coolant in a bottom portion of the canister.
[0027] In another general implementation, a method of managing spent fuel rods includes removing a first batch of spent fuel rods from a nuclear reactor; at a first time, installing the first batch of spent fuel rods in a spent fuel canister, the first batch of spent fuel rods generating decay heat at a first decay heat rate; submerging the spent fuel canister in a heat transfer fluid to remove decay heat from the first batch of spent fuel rods; removing decay heat from the first batch of spent fuel rods using the spent fuel canister for a time period at a rate greater than the first decay heat rate; at a second time subsequent to the first time, installing a second batch of spent fuel rods in the spent fuel canister, the second batch of spent fuel rods generating decay heat at a second decay heat rate greater than the first decay heat rate; and removing decay heat from the first and second batch of spent fuel rods at a rate at least as great as a sum of the first and second decay heat rates.
[0028] In a first aspect combinable with the general implementation, installing the first batch of spent fuel rods in a spent fuel canister includes installing the first batch of spent fuel rods in a spent fuel canister directly from the nuclear reactor.
[0029] A second aspect combinable with any of the previous aspects further includes removing at least a portion of the first batch of spent fuel rods; and installing the portion in a dry cask.
[0030] Various implementations described in this disclosure may include none, one, some, or all of the following features. For example, decay heat removal from spent nuclear fuel may be achieved through a canister into a pool rather than directly to a pool, thereby increasing an ease of handling of spent nuclear fuel and providing an additional safety barrier to fission product release. Further, in the case of loss of pool liquid or loss of recirculation of pool liquid (e.g., water), such as, due to a loss of power incident, decay heat removal from spent nuclear fuel may be achieved through the canister to ambient air. The decay heat removal rate may be substantially similar or identical to that achieved to the pool during normal operating conditions. In some implementations, a desired decay heat removal may be achieved without any operator action or power needed.
[0031] The details of one or more implementations of the subject matter described in this specification are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the subject matter will become apparent from the description, the drawings, and the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 is a block diagram illustrating a system of spent fuel management for a nuclear reactor systems.
[0033] FIGS. 2A-2C illustrate schematic views of an example implementation of a spent fuel canister operating in normal conditions having one stack or two stacks of spent fuel rods.
[0034] FIGS. 3A-3B illustrate schematic views of example racks fur holding spent fuel rods.
[0035] FIG. 4 illustrates a schematic view of an example implementation of a spent fuel canister operating in abnormal conditions.
[0036] FIGS. 5A-5B illustrate schematic views of an example implementation of a spent fuel canister that includes an external heat exchanger and is operating in normal conditions.
[0037] FIG. 5C illustrates a schematic view of an example implementation of a spent fuel canister t a includes an external heat exchanger and is operating in abnormal conditions.
[0038] FIGS. 6A-6B illustrate schematic views of another example implementation of a spent fuel canister that includes an external heat exchanger and is operating in normal conditions.
[0039] FIG. 6C illustrates a schematic view of another example implementation of a spent fuel canister that includes an external heat exchanger and is operating in abnormal conditions.
[0040] FIG. 7 is a flow chart illustrating an example method of dissipating decay heat generated by a spent fuel rod.
[0041] FIG. 8 is a flow chart illustrating an example method of managing spent fuel rods from a nuclear reactor system.
DETAILED DESCRIPTION
[0042] FIG. 1 is a block diagram illustrating a technique of managing spent fuel 104 from one or more nuclear reactors 152 in a nuclear reactor power system 150 . The technique involves removing spent nuclear fuel rods 104 from nuclear reactors 152 and transferring the spent fuel rods 104 to a spent fuel management system 154 that facilitates removal of residual decay heat produced by the spent fuel rods 104 . Spent fuel management system 154 includes multiple spent fuel canisters 100 submerged in a spent fuel pool 156 filled with fluid 158 . Fluid 158 provides a heat sink for receiving and dissipating the decay heat from spent fuel rods 104 . As described in detail below, canisters 100 can be configured to operate passively, e.g., without operator intervention or supervision, under both normal and abnormal emergency conditions. In some examples, canisters 100 provide a long term decay heat removal solution for spent fuel rods 104 . For example, canisters 100 can be capable of achieving a substantially constant heat removal rate (e.g., a heat removal rate of about 0.3 MW, 0.4 MW, or 0.8 MW) in various normal and abnormal operating conditions. The number of nuclear reactors 152 and canisters 100 in FIG. 1 are not indicative of any particular implementation or implementation, and are depicted for illustrative purposes only.
[0043] With respect to nuclear reactors 152 , a reactor core 20 is positioned at a bottom portion of a cylinder-shaped or capsule-shaped reactor vessel 70 . Reactor core 20 includes a quantity of nuclear fuel rods (e.g., fissile material that produces a controlled nuclear reaction) and optionally one or more control rods (not shown). In some implementations, nuclear reactors 152 are designed with passive operating systems employing the laws of physics to ensure that safe operation of the nuclear reactor 152 is maintained during normal operation or even in an emergency condition without operator intervention or supervision, at least for some predefined period of time. A cylinder-shaped or capsule-shaped containment vessel 10 surrounds reactor vessel 70 and is partially or completely submerged in a reactor pool, such as below waterline 90 , within reactor bay 5 . The volume between reactor vessel 70 and containment vessel 10 may be partially or completely evacuated to reduce heat transfer from reactor vessel 70 to the reactor pool. However, in other implementations, the volume between reactor vessel 70 and containment vessel 10 may be at least partially filled with a gas and/or a liquid that increases heat transfer between the reactor and containment vessels.
[0044] In a particular implementation, reactor core 20 is submerged within a liquid, such as water, which may include boron or other additives, which rises into channel 30 after making contact with a surface of the reactor core The upward motion of heated coolant is represented by arrows 40 within channel 30 . The coolant travels over the top of heat exchangers 50 and 60 and is drawn downward by density difference along the inner walls of reactor vessel 70 thus allowing the coolant to impart heat to heat exchangers 50 and 60 . After reaching a bottom portion of the reactor vessel, contact with reactor core 20 results in heating the coolant, which again rises through channel 30 .
[0045] Although heat exchangers 50 and 60 are shown as two distinct elements in FIG. 1 , heat exchangers 50 and 60 may represent any number of helical coils that wrap around at least a portion of channel 30 .
[0046] Normal operation of the nuclear reactor module proceeds in a manner wherein heated coolant rises through channel 30 and makes contact with heat exchangers 50 and 60 . After contacting heat exchangers 50 and 60 , the coolant sinks towards the bottom of reactor vessel 110 in a manner that induces a thermal siphoning process. In the example of FIG. 1 , coolant within reactor vessel 70 remains at a pressure above atmospheric pressure, thus allowing the coolant to maintain a high temperature without vaporizing (e.g., boiling).
[0047] As coolant within heat exchangers 50 and 60 increases in temperature, the coolant may begin to boil. As the coolant within heat exchangers 50 and 60 begins to boil, vaporized coolant, such as steam, may be used to drive one or more turbines that convert the thermal potential energy of steam into electrical energy. After condensing, coolant is returned to locations near the base of heat exchangers 50 and 60 .
[0048] FIGS. 2A-2C illustrate schematic views of an example implementation of a spent fuel canister 200 operating in normal conditions having one stack or two stacks of spent fuel rods. Canister 200 includes a submersible vessel 202 that contains spent fuel rods 204 and coolant 206 surrounding the spent fuel rods 204 . As shown schematically in FIG. 2A , canister 200 (filled to a coolant level 201 ) is supported in a spent fuel pool 256 filled with fluid 258 (e.g., water or some other suitable coolant). In some implementations, the fluid 258 in spent fuel pool 256 (filled to fluid level 203 ) is continuously or intermittently circulated by pumps or other hardware to improve heat transfer between vessel 202 and the fluid 258 . Circulation of the fluid 258 , in some aspects may increase the effectiveness of convective heat transfer between the canister 200 and the fluid 258 .
[0049] Vessel 202 , in the example implementation, facilitates the dissipation of decay heat from multiple spent fuel rods 204 . in this example, vessel 202 is an elongated capsule-shaped container, having a cylindrical main body with two elliptical or hemispherical heads on either end (e,g., the top head 205 and the bottom head 207 ). The shape of vessel 202 , in this example provides a relatively large amount of available surface area (e.g., relative to the available volume) to facilitate convective heat transfer with both the coolant 206 contained within the vessel 202 and the fluid 258 surrounding the vessel 256 in the spent fuel pool 256 . The shape of the vessel 202 also may facilitate gravity driven natural circulation of the contained coolant 206 . In some examples, vessel 202 defines an outer diameter of between about 7 and 12 ft. and a length of about 72 D. In some examples, vessel 202 defines a surface area of about 1600 ft. 2 Vessel 202 can be sized to lengths and diameters that can be accommodated in typical commercial nuclear spent fuel pools (e.g., 30 to 50 ft. in length).
[0050] Vessel 202 , in this example, is hermetically sealed and capable of pressurization to a specified design limit (e.g., 400-500 psia). As discussed below, the design limit pressure of vessel 202 may be particularly significant to vessel heat removal in abnormal operating conditions. The cylindrical shell 208 of vessel 202 , in this example, is a thin-walled construction fashioned from a corrosion resistant and heat conductive material (e.g., steel). In general, cylindrical shell 208 conducts heat and withstands pressure, thermal, radiation, and seismic induced stresses. The cylindrical shell 208 can be fabricated using materials approved for use in nuclear reactor pressure vessels. For example, in some implementations, cylindrical shell 208 includes a steel base material such as SA302 GR B, SA533 GR B, Class 1, SA 508 Class 2, or SA 508 Class 3 that may be clad with TYPE 308L, 309L TYPE 304 austenitic stainless steel. Other base materials can be implemented such as 161MnD5, 20MnMoNi55, 22NiMoCr3 7, 15Kh2MFA(A), 15Kh2NMFA(A) with Sv 07Kh25N13 and/or Sv 08Kh19N10G2B austenitic cladding. In some examples, cylindrical shell 208 does not provide any shielding to block or otherwise inhibit potentially harmful radiation generated by spent fuel rods 204 . However, in some other examples, cylindrical shell 208 is provided with radiation shielding. Cylindrical shell 208 can be fabricated using rolled plate or ring forgings. The wall thickness of cylindrical shell 208 can be between about 1.5 and 4.5 inches. In any event, the material and thickness of cylindrical shell 208 provides sufficient strength to withstand stresses associated with the design limit pressurization.
[0051] Spent fuel rods 204 are secured in place near the bottom of vessel 202 inside the riser channel 216 and supported by a lower support plate 214 (e.g., as also shown in FIG. 29 ) and lower support structure 211 . As shown, the lower support plate 214 and riser channel 216 form a “basket” which cradles spent fuel rods 204 and facilitates natural circulation of coolant 206 . In this example, fuel barrel support/shield 210 includes a fuel barrel and radiation shield that supports a plurality of individual racks 212 . It is attached to lower support plate 214 and channel riser 216 . Channel riser 216 is supported by upper support ring 218 and upper support structure 213 . Racks 212 receive respective spent fuel rods 204 and maintain them in a relatively stable, e.g., non-critical, condition. For example, racks 212 can he fashioned from a material that includes a neutron absorber (e.g., boron) to inhibit criticality events. FIG. 2A shows a single stack of spent fuel 204 whereas FIG. 2C shows a double stack of spent fuel 204 .
[0052] FIG. 3A shows a first example fuel barrel support/shield structure 310 a with a particular number (e.g., 37) of available racks 312 a to accommodate respective spent fuel rods. FIG. 3B shows a second example fuel barrel support/shield structure 310 b with another number (e.g., 97) of fuel accommodating racks 312 b. Support structure 310 b is significantly larger than support structure 310 a, and therefore may require a larger vessel. For example, support structure 310 a can be incorporated in a vessel having a 7 ft. outer diameter, while support structure 310 b can be incorporated in a vessel having a 12 ft. outer diameter. The racks can be arranged to accommodate a wide variety of fuel types such as those typical of boiling water reactors (e.g., 8×8, 9×9, or 10×10 fuel assemblies) or the larger pressurized water reactor fuel assemblies (e.g., 17×17 fuel bundles).
[0053] In these illustrations, racks 312 a and 312 b are rectilinear in cross-section defining an open area of about 11 and 28 ft 2 respectively. Of course, other suitable shapes (e.g., circular, hexagonal, triangular, etc.) sizes can also be implemented. Further, as shown, racks 312 a and 312 b are arranged in a symmetrical, tightly packed honeycomb configuration. In some examples, this geometric configuration is provided for the dual purposes of heat removal and criticality mitigation. However, other suitable configurations can also be effectively implemented. For instance, racks 312 a and 312 b can be spaced apart from one another (as opposed to tightly packed), or arranged in some other symmetrical configuration quadrilateral configuration), as opposed to a honeycomb shape.
[0054] Turning back to FIG. 2A , upper support ring 218 and lower support plate 214 forms the base of support for the riser channel 216 . In addition, lower support plate 214 may have sufficient strength to bear the weight of spent fuel rods 204 . Lower support plate 214 allows coolant 206 to flow upward past spent fuel rods 204 for convective heat transfer from the spent fuel rods 204 to the coolant. For example, lower support plate 214 can include small perforations or large openings that allow naturally circulating coolant 206 to flow up through the support plate and past spent fuel rods 204 .
[0055] The illustrated riser 216 extends upward from lower support plate 214 to surround the fuel barrel support/shield 210 and the spent fuel rods 204 supported in racks 212 . As shown, riser 216 extends from a point near the top of the lower support plate 214 to the top of the upper support ring 218 , a point that is approximately halfway to the vessel's upper head flange 219 . For example, riser 216 can have a height of about 30 ft. In some examples, riser 216 is cylindrical in shape with a rounded shaped exit, so as to reduce form losses in the naturally circulating coolant 206 .
[0056] The example riser 216 defines a hollow bore 220 that serves to direct coolant 206 upward through the interior of vessel 202 , and a narrow annulus 222 that directs coolant downward along the inner wall of vessel 202 . Upper support ring 218 peels radially inward from the cylindrical shell 208 to the top of riser 216 . Similar to support plate 214 , upper support ring 218 also includes perforations or large openings that allow naturally circulating coolant 206 to pass downward through the upper support ring 218 and through annulus 222 .
[0057] Vessel 202 may initially be filled with an amount of liquid coolant 206 . In particular, the vessel 202 is filled with at least enough coolant 206 to place the liquid level 201 above the top of the upper support ring 218 . In some examples, vessel 202 is filled with about 35 m 3 of liquid coolant 206 . The coolant can include water and/or some additional type of coolant. For instance, coolant 206 under natural circulation conditions may generate a convective heat transfer coefficient of between about 1000-2500 (W/m 2 K on the inside surface of cylindrical shell 208 . Coolant 206 can he engineered to undergo a liquid-to-gas phase change under certain conditions (e.g., when convective heat transfer to the ambient fluid 258 in the spent fuel pool 256 has significantly decreased) to maintain the heat removal rate at a substantially constant level in abnormal operating conditions, as explained in detail below.
[0058] In operating under normal conditions as shown in FIG. 2A (e.g., no loss of power or loss of fluid 258 ) vessel 202 is submerged in the spent fuel pool fluid 258 . Natural circulation of the coolant 206 inside of vessel 202 is established by the buoyancy force generated as a result of the density and elevation differences between hot coolant 206 in contact with the spent fuel 204 and cooler coolant 206 in annulus 222 . That is, when coolant 206 , in contact with the spent fuel 204 , is heated by the decay heat emanating from spent fuel rods 204 , the coolant 206 becomes less dense and begins to rise. The rising coolant 206 is directed upward through racks 212 holding spent fuel rods 204 . As the coolant 206 flows up past the spent fuel rods 204 , it receives even more heat, which makes it continue to flow upward. Riser 216 directs the heated coolant 206 upward through bore 220 , away from spent fuel rods 204 and toward the exit of the channel riser 216 near the top of the upper support ring 218 . Coolant 206 emerging from riser 216 is cooled down through convective heat transfer with the inner surface of vessel 202 . The heat is conducted through the wall of vessel 202 then transferred by convection to the spent fuel pool fluid 258 . The cooled coolant 206 becomes denser and is therefore drawn downward by gravity. The sinking coolant 206 is directed trough the perforated upper support ring 218 of support structure 210 and through annulus 222 , through the perforated lower support plate 214 and ultimately returning to the lower head 207 of vessel 202 .
[0059] FIG. 4 illustrates a schematic view of an example implementation of spent fuel canister 200 operating in abnormal conditions. In sonic implementations, spent fuel canister 200 is designed to operate in abnormal operating conditions, while maintaining a substantially constant rate of decay heat removal. In some aspects, the abnormal operating condition is an emergency situation where spent fuel pool 256 has been drained or the fluid 258 has evaporated (as shown in FIG. 4 ). However, other types of abnormal operating conditions may also occur (e.g., loss of fluid circulation in the spent fuel pool 256 ). In such abnormal operating conditions, an amount of convective heat transfer between vessel 202 and the surrounding ambient environment may be significantly reduced. The reduced rate of heat transfer ultimately causes liquid coolant 206 in contact with the spent fuel 204 to undergo a liquid-to-gas phase change. A low density, two-phase coolant mixture 206 c rises up through the spent fuel 204 and exits the top of the riser channel 216 . At the top of the riser 216 , the gas phase coolant 206 a and the liquid phase coolant 206 b separate from the two-phase coolant 206 c by gravity. The liquid phase coolant 206 b travels downward through the perforated upper support ring 218 into the annulus 222 . The gas phase coolant 206 a continues to travel upward in the vessel 202 to the upper head 205 . When the gas phase coolant 206 a comes in contact with the inside wall of the vessel 202 , it exchanges heat with the wall to produce a condensate 206 d. The condensate 206 d may be in the form of a liquid film or droplets that travel downward along the inside wail of the vessel 202 . The condensate 206 d collects in the region above the upper support ring 218 and mixes with the downward flowing liquid coolant 206 b. The condensate 206 d and the liquid phase coolant 206 b travel downward through the annulus, through the perforated lower support plate 214 and lower head 207 plenum and back upward through the spent fuel racks 212 .
[0060] In this example, the canister can transition from liquid cooling (e.g., water) to air cooling in the spent fuel pool 256 without the need for operator actions or external power. As noted above, the heat removal rate of the air cooled canister 200 may be substantially equal to that of the liquid cooled canister 200 . In particular, the liquid-to-gas phase change may cause the inner cavity of vessel 202 to pressurize. Pressurization of vessel 202 increases the saturation temperature within the vessel 202 , and thus raises the temperature of its outer surface. The increased outer surface temperature of vessel 202 increases both the thermal radiation heat transfer rate to the surroundings and the free convection heat transfer rate with the ambient air 260 (as opposed to liquid 258 in the spent fuel pool during normal operating conditions) to a point where the overall heat removal rate of canister 200 is acceptable. For example, the large surface area and high surface temperature of vessel 202 may be sufficient to remove heat from the canister 200 to the ambient air 260 at substantially the same rate as with the fuel pool fluid 258 .
[0061] FIGS. 5A-5B illustrate schematic views of an example implementation of a spent fuel canister 400 that includes an external heat exchanger 424 and is operating in normal conditions. As shown, heat exchanger 424 includes a horizontal upper tube header 223 a and a horizontal lower tube header 223 b joined together by a series of c-shaped vertical heat exchanger tubes 226 . The heat exchanger tubes can be 2 to 4 inches in diameter and 15-20 feet in length. The upper tube header 223 a, in this example, is connected to cylindrical shell 208 below the coolant level 201 and above the upper support ring 218 by header conduit 225 a. The lower tube header 223 b is connected to annulus 222 by header conduits 225 b. In some examples, header conduits 225 a and 225 b are sloped such that liquid flowing through the conduits is always in the downward direction. The heat exchanger 424 is designed to withstand hill pressure and temperatures during normal and abnormal conditions.
[0062] As shown in FIG. 5A , during normal conditions, hot liquid coolant 206 rises through the bore 220 to the outlet of the riser 216 . Approximately half of the liquid coolant 206 enters the upper header conduits 225 a into heat exchanger 424 where it transfers heat to the spent fuel pool fluid 258 . The remaining half of the liquid coolant travels through the perforated upper support ring 218 into the annulus 222 where it transfers heat to the spent fuel pool fluid 258 by convection and conduction heat transfer through the vessel 202 walls. The flow paths for the coolant 206 , in this example, are established by natural circulation created by the buoyancy force established by the density difference of the coolant in the bore 220 and the annulus 222 and the relative elevation of their thermal centers.
[0063] FIG. 5C illustrates a schematic view of an example implementation of a spent fuel canister 400 that includes an external heat exchanger 424 and is operating in abnormal conditions. In this example, although similar to that illustrated in FIG. 4 , the addition of heat exchanger 424 provides additional surface area for natural circulation cooling. Convection heat transfer inside the tubes can increase the heat removal rate capacity of the canister thereby reducing the overall height of the canister. In the present example, a sixty-five tube heat exchanger of 16 ft. tube length can reduce the canister height by at about 30% (e.g., from 72 feet to 50 feet) while rejecting the same amount of heat, 0.35 MW to the ambient air 206 . In some examples, heat exchanger 424 is a sixty-five tube heat exchanger or an approximately 150 tube heat exchanger. The number and lengths of heat exchanger tubes 226 can be selected to provide a wide range of desired heat removal rates.
[0064] FIGS. 6A-6B illustrate schematic views of another example implementation of a spent fuel canister 500 that includes an external heat exchanger 525 and is operating in normal conditions. As shown, heat exchanger 524 includes a horizontal upper tube header 223 a, a horizontal lower tube header 223 b joined together by a series of c-shaped vertical heat exchanger tubes 226 . The heat exchanger tubes can be 2 to 4 inches in diameter and 15-20 feet in length. In the illustrated example, the heat exchanger 525 is connected to cylindrical shell 208 between the level 201 and the upper support ring 218 by header conduit 225 a. The lower tube header 223 b is connected to annulus 222 by header conduits 225 b. Header conduits 225 a and 225 b are sloped such that liquid flowing through the conduits is always in the downward direction. The heat exchanger 524 , in some aspects, is designed to withstand full pressure and temperatures during normal and abnormal conditions. During normal conditions, the heat transfer mechanism may be identical or substantially similar to the same as those described for FIG. 2A .
[0065] FIG. 6C shows canister 500 operating under abnormal conditions, rejecting heat to ambient air 206 . The liquid phase coolant behaves as described previously for FIG. 4 . However, because heat exchanger 524 is connected to the gas phase region of the canister, (e.g., through riser 216 ) a portion of the gas phase coolant 206 a is condensed inside the heat exchanger tubes. This creates a low pressure region inside the tubes 526 which draws additional gas phase coolant 206 a into the tubes. The condensate 206 d inside the tubes 526 falls by gravity through the tubes 526 into the cylindrical shell. The condensate mixes with the two-phase coolant 206 c in the region above the upper support ring 218 . The liquid phase coolant 206 b travels downward by gravity through the perforated upper support ring 218 into the annulus 222 , through the perforated lower support plate 214 , through the plenum formed by the lower head 207 . It flows upward through the spent fuel racks 212 thereby cooling the spent fuel 204 .
[0066] Another implementation of the present disclosure features various methods of dissipating decay heat generated by a spent fuel rod. FIG. 7 illustrates an example method 700 for dissipating decay heat. The method includes, at step 702 , submerging a spent fuel canister in a heat transfer fluid contained in a spent fuel pool. As described above, the spent fuel canister can include a cylindrical shell defining an interior cavity which contains the spent fuel rod. At step 704 , decay heat is transferred from the spent fuel rod to liquid coolant contained within the canister. In some implementations, the coolant is circulated within the canister via natural circulation to facilitate heat transfer. At step 706 , the decay heat is transferred from the coolant, through a wall of the canister, to the heat transfer fluid of the spent fuel pool. A rate at which heat is transferred from the spent fuel rod is at least as great as orate at which the spent fuel rod produces decay heat.
[0067] Method 700 can also optionally include, at step 708 , exposing the canister to ambient air due to a loss of spent fuel pool fluid. At step 710 , based on the exposure to ambient air, a portion of the coolant inside the canister is phase changed from a liquid to a gas. At step 712 , heat is transferred, through a wall of the canister, from the gas phase coolant to the ambient air. At step 714 , the gas phase coolant is condensed back to a liquid and circulated (e.g., via natural circulation) within the canister.
[0068] Yet another implementation of the present disclosure features various methods of managing spent fuel rods by cycling them through spent fuel canisters. FIG. 8 illustrates an example method 800 for managing spent fuel rods. The method includes, at step 802 , removing a first batch of spent fuel rods from a nuclear reactor. At step 804 , the first batch of spent fuel rods is installed in a spent fuel canister (e.g., spent fuel canister 100 ) at a first time (T 1 ). At step 806 , the spent fuel canister is submerged in a heat transfer fluid (such as contained in spent fuel pool 156 ). At step 808 , the canister is used to remove decay heat from the first batch of spent fuel rods for a time period (T). At step 810 , a second batch of spent fuel rods is installed within the spent fuel canister at a second time (T 2 ). The heat removal rate of the spent fuel canister is at least as great as the combined decay heat rate of the first and second batches of spent fuel rods at T 2 . As discussed in context of the first and second examples below, the example method of FIG. 8 can be used to continuously manage spent fuel from a nuclear reactor.
[0069] In some aspects, an example spent fuel management system (e.g., spent fuel management system 154 ) that includes a spent fuel pool and multiple spent fuel canisters according to the present disclosure (e.g., spent fuel canister 100 , 200 , 400 , and/or 500 ) manages spent fuel from nuclear reactors (e.g., 1-12 nuclear reactors 152 ) each effectively refueled once every twenty-four months, with a spent fuel batch of one-half core, approximately 18 fuel assemblies being removed every two months. Each batch of spent fuel produces approximately 0.2 MW of decay power after twenty days, and 0.1 MW of decay power after six months. Spent fuel that has decayed for six months can be discharged from the spent fuel canisters into, for example, a typical liquid coolant filled, non-pressurized, spent fuel pool. After an additional period of cooling, for example 5-10 years, the spent fuel can be discharged to a dry cask. In this example, there is sufficient liquid coolant 158 in the spent fuel pool 156 to provide 20 days of cooling before transitioning to cooling by ambient air. The system includes two spent fuel canisters, each capable of achieving at least 0.5 MW of decay heat removal when fully immersed in spent fuel pool coolant 158 and 0.35 MW decay heat removal after the 20 day transition cooling period. Table 1 below illustrates an example linear sequence for canister loading and unloading to accommodate spent fuel from the nuclear reactor. In Table 1, “T” is in months and “B#” represents a particular batch of spent fuel. A “+” indicates that the batch is loaded into the canister and a “−” indicates that the batch is removed.
[0000]
TABLE 1
Canister #
T = 0
T = 2
T = 4
T = 6
T = 8
T = 10
Canister 1
+B1
+B3
−B1
0.35 MW
0.5 MW
+B5
0.5 MW
Canister 2
+B2
+B4
−B2
0.35 MW
0.5 MW
+B6
0.5 MW
Canister #
T = 12
T = 14
T = 16
T = 18
T = 20
T = 22
T = 24
Canister 1
−B3
−B5
−B7
−B9
+B7
+B9
+B11
+B13
0.5 MW
0.5 MW
0.5 MW
0.5 MW
Canister 2
−B4
−B6
−B8
+B8
+B10
+B12
0.5 MW
0.5 MW
0.5 MW
[0070] In the example sequence presented in Table 1, all of the spent fuel batches would have decayed for eight months prior to discharge. This approach, in some aspects, eliminates the potential risks associated with having higher power density spent fuel placed directly next to lower power density spent fuel. The higher power density spent fuel presents the greater risk of zirconium cladding ignition in air in the event of a loss of spent fuel pool water 158 which could potentially ignite the lower power density spent fuel.
[0071] In another example spent fuel management system, the system may manage spent fuel from nuclear reactors (e.g. 1-12 nuclear reactors 152 ) each effectively refueled once every twenty-four months, with a spent fuel batch of one-half core being removed every two months. Each batch of spent fuel provides 0.2 NM of decay power after twenty days, and 0.1 MW of decay power after six months. Spent fuel that has decayed for six months can be discharged from the spent fuel canisters into, for example, a typical liquid coolant filled, non-pressurized, spent fuel pool. After an additional period of cooling, for example 5-10 years, the spent fuel can be discharged to a dry cask. The system includes a single spent fuel canister capable of achieving at least 0.65 MW decay heat removal when fully immersed in spent fuel pool coolant 158 and 0.45 MW decay heat removal after the 20 day transition cooling period. Table 2 below illustrates a linear sequence for canister loading and unloading to accommodate spent fuel from the nuclear reactor using the larger spent fuel canister.
[0000]
TABLE 2
Canister #
T = 0
T = 2
T = 4
T = 6
T = 8
T = 10
Canister 1
+B1
+B2
+B3
−B1
−B2
−B3
0.35 MW
0.5 MW
0.65 MW
+B4
+B5
+B6
0.65 MW
0.65 MW
0.65 MW
Canister #
T = 12
T = 14
T = 16
T = 18
T = 20
T = 22
T = 24
Canister 1
−B4
−B5
−B6
−B7
−B8
−B9
−B10
+B7
+B8
+B9
+B10
+B11
+B12
+B13
0.65 MW
0.65 MW
0.65 MW
0.65 MW
0.65 MW
0.65 MW
0.65 MW
[0072] Note that this larger spent fuel canister, in some aspects, provides sufficient space to accommodate a six month discharge of the spent fuel batches.
[0073] In another example spent fuel management system, the system may manage spent fuel from a single nuclear reactor effectively refueled once every forty-eight months, with a spent fuel hatch of one-full core (e.g. 37 assemblies) being removed and replaced. Each batch of spent fuel produces 0.4 MW of decay power after twenty days and 0.2 MW of decay power after six months. Spent fuel that has decayed for six months can he discharged from the spent fuel canisters into, for example, a typical liquid coolant filled, non-pressurized, spent fuel pool. After an additional period of cooling, for example 5-10 years, the spent fuel can be discharged to a dry cask. The system includes a single spent fuel canister capable of achieving at least 0.85 MW decay heat removal when fully immersed in spent fuel pool coolant 158 and 0.6 MW decay heat removal after the 20 day transition cooling period. Table 3 below illustrates a linear sequence for canister loading and unloading to accommodate spent fuel from the nuclear reactor using the larger spent fuel canister.
[0000]
TABLE 3
Canister #
T = 0
T = 4 yrs
T = 8 yrs
T = 12 yrs
T = 16 yrs
T = 18 yrs
T = 24 yrs
Canister 1
+B1
+B2
−B1
−B2
−B3
−B4
−B5
0.7 MW
0.85 MW
+B3
+B4
+B5
+B6
+B7
0.85 MW
0.85 MW
0.85 MW
0.85 MW
0.85 MW
[0074] The use of terminology such as “front,” “back,” “top,” “bottom,” “over,” “above,” and “below” throughout the specification and claims is for describing the relative positions of various components of the system and other elements described herein. Similarly, the use of any horizontal or vertical terms to describe elements is for describing relative orientations of the various components of the system and other elements described herein. Unless otherwise stated explicitly, the use of such terminology does not imply a particular position or orientation of the system or any other components relative to the direction of the Earth gravitational force, or the Earth ground surface, or other particular position or orientation that the system other elements may be placed in during operation, manufacturing, and transportation.
[0075] A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made. For example, advantageous results may be achieved if the steps of the disclosed techniques were performed in a different sequence, if components in the disclosed systems were combined in a different manner, or if the components were replaced or supplemented by other components. Accordingly, other implementations are within the scope of the following claims. | A spent nuclear fuel rod canister includes a submersible pressure vessel including a casing that defines an interior cavity, the casing including a corrosion resistant and heat conductive material with a thermal conductivity of above about 7.0 watts per meter per kelvin; and a rack enclosed within the interior cavity and configured to support one or more spent nuclear fuel rods. | 6 |
TECHNICAL AREA
[0001] The present invention relates to an infusion device and in particular to a compact and easy to use mechanical driven infuser.
BACKGROUND OF INVENTION
[0002] For a number of years infusers have been used that provides the patient or user with the means of administering a drug in an easy way without the need for a medically trained person, such as a physician or nurse to handle the device.
[0003] One drawback with these infusers is that they have a medicament container of a certain length as well as a plunger rod acting on said medicament container for delivering a dose of medicament, also having a certain length, whereby the total length of a device has to be at least the length of the medicament container and the plunger rod. If a drive member is used, such as for instance a drive spring, the length of the device is further increased.
[0004] One way of handling this is to make at least the plunger rod shorter or not adding so much to the overall length. One solution to this is to have a flexible plunger rod, which is disclosed for example in EP 1 583 573 where the plunger rod may be bent or formed as a circle. Another solution is disclosed in EP 1 276 529 having a bendable plunger rod with a ratchet on a side surface, where the plunger rod is bent around a cogwheel, for driving the plunger rod.
[0005] The drawback with these solutions is that the length may not be increased by the whole length of the plunger rod, but at least by some amount because the circle formed by the bent plunger rod also adds to the length. Further, the dimensions of the device in other directions are increased considerably by these solutions, providing a rather bulky device.
[0006] The above mentioned solutions utilize some sort of power spring wound around a shaft or the like positioned in the centre of the circle formed by the curved plunger rod. These power springs often act directly or almost directly on the curved plunger rod, such as with the device of EP 1 276 529 where the power spring acts on the cog wheel.
[0007] The drawback with this drive solution is that it complicates the addition of functions such as activation mechanisms, constant infusion speed mechanism, automatic stop mechanisms, just to mention a few. This is mainly because the plunger rod surrounds and thereby blocks access to the plunger drive spring without enlarging the device.
[0008] Regarding the infusion speed control aspect, some solutions have been device, such as for example in EP 1 326 659 where an electric motor is utilized for driving the flexible plunger rod. Also document WO 2010/112377 discloses a device utilizing electric motors for driving and controlling the movement and speed of the plunger rod.
[0009] The drawback with this is that the device has to rely on electric power in order to deliver a dose of medicament. If any batteries used are depleted, the device cannot be used at all, which may be critical for some types of drugs.
BRIEF DESCRIPTION OF INVENTION
[0010] The aim of the present invention is to remedy the above drawbacks with the state of the art devices.
[0011] According to one major aspect of the invention the piston plunger preferably comprises a number of distinct segments being inter-connectable to each other for forming an elongated piston plunger. In this aspect it is to be noted that the segments are not connected to each other beforehand. They are each distinct separate components that can be positioned inside the device in many ways.
[0012] The segments have members that provide a connection between the successive segments such that adding and connecting of segments forms an elongated piston plunger. This provides an advantage in that the space required for the plunger rod segments is much lesser than the space required for a flexible piston plunger. The interconnection of the segments preferably provides a locking in the longitudinal direction of the piston plunger, thereby acting as if it was a solid plunger rod.
[0013] The segments may be interconnected successively during delivery of a dose of medicament, whereby a subsequent segment is put in position and inter-connected with a previous segment as the piston plunger advances during infusion. This provides the possibility of arranging the segments in a pile or stack, in turn providing as very compact and space-saving design of the piston plunger. It is of course feasible to have more than one pile or stack of segments.
[0014] In order to advance and position subsequent segments of the piston plunger, especially when placed in a stack, a force member may be provided, capable of acting on said stack of piston plunger segments for successively interconnecting piston plunger segments. The force member may then act on the whole stack or pile, pushing on the last segment to be inter-connected so that each subsequent segment is pushed into place in relation to a previous segment. The force member may be a spring member or the like being in a tensioned state before activation of the infusion and the inter-connection of the segments.
[0015] Preferably the piston plunger is threaded and cooperates with a drive nut for the advancement of the piston plunger during infusion. In this aspect, the piston plunger segments are arranged with threads, designed to interact with the drive nut connected to said mechanical drive means.
[0016] An advantageous design of the piston plunger segments regarding both piling in stacks and interacting with a drive nut, the segments have a generally rectangular cross-section and having thread segments on the corners of the rectangles.
[0017] Further, in order to have a compact mechanical drive means, it may comprise a flat spiral spring preferably arranged in a rotatable spring housing. Thereby the length of the device is not affected by the mechanical drive means acting on the piston plunger. Rather, when a rotating spring housing is provided, a compact a drive member arranged between said spring housing and said drive nut may be arranged.
[0018] The device may further comprise an infusion speed control mechanism operatively connected to said mechanical drive means if that is a requirement. Preferably the infusion speed control mechanism comprises a centrifugal brake. The advantage with this is that a purely mechanical speed control may be obtained, thereby avoiding any electrically driven solutions. A mechanical centrifugal brake is also not so space-consuming and may be made very compact. In order to provide a proper function of the centrifugal brake, a transmission may be arranged between said mechanical drive means and said centrifugal brake.
[0019] Preferably the device may further comprise a penetration mechanism, capable of extending said infusion needle into an infusion site. Thereby the user does not necessarily have to perform the penetration manually, which is an advantage for some users who do not like the concept of needles and the penetration thereof. Then a penetration performed by the device is preferable. In addition to the penetration the penetration mechanism may further be capable of retracting said infusion needle upon completion of dose delivery. Then the device is harmless after performed infusion and the risk of unintentional needle sticks is removed.
[0020] The device may further be arranged with a manually operable operation mechanism, for activating delivery of a dose of medicament, such as a turnable knob, wherein turning of the knob a certain rotational distance activates the penetration mechanism. A turnable knob is an intuitive component that a user has no problems as how to handle. The turning motion of the knob may also be advantageous in that it may easily be transferred to other components of the device for initiating and/or performing additional functions, such as activating of infusion and withdrawal of the infusion needle.
[0021] These and other aspects of, and advantages with, the present invention will become apparent from the following detailed description of the invention and from the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
[0022] In the following detailed description of the invention, reference will be made to the accompanying drawings, of which
[0023] FIG. 1 is a side view of an embodiment of the present invention,
[0024] FIG. 2 is a side view of the device of FIG. 1 turned 180 degrees,
[0025] FIG. 3 is an exploded view of the device of FIG. 1 ,
[0026] FIG. 4 is a partly exploded view of the device of FIG. 1 with the proximal housing part removed for clarity,
[0027] FIG. 5 is a partly exploded view of the device of FIG. 1 with the distal housing part removed for clarity,
[0028] FIG. 6 a is a detailed view of the piston plunger comprised in the present invention,
[0029] FIG. 6 b is a detailed view of a piston plunger segment comprised in the piston plunger according to the present invention,
[0030] FIG. 7 a is a detailed view of the piston plunger according to the invention with a spring unit and follower,
[0031] FIG. 7 b is a detailed view of a magazine to house the piston plunger,
[0032] FIG. 8 shows a partly exploded view of the device according to FIG. 1 ,
[0033] FIG. 9 shows a partly exploded view according to FIG. 8 and turned 180 degrees,
[0034] FIG. 10 shows a partly exploded view of a penetration mechanism according to one aspect of the invention,
[0035] FIG. 11 shows a further partly exploded view of the penetration mechanism,
[0036] FIG. 12 show a perspective view of the device of FIG. 1 with the distal housing part removed for clarity,
[0037] FIG. 13 shows a perspective view of the device of FIG. 1 with the proximal housing part removed for clarity,
[0038] FIG. 14 shows a view of the distal housing part and a part of an operation mechanism,
[0039] FIGS. 15 a, b show details views of a knob comprised in the present invention,
[0040] FIG. 16 shows a detailed view of a component comprised in an auto-stop mechanism,
[0041] FIGS. 17 to 29 show different functional positions of the device during use.
DETAILED DESCRIPTION OF THE INVENTION
[0042] The embodiment of an infusion device shown in the drawings comprises a housing, which may be in two housing parts 10 , 12 . It is of course feasible that it comprises more than two housing parts. Preferably, the complete housing has a generally rectangular shape having a measure or thickness as seen along a proximal-distal axis 14 that is much less than the dimensions in the other two directions, vertical 16 and horizontal 18 . The housing is arranged with an operating means, 20 in the embodiment shown as a turnable knob on the distally directed housing surface.
[0043] On the proximally directed housing surface, an opening is arranged, through which an Allen keyhole 22 is accessible, FIG. 2 . The Allen keyhole 22 is arranged on a shaft 24 , FIG. 4 , rotatably arranged inside the housing and journalled with a distal end in a seat 26 on the inner surface of the distal housing part 10 . A proximal end of the shaft 24 is arranged with a number of arms 28 that extend from a hub 30 in a generally circumferential direction. The free ends of the arms 28 are arranged with radially outwardly directed edges 32 . The hub 30 with the arms 28 is intended to fit into a seat 34 , FIG. 5 , on the inner surface of the proximal housing part 10 . The seat 34 is surrounded by an annular ledge 36 having radially inwardly directed teeth 38 of a certain configuration. The teeth 38 are intended to cooperate with the free ends of the arms 28 as will be described.
[0044] The shaft 24 is further arranged with a slit 40 , FIGS. 4 and 5 , along its length. Further, around the shaft 24 is a flat spiral spring 42 , FIG. 4 , wound, wherein the inner end of the spiral spring 42 fits into the slit 40 , thereby locking the spring 42 to the shaft 24 . The spring 42 is further arranged inside a spring housing 44 designed as a generally tubular part. The inner surface of the tubular part is arranged with a locking segment 46 , FIG. 4 , into which an outer end of the spiral spring 42 fits, thereby locking the spiral spring 42 to the spring housing 44 . The spring housing 44 is further arranged with a sidewall 48 , FIG. 5 , having a central opening 50 , through which the shaft 24 can extend. On the outer circumferential surface of the spring housing 44 a ratchet 52 is arranged. The ratchet 52 is intended to cooperate with a cogwheel 54 of a drive member 56 , where the cogwheel 54 preferably is bevelled. The drive member 56 comprises a shaft 56 where the cogwheel 54 is attached to one end such that the shaft 56 extends generally in the radial direction of the spring housing 44 as seen in FIG. 4 along line 58 . The shaft 56 is journalled in the proximal housing part 10 by support members 60 , FIG. 5 . A second cogwheel 62 is arranged at the second end of the shaft 56 , FIG. 5 . The second cogwheel 62 is arranged to be in contact with teeth 64 of a drive nut 66 , where the teeth 64 extend around the circumference of the drive nut 66 . The drive nut 66 is further arranged with a central opening 68 , FIG. 4 , which opening 68 is arranged with threads 70 . The threads 70 of the drive nut 66 are intended to interact with a threaded piston plunger 72 . The spring housing 44 is further arranged with indicia or markings 73 , FIG. 5 , in the embodiment shown a series of curved lines on the outer surface of the sidewall 48 . These markings 73 are visible in a window or opening 75 on the distal housing part FIG. 1 , as will be explained below.
[0045] In the embodiment shown the piston plunger is of a certain configuration, FIG. 6 a, b . The piston plunger generally has a rectangular configuration as seen in a cross-sectional view. Each corner of the rectangular piston plunger 72 is arranged with thread segments 74 . Further the piston plunger is divided up into a number of piston plunger segments. The end of the first piston plunger segment 76 that is to be in contact with a medicament container 78 , FIG. 3 , is arranged with a generally circular pusher plate 80 having a diameter somewhat less than the inner diameter of the medicament container. The first piston plunger segment 76 has a certain length. The following piston plunger segments 82 , FIG. 6 a, are somewhat shorter. All piston plunger segments are arranged with connection members that comprise generally vertically arranged cut-outs 84 at their distal ends. The side walls 86 of the cut-outs 84 are arranged with generally vertically directed grooves 88 , having a certain configuration. Further, each piston plunger segment apart from the first segment, is arranged with a proximally directed nose 90 designed to fit into the cut-out 84 of a previous plunger segment 82 . Further the nose 90 is arranged with generally vertically extending ledges 92 having similar configuration as the grooves 88 of the cut-out 84 , whereby the ledges 92 may fit into the grooves 88 as seen in FIG. 6 b.
[0046] The piston plunger segments 82 are arranged in a generally vertical stack on top of each other and directed such that the corners with the thread segments extend generally horizontally, FIG. 7 a . The stack of piston plunger segments is held in place inside the housing by a magazine 94 providing side supports on three sides. The fourth side is arranged with an elongated slit 96 , FIG. 7 b . In the slit a flat band spring 98 is arranged having a first upper end attached to a fixture post 100 on the magazine 94 , FIG. 7 a . The second lower end is attached to a piston plunger follower 102 inside that magazine 94 , FIG. 7 a . The function of the described components will be explained below.
[0047] The proximal end of the piston plunger 72 extends into a space in the device intended to accommodate the medicament container 78 , FIG. 8 . The space is accessible via a hingedly attached lid 104 , FIG. 1 , on an upper area of the housing. Inside the space a holder or cartridge retainer 106 , FIG. 3 , 11 , is arranged, on which the medicament container may be placed. The cartridge retainer 106 is arranged slidable in a longitudinal direction inside the housing guided by its longitudinal edges 108 , FIGS. 8 and 9 , fitting into guides 110 on each housing part, FIG. 8 . Further a cogwheel segment 111 of a cartridge cam 112 , is turnably attached to posts 114 , FIG. 9 , on the proximal housing part 12 . An upper surface of the cartridge cam 112 is arranged with a curved ridge 116 , FIG. 9 , which ridge cooperates with downwardly directed protrusions 118 on the underside of the cartridge retainer 106 . The cogwheel segment 111 of the cartridge cam 112 is further connected to a ratchet segment 120 , FIG. 9 , arranged on an outer surface of the operation member 20 , in the embodiment shown a turnable knob. The function of the knob and the cartridge cam will be explained in detail below.
[0048] The cartridge retainer 106 is further arranged with an end piece 122 , FIG. 9 , which is intended to be in contact with an end of the container 78 , comprising a septum (not shown). The end piece 122 is further arranged with a hollow needle piece 124 , FIG. 9 , intended to pierce the septum of the container, as will be described. The needle piece 124 extends through the end piece and is further provided with a bend of generally ninety degrees. At the lower end of the needle piece, a first end of a flexible tube 126 (not shown) is attached. Further, a second end of the flexible tube is attached to a distal end of an infusion needle 128 , FIG. 10 . The infusion needle is attached to a generally cylindrical needle hub 130 , which in turn is positioned inside a generally cylindrical needle plunger 132 . The needle plunger 132 is in turn positioned inside a generally tubular guide piece 134 , being a part of the proximal housing part 10 . A lower end of the guide piece is open towards the proximal direction and the opening is arranged with a ruptable membrane 136 . The needle plunger 132 is further arranged with transversally extending arms 138 , FIGS. 10 and 11 . Each arm is arranged with a chamfered side surface 140 , which chamfered surfaces 140 are intended to cooperate with ledges 142 , FIG. 5 , on an inner surface of the knob 20 . The needle plunger 132 is urged in the distal direction by a spiral spring 143 acting between the transversal arms 138 and the inner surface of the proximal housing part, FIG. 10 .
[0049] The device is further arranged with an infusion speed control mechanism 144 , that preferably is capable of providing a constant infusion speed during the infusion. It comprises a transmission, FIGS. 12 and 13 , with a first cogwheel 146 , FIG. 12 , with a small diameter acting on the ratchet 52 on the outer surface of the spring housing 44 . The first cogwheel 146 is attached to a second cogwheel 148 having a larger diameter, wherein the first and second cogwheels 146 , 148 are rotatably arranged to a first shaft 150 . The second cogwheel 148 is in engagement with a third cogwheel 152 having a smaller diameter. The third cogwheel 152 is attached to a fourth cogwheel 154 having a larger diameter. The third and the fourth cogwheel 152 , 154 are rotatably arranged to a second shaft 156 . The fourth cogwheel is then in engagement with a fifth 158 cogwheel having a smaller diameter, FIG. 13 . The fifth cogwheel 158 is attached to a sixth cogwheel 160 having a larger diameter. The fifth and the sixth cogwheels 158 , 160 are rotatably arranged to a third shaft 162 . The sixth cogwheel 160 is in engagement with a seventh cogwheel 164 . The seventh cogwheel 164 is attached to a centrifugal brake 166 , comprising a number of arms 168 attached to a hub 170 , FIG. 12 , where the seventh cogwheel 164 and the hub 170 are rotatably arranged to a fourth shaft 172 . The arms 168 of the centrifugal brake 166 extend generally in circumferential direction, having their free ends becoming trailing ends when the hub rotates. The outer surfaces of the arms 168 are arranged with ledges 174 . The hub 170 with its arms 168 is positioned in a generally tubular piece 176 attached to the inner surface of the distal housing part 12 . The diameter of the tubular piece 176 is chosen such that there is a small gap between the ledges 174 of the arms 168 and the inner surface of the tubular piece 176 when the hub 170 is not rotating. The centrifugal brake 166 is further arranged with transversally extending arms 178 attached to the hub 170 . The free ends of the arms 178 are arranged with end pieces 180 , FIG. 14 , extending generally perpendicular to the extension of the arms 178 .
[0050] The device is further arranged with an operation mechanism 182 . The operation mechanism 182 comprises the previously mentioned knob 20 , FIG. 14 . Further, it comprises a start linkage 184 designed with an arm 186 attached to a cylindrical hinge 188 fitting into a post 190 in the proximal housing part 10 . The arm 186 extends towards and into the knob 20 . At the end of the arm a contact surface 192 is arranged, which is intended to interact with a protrusion 194 inside the knob 20 , as will be explained. Further the arm 186 of the start linkage 184 is arranged with a branch 196 extending towards the centrifugal brake 166 , and intended to interact with the end pieces 180 of the transversal arms 178 of the hub 170 . At an inner end of the arm 186 a spring element 198 is arranged.
[0051] The operation mechanism is further arranged with a movement member arranged as a spring 200 provided with two arms 202 , 204 , each in turn arranged with an end piece 206 , 208 directed generally perpendicular to the arms 202 , 204 . The first end piece 206 of the spring is attached to the distal housing part, FIG. 12 . The second end piece is in an initial position held by a hook 210 , FIG. 12 , adjacent the opening in the distal housing part intended for the knob 20 . When the knob is operated during use, as will be described, the second end piece will fit into a seat 212 in a generally radially protruding ledge 214 attached to the knob, FIG. 15 .
[0052] The device is further arranged with an auto-stop mechanism 216 , FIG. 11 . It comprises a beam 218 provided with a proximal end 220 , FIG. 15 . The proximal end 220 is arranged with a downwardly directed ledge 222 , intended to be in sliding contact with a curved surface 224 , FIG. 12 , on the inner surface of the proximal housing part 10 . Further a flexible arm 226 is arranged on a side surface of the beam 218 , the arm 226 being flexible in the proximal-distal direction 14 . The arm 226 is arranged with a distally directed ledge 228 , the ledge being provided with a bevelled surface 230 . The arm 226 and the ledge 230 are arranged to come in contact with a proximally directed protrusion 232 on the knob 20 , FIG. 15 . The protrusion of the knob is also arranged with a bevelled surface 234 , intended to interact with the bevelled surface 230 of the arm 210 of the beam 202 , as will be explained. Further, the proximal part of the beam 218 is arranged with an arm 236 extending from the underside of the beam 218 and towards the spring housing 44 as seen in FIG. 13 . The free end of the arm 236 is arranged with a downwardly directed protrusion 238 , which protrusion 238 is intended to interact with a groove 240 , FIGS. 4 and 13 , arranged on the outer surface of the spring housing 44 , as will be explained.
[0053] The beam 218 is arranged with a distal part 242 being directed more upwards than the proximal part as seen in FIG. 12 , giving the beam a curved shape as seen in the proximal direction of the device. The upper end 244 of the distal end of the beam 218 is positioned adjacent the drive nut 66 and the piston plunger 72 , FIG. 12 , for reasons that will be explained below.
[0054] Intended Function of the Device
[0055] The device is usually delivered without a medicament container. Thus, before use, a medicament container 78 has to be inserted into the device. The lid 104 at the upper end of the device is then opened, FIG. 17 , whereby the space and the cartridge retainer 106 are accessible. The medicament container 78 is then inserted with a neck portion towards the end piece 122 of the cartridge retainer 106 . The lid is then closed.
[0056] The device is now made ready. This may be done by inserting an alien key into the hole 22 on the proximal surface of the device and turning the shaft 24 in the anti-clockwise direction. This causes the arms 28 of the hub 30 to slide over the teeth 38 because of the direction of the arms in relation to the teeth. Because the inner end of the spiral spring is attached to the turning shaft 24 the spiral spring is tensioned. When the user stops turning the shaft, it is locked against rotating back because of the edges 32 of the arms now locking against the teeth 38 . The device is now ready for delivering a dose of medicament.
[0057] In the initial position, the knob is in the rest or delivery position as seen in FIG. 17 . In this position, as seen in FIG. 128 , the ratchet segment 120 of the knob 20 is not yet in engagement with the cartridge cam. The contact surface 192 of the operation mechanism 182 is on the inner surface of the knob, unaffected. As seen in FIG. 19 , this position of the operation mechanism causes the branch 196 to be in the path of the end pieces 180 of the arms 178 of the hub 170 , whereby rotation of the hub 170 of the constant speed control mechanism 144 is prevented. The process up to this point may be done without the device being in contact with the patient. In order to be able to deliver a dose of medicament to the patient, the proximal surface of the device has to be in contact with some part of the body of the patient, i.e. to releasibly attach the device to the body. This may be performed in many ways, by straps, by merely pressing it manually, but preferably the proximal surface is arranged with some sort of adhesive, like sticky tape, with which the device may be fastened to the body. One variant is to have double-sided sticky tape on the proximal surface with an outer protective layer that is peeled off before attachment.
[0058] When the device is activated, the user initially turns the knob to the first position, as seen in FIG. 1 , displaying the pause sign. This turning of the knob causes its ratchet segment 120 to engage the cogwheel segment 111 of the cartridge cam, whereby the cartridge cam is turned around its contact point with the proximal housing part. The turning of the cartridge cam causes in turn the curved ridge 116 to act on the protrusions 118 of the cartridge retainer 106 , causing the cartridge container 106 to be moved linearly, guided by the guides for the cartridge retainer 110 , such that the end piece 122 is moved towards, and in contact with, the neck portion of the medicament container 78 . The medicament container 78 is in turn held in longitudinal position by the proximal end of the piston plunger 72 with the pusher plate 80 being in contact with the stopper of the medicament container. The movement of the end piece causes the needle piece 124 to penetrate the septum of the medicament container, thereby creating a passage for the medicament through the septum. The medicament can now flow into the flexible tube and to the infusion needle.
[0059] The turning of the knob also initiates the penetration by the infusion needle. The ledges 142 on the inner surface are inclined, as seen in FIG. 20 and in FIG. 15 , and the chamfered surfaces 140 of the transversal arms 138 of the needle plunger 132 , will slide on these inclined surfaces, whereby the needle plunger 132 is pushed in the proximal direction against the force of the needle plunger spring 143 . The infusion needle will rupture the membrane 136 and extend out of the device as shown in FIG. 20 .
[0060] Initiation of Infusion
[0061] In order to start the infusion, the user turns the knob a step further to the position indicated by a “play” arrow, FIG. 21 . This causes the protrusion 194 inside the knob 20 , FIG. 22 , to come in contact with the contact surface of the start linkage 184 , whereby it will turn around its hinge 188 . The turning of the start linkage will cause the branch 196 to move out of contact with the end pieces 180 of the arms 178 of the hub, whereby the hub is free to rotate, FIG. 23 . Because of the chain of cogwheels of the transmission of the speed control mechanism, the spring housing 44 is free to rotate due to the force of the tensioned flat spiral spring 42 . The knob is held in this position in that the end piece of 208 of the spring during rotation is moved from the hook 210 to the seat 212 of the ledge 214 of the knob 20 , FIG. 22 . This new position of the spring will urge the knob to turn in this direction. However, the knob is prevented from turning further because the protrusion 232 of the knob 20 with its bevelled surface 234 is in contact with the bevelled surface 230 of the ledge 228 of the flexible arm 226 , FIG. 24 .
[0062] Infusion Operation
[0063] The rotation of the spring housing 44 will cause its ratchet 52 to move around the circumference, thereby acting on the cogwheel 54 of the drive member. The rotation of the second cogwheel 62 of the drive member 54 will, due to the engagement with the drive nut 66 , cause the latter to rotate. In turn, the rotation of the drive nut 66 will cause the piston plunger 72 to move in the proximal direction by the engagement between the drive nut and the thread segments 74 . When the first piston plunger segment 76 has moved a distance in the proximal direction, the space behind the first segment is so large that a subsequent piston plunger segment 82 may be pushed in the vertical direction by the flat band spring 98 acting on the lowermost positioned piston plunger follower 102 . When the following piston plunger segments are pushed upwards in the vertical direction, they are connected to a previous piston plunger segment in that the ledges 92 of the nose 90 of the subsequent segment fit into the grooves 88 of the cut-out 84 of the previous segment, thereby sequentially “building” a continuous piston plunger 72 with the segments. The process of the infusion sequence is also visible in the opening 75 where the indicia 73 on the spring housing 44 pass.
[0064] Speed Control of Infusion
[0065] The movement of the piston plunger 72 in the proximal direction will cause the stopper of the medicament container to move inside the container, whereby medicament is pushed through the needle piece 124 , the flexible tube 126 and the infusion needle 128 . A constant speed of the piston plunger 72 is ascertained by the constant speed control mechanism in that the rotation of the spring housing 44 is transmitted to the hub 170 of the centrifugal brake 166 via the transmission of cogwheels 146 , 148 , 152 , 154 , 158 , 160 and 164 . The rotation of the hub 170 will cause the arms 168 to move in the radial direction if the speed is increased over a pre-set level. The movement in the radial direction will cause the ledges 174 of the arms 168 to be moved in contact with the tubular piece 176 , causing a contact friction between the ledges of the arms and the tubular piece that will reduce the speed. In this manner the speed will be kept more or less constant when the arms are moved in and out of contact with the tubular piece during rotation.
[0066] Pausing of the Infusion
[0067] The user may pause the infusion by turning the knob 20 back to the “pause” position against the force of the spring 200 . This will cause the contact surface 192 of the start linkage 184 to move out of contact with the protrusion 194 of the knob, which in turn will cause the start linkage to swing back to its initial position by the spring element 198 . This in turn will cause the branch 196 to move in the path of the end pieces 180 of the arms 178 of the hub 170 , whereby the rotation of the hub is blocked. This in turn will stop the rotation of the spring housing 44 via the transmission, and also the rotation of the drive nut, thereby stopping the movement of the piston plunger 72 .
[0068] Auto-Stop Function
[0069] When the infusion sequence is about to end when the medicament container has been emptied, there will be a space 246 behind the last of the piston plunger segments 82 , FIG. 25 . Because the upper end 244 of the beam constantly has been in contact with and underside of the piston plunger, it is now free to move upwards into the space. Due to this and the form of the beam, the arm 236 is moved towards the spring housing, whereby the protrusion 238 of the arm 236 comes in contact with the outer surface of the spring housing 44 and when the groove 240 of the spring housing comes in position in relation to the protrusion, the latter will be forced into the groove and the rotation of the spring housing is blocked, FIG. 26 .
[0070] When the protrusion 238 enters the groove 240 the force of the spiral spring on the spring housing will cause the beam to be lifted somewhat in the vertical direction. This movement of the beam will cause the flexible arm 226 and its ledge to be moved out of contact with the protrusion of the knob 232 FIG. 27 . Due to the force of the spring 200 acting on the knob 20 and urging it in the clock-wise direction, the knob will be turned in this direction. On the inner surface of the knob, the ledge that the transversal arm is resting on is terminated at 246 , FIGS. 27 and 15 b , whereby the needle plunger is free to be moved in the distal direction by the needle plunger spring 143 . This now causes the infusion needle to be withdrawn from the infusion site. The device may now be removed and discarded.
[0071] Manual Stop
[0072] Instead of the automatic stopping of the device, it may be stopped manually by turning the knob further, FIG. 1 , against the force between the flexible arm 226 and the protrusion 232 of the knob, FIG. 28 . This will cause the flexible arm 226 to move in the proximal direction such that the protrusion 232 of the knob can pass. The arm will then flex back whereby the ledge 228 of the arm 226 prevents the user from turning back the knob. At the same time, the contact surface 192 of the start linkage 184 is moved out of contact with the protrusion 194 of the knob, which will stop the rotation of the spring housing 44 via the transmission in the same manner as when the infusion is paused as described above. However, in this position, the knob may not be turned back, thereby avoiding unintentional activation of the device again.
[0073] Further, in this position, the ledge that the transversal arm is resting on is terminated, whereby the needle plunger is free to be moved in the distal direction by the needle plunger spring, in the same manner as with the auto-stop function. This now causes the infusion needle to be withdrawn from the infusion site. The device may now be removed and discarded.
[0074] It is to be understood that the embodiment described above and shown in the drawings is to be regarded only as a non-limiting example of the invention and that it may be modified in many ways within the scope of the patent claims.
COMPONENT LIST
[0075] 10 proximal housing part
[0076] 12 distal housing part
[0077] 14 proximal-distal direction
[0078] 16 vertical direction
[0079] 18 horizontal direction
[0080] 20 knob
[0081] 22 alien key hole
[0082] 24 shaft
[0083] 26 seat
[0084] 28 arms
[0085] 30 hub
[0086] 32 edge
[0087] 34 seat
[0088] 36 annular ledge
[0089] 38 teeth
[0090] 40 slit
[0091] 42 flat spiral spring
[0092] 44 spring housing
[0093] 46 locking segment
[0094] 48 sidewall
[0095] 50 central opening
[0096] 52 ratchet
[0097] 54 cogwheel
[0098] 56 drive member, shaft
[0099] 58 line
[0100] 60 support member for shaft
[0101] 62 second cogwheel
[0102] 64 teeth
[0103] 66 drive nut
[0104] 68 central opening of drive nut
[0105] 70 threads of central opening
[0106] 72 piston plunger
[0107] 74 thread segments
[0108] 76 first piston plunger segment
[0109] 78 medicament container
[0110] 80 pusher plate
[0111] 82 following piston plunger segments
[0112] 84 cut-out of piston plunger segment
[0113] 86 side walls of cut-out
[0114] 88 groove
[0115] 90 nose
[0116] 92 ledge
[0117] 94 magazine
[0118] 96 slit
[0119] 98 flat band spring
[0120] 100 fixture post on magazine
[0121] 102 piston plunger follower
[0122] 104 lid
[0123] 106 cartridge retainer
[0124] 108 longitudinal edge of cartridge retainer
[0125] 110 guides for cartridge retainer
[0126] 111 cogwheel segment
[0127] 112 cartridge cam
[0128] 114 posts for cartridge cam
[0129] 116 curved ridge
[0130] 118 protrusions on cartridge retainer
[0131] 120 ratchet segment
[0132] 122 end piece
[0133] 124 needle piece
[0134] 126 flexible tube (not shown)
[0135] 128 infusion needle
[0136] 130 needle hub
[0137] 132 needle plunger
[0138] 134 guide piece
[0139] 136 membrane
[0140] 138 transversal arms
[0141] 140 chamfered surface of the arms
[0142] 142 ledges of the knob
[0143] 143 needle plunger spring
[0144] 144 constant speed control mechanism
[0145] 146 1'st cogwheel
[0146] 148 2'nd cogwheel
[0147] 150 1'st shaft
[0148] 152 3'rd cogwheel
[0149] 154 4'th cogwheel
[0150] 156 2'nd shaft
[0151] 158 5'th cogwheel
[0152] 160 6'th cogwheel
[0153] 162 3'rd shaft
[0154] 164 7'th cogwheel
[0155] 166 centrifugal brake
[0156] 168 arms of centrifugal brake
[0157] 170 hub
[0158] 172 4'th shaft
[0159] 174 ledges of arms
[0160] 176 tubular piece of centrifugal brake
[0161] 178 arms of the hub
[0162] 180 end pieces
[0163] 182 operation mechanism
[0164] 184 start linkage
[0165] 186 arm of start linkage
[0166] 188 hinge
[0167] 190 post
[0168] 192 contact surface
[0169] 194 protrusion of knob
[0170] 196 branch
[0171] 198 spring element
[0172] 200 spring as movement member
[0173] 202 , 204 arms of spring
[0174] 206 , 208 end pieces of arms
[0175] 210 hook for spring
[0176] 212 seat
[0177] 214 ledge of knob
[0178] 216 auto-stop mechanism
[0179] 218 beam
[0180] 220 proximal end
[0181] 222 ledge
[0182] 224 curved surface
[0183] 226 flexible arm
[0184] 228 ledge of arm
[0185] 230 bevelled surface of ledge
[0186] 232 protrusion of knob
[0187] 234 bevelled surface of protrusion
[0188] 236 arm
[0189] 238 protrusion
[0190] 240 groove of spring housing
[0191] 242 distal part of beam
[0192] 244 upper end of distal part
[0193] 246 space
[0194] 248 termination of ledge of knob | The present invention relates to an infusion device comprising a housing ( 10, 12 ); a compartment inside said housing for positioning a medicament container ( 78 ), an infusion needle ( 124 ) arranged to said housing, being connectable to said medicament container for delivering a dose of medicament, a piston plunger ( 72 ) arranged in said housing capable of acting on said medicament container for delivering a dose of medicament, mechanical drive means capable of acting on said piston plunger for delivering a dose of medicament. The invention is characterised in that said piston plunger comprises a number of distinct segments ( 82 ) being inter-connectable to each other for forming an elongated piston plunger. | 0 |
The present invention relates generally to locking devices, but more particularly to locking mechanisms which employ a cable which is capable of being formed into two or more loops so as to encircle and retain two or more different objects. More specifically, it relates to locking mechanisms which are quickly and easily locked or set but which can only be released or opened with the use of a key.
BACKGROUND OF THE INVENTION
It is frequently desirable to be able to fasten or mount a given object, such as sports implements like golf clubs or tennis paraphernalia, to a support such as a stationary post to prevent the same from being lost or stolen. To facilitate this, it is desirable to have fastening or locking mechanisms which can be expanded to accommodate articles or objects of different sizes. Also, it is desirable to have such mechanism be small and compact so as to be easily transported and stored, as desired.
Devices of this nature have heretofore been provided, but all such prior devices fall short of the necessary construction and operation to provide the desired end result.
Devices heretofore provided for use in this general security area have been extremely large in size and have been cumbersome and awkward in usage under certain circumstances. Further, they have been relatively large such that transporting and storing such devices has been difficult and awkward.
OBJECTS OF THE INVENTION
In view of the foregoing, it is an object of the present invention to provide a locking mechanism which is capable of providing two or more loops in a cable whereby a plurality of different objects can be encircled and retained in connected relation.
Another object of the present invention is to provide a locking mechanism as characterized above which can be quickly actuated to firmly grip a cable at several specific locations therealong, but which can be quickly released so as to free the objects retained thereby.
Another object of the present invention is to provide a locking mechanism as characterized above which employs two or more wedge-shaped elements which effectively cooperate to grip the cable along its length at several predetermined locations.
A still further object of the present invention is to provide a locking mechanism as characterized above which can be set or caused to firmly grip a cable merely by a human operator giving a slight squeeze to a housing.
An even further object of the present invention is to provide a locking mechanism as characterized above wherein a spring loaded lever is caused to automatically engage and retain the wedge-shaped elements after the human operator has lightly squeezed the housing.
Another even still further object of the present invention is to provide a locking mechanism as characterized above wherein a key operated device is employed for releasing such lever so as to permit the wedge-shaped elements to return to a retracted position releasing the cable.
Another object of the present invention is to provide a locking mechanism as characterized above which is simple and inexpensive to manufacture and which is rugged and dependable in operation.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features which I consider characteristic of my invention are set forth with particularity in the appended claims. The invention itself, however, both as to its organization and mode of operation, together with additional objects and advantages thereof, will best be understood from the following description of specific embodiments when read in combination with the accompanying drawings, in which:
FIG. 1 is a perspective view of a locking mechanism according to the present invention;
FIG. 2 is a sectional view taken substantially along line 2--2 of FIG. 1 of the drawings;
FIG. 3 is a sectional view of the locking mechanism taken substantially along line 3--3 of FIG. 2;
FIG. 4 is a sectional view of the mechanism taken substantially along line 4--4 of FIG. 3; and
FIG. 5 is a sectional view similar to that of FIG. 3 of the drawings, but showing the mechanism in its locked or cable gripping position.
Like reference characters indicate corresponding parts throughout the several views of the drawings.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 of the drawings, there is shown therein a locking mechanism 10 according to the present invention. It comprises a body or housing 12 having a cover 14, and a flexible cable 16. One end 16a of cable 16 is secured within the cover 14 of housing 12.
As shown most particularly in FIGS. 3 and 4 of the drawings, the cover 14 is formed with an opening 14a for receiving end 16a of cable 16. Cover 14 is further formed with an enlarged opening 14b, and a large recess 14c which extends substantially the entire length and width of cover 14.
As will be readily apparent to those persons skilled in the art, the body or housing 12, including cover 14, may be formed of substantially any desired material, but is deemed best made of tough, unbreakable plastic material. Such housing and cover therefore may be formed in a machining process or they may be cast or molded to provide the desired shapes and configurations as will hereinafter become more apparent.
A ferrule 18 is firmly secured to the end 16a of cable 16 after the latter has been inserted in opening 14a. Thus, ferrule 18 is cause to be able to abut the annular shoulder 14d formed in cover 14 between the openings 14a and 14b. Plastic or other appropriate material 20 is provided to close the recess 14c in the upper portion of cover 14, end portion 16a of cable 16 thereby being firmly secured and anchored in the cover 14.
The opposite end 16b of cable 16 is provided with a generally tapered and generally semi-rigid leader 22 to facilitate insertion of end portion 16b as will hereinafter be explained in greater detail.
Attached to or formed integrally with cover 14 are a pair of alignment members 24 and 26, each of which is formed with an end portion of reduced size, as shown at 24a and 26a, to thereby provide shoulders 24b and 26b, respectively.
Also formed integrally with cover 14 is a pair of wedge-shaped elements 28 and 30. Wedge-shaped element 28 is formed with a bottom wall 28a and slanted opposite side walls 28b. Element 30 is formed with a bottom wall 30a and slanted opposite side walls 30b. As shown most particularly in FIG. 4 of the drawings each of the wedge-shaped elements 28 and 30 is formed with a through opening as shown at 28c and 30c, which holes are aligned so as to receive a pin 32.
The body 12 of locking mechanism 10 is formed by a molding or casting process in two halves 12a and 12b. It is deemed preferable to form such body 12 of hard non-breakable plastic to ensure the integrity of the locking mechanism 10. As shown in the drawings, the lower portions 24a and 26a of the guide members 24 and 26 are formed with through openings for receiving guide pins 34 and 36 respectively. These guide pins have opposite end portions which move within elongated recesses formed in housing 12 as shown in FIG. 2 at 12c and 12d with respect to pin 34. Compression springs 38 and 40 are positioned between the bottom wall of housing 12 and the shoulders 24b and 26b, respectively, of the guide members 24 and 26. Thus, the compression spring 38 operates against the shoulder 24b of guide member 24 and the compression spring 40 operates against the shoulder 26b of guide member 26. As will be readily apparent to those persons skilled in the art, this enables the guide members 24 and 26 together with the cover 14 and wedge-shaped elements 28 and 30 to be biased to an open or retracted position as shown in FIG. 3.
Housing 12 is also formed with aligned through openings in its opposite end walls to form two generally parallel passageways as shown at 42 and 44 in FIG. 1. Such passageways are aligned with the wedge-shaped elements 28 and 30, respectively, for purposes which will hereinafter be explained in greater detail.
Positioned centrally within the body or housing 12 is a lever 46. One end 46a of lever 46 is formed with a through opening for receiving a key operated locking mechanism 48 which is mounted within a through opening in one of the walls of the housing 12. The other end 46b of lever 46 is formed with a cutout 46c which, as will hereinafter be explained in greater detail, cooperates with the aforementioned pin 32 which extends between the elements 28 and 30 as shown most particularly in FIG. 4 of the drawings. A torsion spring 50 is provided and has one end portion 50a engaging the housing 12. The opposite end 50b of torsion spring 50 engages lever 46 to thereby bias lever 46 toward engagement of cutout 46c with pin 32.
Fastening means in the form of rivets or bolts 52 are provided to retain the two halves 12a and 12b of the housing 12 in assembled relation as above described.
When it is desired to employ the subject locking mechanism 10, it is merely necessary to encircle an object with the cable 16, and thereafter to thread the leader 22 through one of the aforementioned passageways 42 and 44. Thereafter, the cable can be drawn firmly about such object and thereafter caused to encircle an additional object. Then, the cable 16 can be inserted through the remaining one of the passages 42 and 44 so as to cause the cable 16 to be drawn firmly about such additional object.
Then, merely by gripping the housing and cover 14 in the palm of a person's hand, the cover is moved toward the housing to drive the wedge-shaped elements 28 and 30 toward the respective cable portions to the position shown in FIG. 5 of the drawings. When the elements 28 and 30 sufficiently engage the respective cable portions, the torsion spring 50 moves the end portion 46b of lever 46 to the position shown in FIG. 5 thereby locking such elements against the cable. That is, the housing 12 is thereby firmly and fixedly secured to the cable 16 to retain the several objects in fixed relation.
By suitable actuation of the key lock 48, the lever 46 is returned to its open position as shown in FIG. 3 of the drawings when it is desired to remove the cable 16 from around the several objects. Such key operation moves lever 46 to its open position against the bias of torsion spring 50. When this occurs, the aforedescribed compression springs 38 and 40 return the cover 14 and guide members 24 and 26, as well as wedge-shaped elements 28 and 30 to their retracted positions. This, of course, releases the respective cable portions from being gripped by the elements 28 and 30. Withdrawing the cable 16 from the aforementioned passageways 42 and 44 thus releases or unlocks the objects retained thereby.
It is thus seen that the present invention provides a locking mechanism which is capable of securing together two or more objects. In this regard, it is contemplated that within the purview of this invention, three or four or more wedge-shaped elements could be provided for gripping cable sections or portions simultaneously to thereby provide three or four or more loops in the encircling cable.
Although I have shown and described certain specific embodiments of my invention, I am well aware that many modifications thereof are possible. The invention, therefore, is not to be restricted except insofar as is necessitated by the prior art and by the spirit of the appended claims. | A locking mechanism for providing one or more loops in a cable for separately encircling and retaining different objects wherein different cable portions are gripped by the locking mechanism merely by an individual squeezing the housing of the mechanism to cause wedge-shaped elements to engage the respective cable portions. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit under any applicable U.S. statute, including 35 U.S.C. § 119(e), to U.S. Provisional Application No. 60/683,987 filed May 23, 2005, in the name of Dennis St. Germain, titled Sling Having Predictable Pre-Failure Warning Indicator and Associated Method.
[0002] This application incorporates by reference U.S. Provisional Application No. 60/683,987 as if fully set forth herein.
FIELD OF THE INVENTION
[0003] This invention relates generally to industrial slings used to lift, move and transport heavy loads and, more particularly, an apparatus for notifying operators/riggers who use synthetic slings of an overload or damage situation that may lead to sling failure.
BACKGROUND OF THE INVENTION
[0004] Wire rope slings made of a plurality of metal strands twisted together and secured by large metal sleeves or collars are common in the industry. During the past thirty years, industrial metal slings have seen improvements in flexibility and strength. However, compared to non-metal or synthetic fiber slings, metal slings are relatively stiff and inflexible.
[0005] Synthetic fiber slings have gained popularity over the last fifteen years and are replacing metal slings in many circumstances. Synthetic slings are usually comprised of a lifting core made of twisted strands of synthetic fiber and an outer cover that protects the core. The most popular design of synthetic slings is a roundsling in which the lifting core forms a continuous loop and the sling has a circular or oval-shaped appearance.
[0006] An advantage of synthetic slings is that they have a very high load-lifting performance strength-to-weight ratio which provides for a lighter, more flexible and even stronger slings than their heavier and bulkier metal counterparts. Even with such advances in the art of sling making, the riggers who use these improved synthetic slings still suffer and endure some of the age old problems of sudden failure and loss of a load caused by a sling breaking without warning because it was fatigued (or overly stretched) from being subjected previously to overload conditions. After a sling has been fatigued, it does not usually provide any physical indication that it was damaged—even to the trained eye. (One of the few advantages of a metal sling over a non-metal sling is that there is equipment available that can be used to conduct a non-destructive test of the metal. For example, similar equipment is routinely used to determine whether the wings of an airplane have become fatigued.)
[0007] Standard break tests have been established for determining how large of a load a sling can endure. Slings are attached to a testing machine that applies a steady but increasing force on the sling until it is unable to withstand the stress of the force being applied to it and the sling ultimately breaks. Such break tests have enabled manufacturers of industrial slings to rate the load-bearing capacity of the sling. The load capacity is determined to be a point well below the load used to break the sling and also below the point where the sling is fatigued or damaged. Most sling manufacturers will affix some type of tag notice on the sling which states the load capacity (rated capacity) of the particular sling. This rated capacity gives the maximum amount of load to which the sling may be subjected and still be considered a safe use of the sling.
[0008] Unfortunately, even conscientious operators/riggers who do not take unsafe shortcuts and who operate in a safe responsible manner sometimes are surprised by a sling breaking in use even when they believed it was being used within the load limits of its rated capacity. For example, when industrial slings are in continuous heavy use over three shifts around the clock, the operators on a later shift may not be aware that someone on an earlier shift had subjected the sling to a substantial overload which may have caused serious damage to the lifting core strands of the sling. When a synthetic fiber sling is overloaded beyond its tensile strength or weight-lifting capacity at maximum stretch, it is considered to be fatigued and may never return to its normal strength and load bearing capacity.
[0009] When subjected to an overload condition above its rated capacity, a roundsling can be permanently damaged/deformed if the load stretches the fibers of the load bearing core material beyond their yield point. An over-loaded sling may be susceptible to fracture at a stress point. This condition is similar to the stretching of a rubber band beyond its point of normal elasticity so that when the load or tension is removed or relieved, the rubber band will never regain its normal configuration and its strand dimensions may be permanently stretched which will cause it to fail under a load which is less than its tensile strength load. As stated previously, it is nearly impossible to determine, upon a cursory visual inspection, that a sling has been damaged because of the large size of such slings (on the order of 6 feet or more) and because the load-bearing core is hidden inside the outer cover.
[0010] Once the load-lifting core of the synthetic sling is stretched beyond its yield point, it can actually change in its physical structure and be restricted at a stress point. To date, there has been no precise method or apparatus available to an operator or rigger to determine if a sling with a protective cover was subjected to an overload or damage-causing condition. If a roundsling has been fatigued or structurally changed, the sling may no longer lift a load according to its maximum rated load capacity and, most importantly, becomes a serious threat to the operators and riggers using the sling.
[0011] Thousands of roundslings are being used on a daily basis in a broad variety of heavy load lifting applications which range from ordinary construction (e.g., skyscrapers and bridges), plant and equipment operations, to ship building (e.g., oil rigs), nuclear power plants and the like. The lifting core fibers of such roundslings may be derived from natural or synthetic materials, such as polyester, polyethylene, nylon, and the like. Although the outer covers of synthetic slings are designed to reduce damage, the core fibers are still susceptible to damage from abrasion, cutting by sharp edges, or degradation from exposure to heat, cold, ultraviolet rays, corrosive chemicals or gaseous materials, or other environmental pollutants.
[0012] In certain instances, the core yarn of a synthetic sling could weaken, melt or disintegrate when subjected to elevated temperatures, or to prolonged exposure to either ultraviolet light or chemicals. Still another safety concern flows from abuse by the user when the core yarn is damaged from abrasive wear when the slings are not rotated and the same wear points are permitted to stay in contact for extended periods of time with a device used for lifting (such as hooks on a crane), or on the edges of the load itself. Such abrasion is accelerated for certain types of synthetic fiber material and especially if the load contact section is under compression or is bunched. Riggers in the field are concerned that the inner lifting core yarn of their roundslings may be damaged on the inside without a means for them to detect such defects through the sling cover. Even if the cover is removed it may be impossible to tell if the lifting core has been damaged to the point where it cannot lift its rated load. Since there is no reasonable non-destructive testing techniques for synthetic fiber slings, a synthetic sling that is only suspected of being damaged must be removed from service for safety reasons.
[0013] The structural integrity of the roundsling lifting core material is difficult to determine when it is hidden inside a protective cover of opaque material which renders the lifting core yarn inaccessible for inspection. A stretched or fatigued roundsling could experience a sudden catastrophic failure without warning to the rigger, which may result in the loss of lives and property. Many in the industry have sought to provide safe slings to its riggers to avoid bodily injury, property damage and product liability claims.
[0014] Several roundsling constructions are known which have a failure indicator. For example, it is known in the art to incorporate a failure indicator synthetic strand as an integral member of the lifting or load-bearing core. The failure indicator strand in prior art constructions was always an extension of the core yarns.
[0015] A popular design of prior art roundslings was to twist a plurality of yarns together to form a single strand; the strand is then rolled into an endless parallel loops of strands that form the core, which is then encased in a protective cover material. If the sling was designed with a prior art failure indicator, an indicator strand would be incorporated into and twisted with the core yarns. The two ends of the indicator strand (sometimes referred to as tell-tails), extend freely through an opening in the cover material. When the sling is subjected to an overload condition, the tell-tail would partially withdraw within the cover and the freely extending tell-tail ends would be visibly shorter than the tell-tails of an undamaged sling; if the overload condition exceeded the maximum rated load of the sling, one or both tell-tails would usually withdraw completely within the cover. In either event, the rigger is warned of the occurrence of a potentially damaged sling by either the absence of one or both tell-tails, or a “significant” withdraw of at least one tell-tail inside the cover. However, there usually was no consistency on how the tell-tails would react when triggered, even when the slings were manufactured under identical conditions.
[0016] A drawback of prior art failure indicators based on an indicator strand is that there is no predictable way of determining when the failure indicator will be triggered. Synthetic slings have a safety factor designed into their construction. For example, if the sling is rated at 6,000 pounds, it typically will not be damaged unless the sling is subjected to a force five times greater (i.e., around 30,000 pounds, a 5-to-1 design factor) than the rated capacity; the tell-tail may be triggered and indicate an overload condition when the sling is subject to a force of between four to five times the rated capacity (i.e., about 24,000 lbs) by retracting into the sling's cover. Therefore, the tell-tail will provide a visual indication that the sling may have been damaged or subjected to a situation that may have been detrimental to the overall condition of the sling before the sling actually is subjected to such a condition. Unfortunately, there was no way of ensuring that the tell-tails would consistently withdraw within the cover at about 24,000 pounds.
[0017] In other words, two slings having prior art failure indicator strands contemporaneously made under the same conditions would have two different trigger points (for example, one sling may trigger at about 22,050 pounds and the other sling may trigger at about 26,000 pounds). In addition, one sling may react to a trigger event by completely withdrawing one of the tell-tails, while the other sling may react to a trigger event by partially withdrawing both tell-tails.
[0018] If the tell-tail is not withdrawn completely within the cover, one rigger's opinion of a “significant withdrawal” towards the opening in the cover may differ from another rigger's opinion. Therefore, a “small” movement of one or both of the tell-tails, which may result from the constant use and handling of the sling, may appear to one rigger as an indication that an overload condition was reached when, in fact, the sling was not subjected to an overload condition. Therefore, the visual inspection of the tell-tails in prior art failure indicators and the eventual determination of a trigger event becomes a subjective test.
[0019] Another prior art roundsling construction utilizes an optical fiber strand that enables the operator/rigger to test it by shining a light on one end of the optical fiber to determine if the light can be seen at the other end of the optical fiber. In U.S. Pat. No. 5,651,572 to Dennis St. Germain, it is taught to incorporate a flexible fiber optic “signal” cable into the lifting core strands of the roundsling.
[0020] As indicated previously, in a roundsling, the lifting core is configured in endless parallel loops of strands which are then encased within a protective cover material. The cover will have openings or orifice slits out of which the two ends of the fiber optic signal strand emerge. The aforesaid ends of the fiber optic cable are designed to extend freely through a slit in the sling's cover so that they are easily accessible by the rigger.
[0021] The optical signal strand member conducts light from a light source at one end to an observer looking at the opposite end for testing the integrity and the continuity of the core strands. The inclusion of the fiber optic cable in the lifting core yarn of the roundsling converts the inaccessible inner core area into an observable test check area by means of the passage of light through the fiber optic component of the lifting core.
[0022] Fiber optic materials are capable of transmitting light into endless parallel relationship with the fibers of the lifting core yarn. This fiber optic signal strand comprises fiber or rod material which permits the propagation of light that enters the fiber material at one end and is totally reflected back inward repeatedly from the fiber wall through the entire length of the fiber optic strand which enables the light being transmitted within the fiber optic cable to pass from one end of the fiber optic cable to the other end. If the light emerges at the other end of the fiber optic cable, it indicates that the integrity of the fiber optic cable throughout the path of the roundsling lifting core bundle is intact and, by reasoning, the integrity of the lifting core yarns are also intact.
[0023] Since the fiber optic cable member is incorporated into the lifting core of the roundsling disclosed in U.S. Pat. No. 5,651,572, it tends to develop somewhat similar breaking or snapping characteristics as the lifting core fiber materials. If the fibers of lifting core yarn break or fracture, then the fiber optic cable will also be damaged which will prevent the transmission of light from one end to the other end of the emerging fiber optic cable. If the light fails to pass from one end of the signal fiber optic cable to the other end, then the rigger is warned that the lifting core strands may be damaged, and to remove the protective cover from the roundsling for further inspection. If, upon inspection, it is determined that the roundsling was damaged, it will be immediately removed from service, and replaced with a new sling.
[0024] Although the apparatus disclosed in U.S. Pat. No. 5,651,572 is currently the leading product for determining whether the lifting core yarns of a synthetic sling have snapped or been damaged, in the stages where the sling has been subjected to an overload condition, the fiber optic signal strand still does not have the identical stretching properties of the load-bearing core yarns. Accordingly, unless the fiber optic cable breaks completely, some light may still be able to traverse the entire length of the fiber optic cable such that the degradation in the intensity of the light may be imperceptible to the naked eye.
[0025] Alternatively, the fiber optic cable, being more brittle than the synthetic core material, may be damaged by normal handling (and dropping) of the sling, or at a force less than the rated capacity of the sling. In such cases, the light transmission through the fiber optic cable may be disrupted causing the fiber optic cable to indicate an overload condition when, in fact, no overload condition was reached.
[0026] Finally, under other excessive or damage-causing situations (e.g., excessive heat, acidic or chemical exposure, and ultraviolet exposure) it can be expected that the fiber optic cable will be affected differently than the synthetic strands of the lifting core. If, for example, a sling with the fiber optic signal cable is exposed to certain chemicals, the fiber optic signal cable may be relatively unaffected (or only its exterior surface is affected leaving the light path through the center of the cable unscathed), while the lifting core has been degraded to the point where it no longer meets its load rating. Therefore, as stated previously, the need to precisely determine whether the load bearing core of a synthetic sling was subjected to an excessive or damage-causing situation still exists.
SUMMARY OF THE INVENTION
[0027] The present invention discloses a pre-failure warning indicator for use with a sling that is more accurate and predictable than prior art indicators. In the present invention, the failure indicator strand is separate and independent from the load-bearing core yarns.
[0028] One of the most popular designs of a roundsling is to twist a plurality of yarns together to form a single strand; the strand is then rolled into endless parallel loops of strands that form the core. In accordance with the present invention, a pre-failure warning indicator includes a separate dedicated strand of material, a ring made of a specially chosen material, and a separate warning fiber having an elongated indicator whip end.
[0029] The dedicated strand is placed proximate and substantially parallel to the loops of core strands of the sling; the ends of the dedicated strand are brought within close proximity (in a preferred embodiment several inches) to each other and are terminated with eyes or another configuration that can secure the ring. The ring is inserted through or secured to both eye terminations, thereby bridging the gap between the ends of the dedicated strand, and usually forms an oval-shaped loop. One end of the warning fiber is attached to one of the eyes of the dedicated strand, and the free end of the warning fiber is placed along the ring and threaded through the opposite eye; the free end of the warning fiber is then double-backed along the length of the ring. A tubular cover material encases the lifting core and the pre-failure warning indicator. The free end of the warning fiber extends through an opening in the cover material and is referred to as the indicator whip.
[0030] In a specific embodiment, a tag is attached to the strand (and preferably one of the terminating eyes) and is also drawn through the slot so that it extends freely outside the cover. The tag is designed to provide an indicator that the sling has been tampered with or sabotaged.
[0031] The ring is designed to fail when the sling is subjected to an excessive or damage-causing situation. A common damage-causing situation is when the sling is over-loaded. The ring will break when the sling is placed in an overload situation, thereby causing the termination eyes to separate, resulting in the complete withdrawal of the whip inside of the cover.
[0032] By choosing the ring carefully, relatively accurate predictions of the force needed to trigger the warning fiber can be made. In addition, the ring may be chosen to fail and thereby convey a damage situation when the sling is being used under unusual environmental conditions (e.g., excessively hot, acidic, or ultraviolet rays from, for example, sunlight).
[0033] Previous indicators either of the fiber optic nature or of the tell-tail type could give false indications of an overload or other internal damage. In the case of fiber optics, the ability to transmit light can be impeded by dirt, grease, and other debris that can retard the transmission of light through the fiber optic cable by jamming the ends. In the case of tell-tails, the movement of the sling's outer cover from friction with a load can give a false implication that the tell-tails were pulling under the cover when it was really the cover moving over the tell-tails. In the current invention, these areas of confusion are eliminated by a simple visual identification of the external warning indicator. Also, the dedicated strand can be locked into place by permanent attachment to the cover. If the cover shifts, the entire assembly of this invention moves with it in concert so a false indication of overload is eliminated.
[0034] Additional objects and advantages will be evident to one skilled in the art after a reading of the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the embodiments of the present invention and, together with the following description, serve to explain the principles of the invention. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred, it being understood, however, that the invention is not limited to the specific instrumentality or the precise arrangement of elements or process steps disclosed.
[0036] In the drawings:
[0037] FIG. 1 is a perspective view of a single-path roundsling which incorporates a predictable pre-failure warning indicator in accordance with the present invention;
[0038] FIG. 2 is an enlarged cross-sectional view of the roundsling illustrated in FIG. 1 taken along line 2 - 2 ;
[0039] FIG. 3 is a side view of a pre-failure warning indicator in accordance with the present invention;
[0040] FIG. 4 is a side view of another embodiment of a pre-failure warning indicator in accordance with the present invention, utilizing multiple rings linked together;
[0041] FIG. 5 is a side view of another embodiment of a pre-failure warning indicator in accordance with the present invention for use with a two-path sling;
[0042] FIG. 6 is a perspective view of a two-path sling incorporating the pre-failure indicator of FIG. 5 ;
[0043] FIG. 7 is a side view of a pre-failure warning indicator in accordance with the present invention which also incorporates a sabotage indicator means; and
[0044] FIG. 8 is a perspective view of a single-path roundsling incorporating the predictable pre-failure warning indicator of FIG. 3 and the sabotage indicator of FIG. 7 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0045] In describing a preferred embodiment of the invention, specific terminology will be selected for the sake of clarity. However, the invention is not intended to be limited to the specific terms so selected, and it is to be understood that each specific term includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
[0046] The subject invention is an apparatus and method for determining whether a synthetic fiber sling has been damaged (because of an overload or other condition that could weaken the sling's load-bearing core) to a point where the sling should be removed from service and returned to the manufacturer for internal inspection and, if necessary, repair or disposal. Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings in which a roundsling having a pre-warning failure indicator in accordance with the present invention is generally indicated at 10 . The various preferred embodiments will be described with reference to the drawing figures that form a part of this description where like numerals represent like elements throughout.
[0047] FIG. 1 illustrates a perspective view of a roundsling in accordance with the present invention. FIG. 1 specifically shows a single-path roundsling, but the principles disclosed herein may be applied to other slings including multiple-path slings. FIG. 2 is a cross-sectional view of the roundsling shown in FIG. 1 taken along line 2 - 2 , and illustrates the primary interior components of a typical roundsling.
[0048] Referring to FIGS. 1 and 2 , the roundsling 10 comprises an inner core 12 encased within an outer protective cover 25 . The outer cover 25 shown in FIG. 2 is meant to convey that the cover 25 is larger than the load-bearing core 12 and moves relatively freely with respect to the load-bearing core 12 and not necessarily that the cover 25 has a cross-sectional shape of an oval. The core 12 is designed to bear the entire weight of the load to be lifted. The primary purpose of the outer cover 25 is to prevent physical damage to the core from abrasion, sharp edges on the load, etc.; the cover 25 will also help to reduce damage to the sling when it is used in an environment that will subject it to harsh elements such as heat, ultraviolet light, corrosive chemicals, gaseous materials, or other environmental pollutants. As will be explained hereinafter, the cover 25 can also be designed to notify a user when physical damage has occurred to the cover.
[0049] The lifting core 12 is preferably made of a single or multiple strands 17 configured in a plurality of endless parallel loops of strands to form a single core or multiple cores, all of which are contained inside the protective cover material 25 . The use of a single strand or multiple strands in this configuration is typical in the construction of roundslings.
[0050] The lifting core 12 of such roundslings may be derived from one or more natural or synthetic materials, such as polyester, polyethylene, nylon, K-Spec® (a proprietary blend of fibers), HMPE, LCP, para-aramid or other types of synthetics. The material chosen for the core primarily depends on the maximum weight the sling is designed to lift and environment in which the sling 10 will be used. Such sling constructions have a high lifting and break strength, lighter weight, high temperature resistance and high durability, compared to wire rope or metal chain slings.
[0051] Referring now to FIG. 3 , the pre-failure warning indicator 11 in accordance with the present invention is illustrated in side view and is shown without the cover 25 and without core 12 . In a preferred embodiment, the sling 10 may be manufactured with only a pre-failure warning indicator 11 , or with both a pre-failure warning indicator 11 and a tamper-evident means 35 . Initially, the operation of the pre-failure warning indicator 11 will be disclosed; the tamper-evident means 35 will be described later with respect to FIG. 7 .
[0052] A separate (preferably single) strand 20 of yarn is dedicated to the pre-failure warning indicator 11 . The dedicated warning strand 20 is located within cover 25 ; it is preferably placed proximate the core 12 and may either be twisted around the load-bearing strands of the core 12 or it may just lay next to the core 12 , as illustrated in FIG. 2 .
[0053] In a different embodiment, it may be desired to permanently affix the dedicated strand 20 to the inside of the cover 25 . When a sling is used over a period of time, the cover will develop wear points at specific locations, for example, where the sling hangs from a crane's hook. Accordingly, it is usually advisable to rotate the cover with respect to the load-bearing core 12 . By securing the dedicated strand 20 to the inner cover, movement of the cover (either intentionally or non-intentionally) will not affect the operation of the pre-failure warning indicator 11 .
[0054] First end 22 and second end 24 of the dedicated strand 20 are terminated in eyes 32 , 34 , respectively. The dedicated strand 20 and eyes 32 , 34 are preferably made of the same material as the core strands 17 .
[0055] The eyes 32 , 34 are connected by a ring 26 , thereby forming an endless loop with the dedicated strand 20 . The shape of the separate dedicated strand 20 generally matches the shape of the endless parallel loops formed by the core strand 17 (i.e., generally circular or oval). Although the term “ring” implies a circularly-shaped object, as used herein “ring” is defined as any closed link or band that will connect the ends of a dedicated strand.
[0056] In one preferred embodiment, the ring 26 is chosen to have a lower tensile strength than the core 12 . The sling manufacturer may choose to do this any number of ways, e.g., by making the ring 26 out of a different material than the dedicated strand 20 , cutting a notch or notches in the ring to physically weaken it, or by making the ring 26 out of the same material as, but of a smaller diameter than, the core strands 17 . When ring 26 is chosen to have a lower tensile strength, the pre-failure warning indicator 11 is designed to trigger and thereby notify the rigger or other users of the sling that the sling 10 has been subjected to an overload condition (i.e., the sling was subjected to a force that was pre-determined to compromise the integrity of the sling, and is sometimes determined to be about four times greater than the sling's rated capacity).
[0057] Attached to first termination eye 32 is a warning indicator fiber 29 . Warning indicator fiber 29 is an elongated strand that is placed substantially parallel to the ring, is threaded through the second termination eye 34 , is then double-backed along the ring 26 towards the first eye 32 , and directed out an opening in the sling cover 25 . (The external end 40 of the warning indicator fiber 29 that extends through the sling cover 25 is sometimes referred to as a “whip.”) Although the sling cover 25 is not shown in FIG. 3 , the preferred orientation of the warning indicator fiber 29 is illustrated, i.e., it forms a substantially “J” shape within the sling cover 25 .
[0058] Referring again to FIG. 1 , the whip 40 of the warning indicator 29 extends freely through cover 25 . Although not necessary, cover patch 30 may be attached (preferably by sewing), to the cover to protect the opening through which the whip end 40 of the warning indicator 29 extends.
[0059] The dedicated strand 20 is preferably made of similar material as the strands 17 of the load-bearing core 12 ; this promotes the relatively equal stretching of all components of the sling 10 . In a preferred embodiment, the ring 26 has a pre-selected lower tensile strength than the material used to make the core strands; in this embodiment, the ring 26 will fail before the lifting core 12 is stretched or fatigued. Alternatively—or in addition—the ring 26 may be designed to have a lower resistance to abrasion, heat, cold, and/or chemical exposure. By carefully choosing the properties of ring 26 , a sling manufacturer can control the condition(s) under which the subject pre-failure warning indicator 11 will trigger.
[0060] In one example, the sling manufacturer may design the ring 26 to fail at 70% of the tensile strength of the inner core. Accordingly, the material from which ring 26 is made and/or its cross-sectional thickness may be chosen to meet the pre-selected tensile strength.
[0061] When the sling 10 is placed under a load that exceeds its recommended rating, ring 26 will fail before damage can occur to either the load bearing core strands 17 that form the core 12 or the dedicated strand 20 . When ring 26 fails, the termination eyes 32 , 34 begin moving in opposite directions away from each other, and the physical distance between the eyes 32 , 34 and/or ends 22 , 24 of the dedicated strand 20 increases.
[0062] As the eyes 32 , 34 move apart, the whip portion 40 of warning indicator fiber 29 (i.e., the end that extends freely outside the cover 25 ) is drawn back inside the cover 25 until it no longer extends through the cover. If the whip end 40 of the warning indicator 29 is not visible, an inspector or rigger will immediately be able to determine that the sling 10 may have been subjected to a condition that would prevent the lifting core 12 from lifting its maximum rated load and will therefore remove the sling 10 from service for further inspection. The double-back configuration of the indicator fiber 29 ensures that the whip end 40 moves twice the distance compared to the distance the eyes 32 , 34 move apart, ensuring that every time a trigger event occurs, the whip end 40 will completely disappear. (It should be noted that the whip end 40 of the warning indicator 29 may be shaded in a high visibility color or otherwise marked, so that its visibility or lack thereof will be more noticeable.)
[0063] An important feature is that the ring 26 is designed to fail before damage occurs to the lifting core, thereby warning the riggers that they must either stop using the sling 10 in the manner in which they are using it or, if they continue, the sling 10 will be permanently damaged. If the rigger stops using the sling, the integrity of the lifting core 12 may remain intact. In this case, the sling 10 can be returned to the manufacturer and the pre-failure warning indicator 11 can be replaced or repaired; usually only the ring 26 will have to be replaced.
[0064] A primary advantage of the pre-failure warning indicator 11 in accordance with this invention is that the ring 26 may be designed to more precisely fail at a controlled point (regardless of whether it is at a specific strength, abrasion, temperature, etc.). The ring 26 can be used as an indicator of an overload condition by making it weaker than the individual core strands 17 . In a second embodiment, the ring 26 can be made from a material that would fail from yarn-on-yarn abrasion damage. In a third embodiment, the ring 26 can be made to fail from excessive temperatures (either heat or cold, or both). In a fourth embodiment, the ring 26 could be made from a material that would deteriorate in the presence of chemicals at a concentration lower than would damage the strands 17 of the load-bearing core. In still another embodiment, the ring 26 can be made of a material or combination of materials that would fail when subjected to more than one of the pre-determined conditions (e.g., overload and excessive heat).
[0065] In all of the above conditions, the ring 26 is preferably designed to fail at the pre-determined or desired condition at a relatively precise point. For example, if the sling is rated to lift 6,000 pounds (with a five-to-one design factor), the ring 26 can be designed to break relatively close to 24,000 pounds every time. Therefore, the ring 26 can be made to fail before the built-in safety factor of 30,000 pounds and well before any damage occurs to the sling 10 . The use of the predictable pre-failure warning indicator 11 as disclosed herein, gives a sling manufacturer a more predictable and accurate way of incorporating a failure notification means into any sling it designs or makes. In other words, the present invention introduces a degree of predictability into the manufacturing of roundslings since the failure point of the ring 26 can be selected and consistently reproduced. In prior art tell-tail indicators, the failure point was unpredictable and was not consistently reproducible.
[0066] A prototype was made in order to meet the following requirements:
Tensile strength of 30,000 lbs.; Vertical Rated Capacity=6,000 lbs. at a 5 to 1 design factor; Overload Warning Indicator triggers at 20,000-25,000 lbs. with a Design Factor between 3 & 4 to 1; Lightweight: 6′ prototype weighs 1.7 lbs; Double contrasting color cover: Outer Green and inner Red for easy cut inspection; Low stretch; Impervious to salt water and most chemicals including oil, diluted acids and bases;
[0074] Made with K-Spec® proprietary blend of high performance core yarn.
[0075] The above prototype was tested and it was determined that the whip 40 of the pre-failure warning indicator 11 consistently disappeared (meaning that ring 26 consistently broke) at between 23,000 and 24,000 lbs and the final tensile strength of the sling 10 was 32,860 lbs.
[0076] When the whip 40 of the warning indicator 29 is no longer visible, the sling 10 should be returned to the sling manufacturer for inspection and/or repair. The ring 26 consistently broke before damage occurred to either the dedicated strand 20 or the load-bearing core 12 . In many cases, the sling manufacturer will only have to replace the ring 26 in order to refurbish the sling and return it service. (In the above example, the ring 26 failed around 24,000 pounds and the sling 10 did not approach its maximum tensile strength of 30,000 pounds.) Under certain conditions, even though the ring 26 may have been designed to fail first, the sling 10 may have degraded to a point where it must be discarded entirely. For example, if the sling 10 was exposed to an acidic environment for an extended period of time, especially after the ring 26 failed, the sling 10 (and, specifically, the strands 17 that make up the load-bearing core) may have been damaged to such an extent that it can no longer meet its rated capacity. (The selection of the material for the core is the primary factor in determining whether the subject sling is impervious to sea water, oil, acids and other chemicals. Also, the cover 25 plays an important factor in protecting the core especially from abrasion or from sharp edges.)
[0077] It should be noted that a person skilled in the art, after reading the present disclosure could produce equivalent embodiments. For example, even though virtually all synthetic slings have a load-bearing core protected by an outer cover, a sling manufacturer can eliminate the outer cover (or shorten the outer cover) so that the ring 26 is visible. In this embodiment, a dedicated strand is not required and an operator can determine that a sling overload condition (or other failure condition) was met by observing the integrity of the ring 26 .
[0078] Referring now to FIG. 4 , another preferred embodiment is disclosed. In this embodiment, pre-failure warning indicator Ha incorporates a plurality of rings 26 a , 26 b , 26 c , etc. connected together (i.e., as links in a chain) between termination eye 32 and termination eye 34 . In this manner, a sling 10 a can be designed to indicate whether it has been subjected to multiple excessive conditions—any one of which could cause the controlled destruction of one of the linked rings 26 a , 26 b , 26 c , etc. and which would then trigger the warning indicator 11 a in a similar manner as when there is only one ring 26 . (Although this example uses three rings 26 a , 26 b , and 26 c , two rings, four rings or more rings may be used depending on the number of failure conditions the sling manufacturer wishes to incorporate into the sling.)
[0079] The warning indicator fiber 29 has a secured end and a whip end. The secured end is attached to one termination eye 32 ; the remainder of the indicator fiber 29 is placed along all of the rings 26 a , 26 b , 26 c ; the indicator fiber is then threaded through the other termination eye 34 , is double-backed along all the rings, and is finally directed through the slit in the cover 25 where the whip is visible to an operator.
[0080] For example, as shown in FIG. 4 , ring 26 a could be designed to fail when the sling is subjected to an overload (excessive weight) condition, ring 26 b could be designed to fail under an excessive heat condition, and ring 26 c could be designed to fail when exposed to a specific concentration of a particular chemical. Therefore, if the sling is subjected to any of the pre-determined failure conditions, one of the rings 26 a , 26 b , 26 c will fail, causing the termination eyes 32 , 34 to pull away from one another, thereby causing the whip portion 40 of the warning indicator whip 29 to completely retract inside the cover 25 . In this manner, a single predictable pre-failure warning indicator 11 c can be used to signal one of a multiple possible failure conditions. By marking the individual rings before assembly of the sling, one can determine the exact condition which the sling was subjected to that caused the pre-failure warning indicator to trigger. So, for example, if ring 26 b failed (and ring 26 a and ring 26 c remained intact), the sling manufacturer would know that the sling was subjected to a high temperature for an extended period of time.
[0081] An improved synthetic roundsling having multiple cores is manufactured by Slingmax, Inc. and is disclosed in U.S. Pat. No. 4,850,629 to Dennis St. Germain. An embodiment disclosed in U.S. Pat. No. 4,850,629 is a two-core roundsling (sold under the brand name TWIN-PATH®) which has two-load lifting cores inside a single cover. The cover is also divided into two separate paths. U.S. Pat. No. 4,850,629 is incorporated by reference as if fully set forth herein.
[0082] Similar to a sling having a single core (and a single pre-failure warning indicator), in a multiple-core or multiple-path roundsling 50 , each core incorporates a predictable pre-failure warning indicator 11 a , 11 b , as taught herein. Referring now to FIG. 5 , a first dedicated strand 20 a is associated with the first core 12 a of a two-path sling 50 and a second dedicated strand 20 b is associated with the second core of the two-path sling. The dedicated strand 20 a is terminated by termination eyes 32 a , 34 a , and dedicated strand 20 b is terminated by termination eyes 32 b , 34 b , respectively. A ring 26 d , 26 e , as disclosed previously in a one-path sling 10 , is incorporated into each path of the two-path sling 50 .
[0083] Referring now to FIG. 6 , whip 40 a is associated with the predictable pre-warning indicator 11 a in the first path of the sling 50 , and whip 40 b is associated with the predictable pre-warning indicator 11 b in the second path. (It should be noted that the warning indicator fiber 29 a is attached to one termination eye 32 a , threaded through the other termination eye 34 a , and the whip end 40 a is passed through the cover 25 a , and operates in a similar manner as the “basic” single-path sling 10 illustrated in FIGS. 1 through 3 using only one ring 26 . Similarly, warning indicator strand 29 b is attached to one termination eye 32 b , threaded through the other termination eye 34 b , and the respective whip end 40 b is passed through the cover, and operates in a similar manner as when there is only one ring 26 .)
[0084] Sling 50 is comprised of a two-path core; as illustrated in FIG. 6 the warning indicator whips 40 a and 40 b are passed through the cover 25 a and emerge in free extension apart from the cover 25 a . This embodiment provides a pre-failure indicator for each path that can convey sling damage or overload when either core of the TWIN-PATH® sling is subjected to a load which exceeds its tensile strength or rated capacity. When this happens, one or both of the extended warning indicator whips, 40 a and/or 40 b , which emerge outside of the cover material 25 a will retract completely within the cover thereby alerting the operator or rigger to a sling overload condition.
[0085] In a Twin-Path® sling having exactly two cores, each core is identical to the other. Referring again to FIG. 5 , an interesting variation for a two-core sling is the ability to design into the sling two distinct and separate damage-indicating parameters into a single sling. For example, in the first path, the ring 26 d could be designed to fail only at a lower tensile strength than the core 12 ; while in the second path, the ring 26 e could be designed to fail only when the sling is exposed to a certain chemical in the environment. The whips 40 a , 40 b of warning indicators 29 a and 29 b can be marked or coded in order to indicate which whip is associated with which ring so that if a ring breaks, the rigger will know the condition that was exceeded (i.e., if ring 26 d breaks it was because the TWIN-PATH® sling was subjected to a load approaching it's maximum load rating; alternatively, if ring 26 e breaks if was because the TWIN-PATH® sling was exposed to the chemical for a period of time such that it deteriorated the integrity of the sling). Therefore, if a three-core sling is made, three separate conditions may be simultaneously and independently tested using the predictable pre-failure indicator 11 taught herein; a four-core sling can be used to simultaneously test for four separate conditions, etc.
[0086] In this manner, if the two-path sling 50 is subjected to either one of the pre-selected conditions to a point that causes either ring 26 d or ring 26 e to fail, the rigger will be alerted and will have more information than would otherwise be available to him. Designing the rings 26 d , 26 e to fail under different situations may also assist the sling manufacturer in analyzing the sling or further improving the sling, if the sling is ever returned for inspection or repair. However, there are situations in which it will be necessary to design the rings 26 d and 26 e to fail under the same condition (e.g., an overload condition).
[0087] The pre-failure warning indicator 11 in accordance with the present invention is designed with a trigger mechanism that will generate a magnified force on the whip end 40 of the external warning indicator 29 in order to move the whip end 40 out-of-sight almost instantaneously, if any of the pre-engineered conditions are met and the ring fails. The reason why the force on the whip end 40 of the warning indicator fiber 29 is magnified is because of the double-back design of the warning indicator fiber 29 through the termination eyes 32 , 34 . After the ring 26 breaks, the termination eyes 32 and 34 separate at a certain speed; however, since the warning indicator fiber 29 is tied to one eye 32 , threaded through the opposite eye 34 , and doubles-back along the ring before emerging through the cover 25 , the whip end 40 of the warning indicator is moving twice as fast (and twice the distance) as the speed (and distance) at which the eyes 32 , 34 are moving away from each other. Accordingly, the whip end 40 withdraws inside the cover entirely so that there is no question as to whether a trigger event occurred.
[0088] Another feature to note, is that because the whip 40 of the warning indicator 29 is moving so fast, it creates a sound that is audible to the operator. Therefore, the present invention not only gives a visual indication that a sling has reached a critical damage point, but also gives an audible warning. The audible warning is especially important when the sling is positioned so that the operator cannot see the whip 40 (e.g., when the sling is hanging thirty feet in the air).
[0089] Another notable feature of the subject pre-failure warning indicator 11 is the ability to warn the rigger of an overload and other dangerous situations without affecting the overall strength of the roundsling 10 . If the rigger stops lifting the load promptly after the pre-failure warning indicator 11 is triggered, the sling 10 retains 100% of its residual strength.
[0090] The color code safety feature of this invention may be achieved by encasing the load-bearing core in two separate covers, each cover having a different color. For example, the outer cover could be green or blue, and the inner cover could be orange or red; since the inner cover is a different color from the outer cover, it will show through whenever the outer cover is cut or worn through. This double-cover feature provides a visible safety warning for any user of the sling that abrasion or other damage not normally detectable, has occurred.
[0091] In another embodiment of the present invention, a pre-failure warning indicator 11 can be adapted with a sabotage or tamper-evident means. Referring now to FIG. 7 , a tamper-evident tag 35 is attached to either the dedicated indicator strand 20 or, preferably, to one of the eyes 32 or 34 . The free end of the tamper-evident tag 35 is passed through the cover via a slit. The slit can be the same one through which the whip 40 passes through.
[0092] If the pre-failure warning indicator 11 is triggered (by, for example, an overload condition), this means that ring 26 has been broken, the ends 22 , 24 of the dedicated strand 20 are free, causing whip 40 to withdraw completely within the cover. Upon inspection, the tamper-evident tag 35 can be easily pulled out from inside the cover 25 along with a portion of the dedicated strand 20 , as illustrated in FIG. 8 , when the pre-failure warning indicator 11 has been triggered. If the whip end 40 of the warning indicator is not visible because of an intentional intervention by a user, the tamper-evident tag 35 will remain secure and cannot be pulled from the cover 25 . In this manner, sabotage of the sling 10 can be evidenced by the supervisor on the work site. (In order to avoid work, some users will cut off the whip end 40 of the warning indicator 29 in an attempt to make it appear that the sling was subjected to a damage situation and, therefore, work must be temporarily stopped so that the sling can be removed for inspection and, if necessary, replaced with a new sling.)
[0093] As part of the inspection process, the inspector may yank on the tamper-evident tag 35 . If the tag is secure, the sling 10 is useable; but, if the tamper-evident tag 35 can be pulled out from inside the cover, the sling 10 must be removed from use because the pre-failure warning indicator 11 has been triggered. Of course, if a saboteur cuts both the whip end 40 and the visible portion of the tamper-evident tag 35 , the inspector will immediately know that the sling 10 has been tampered with, and should remove the sling from service.
[0094] It is important to note that no other prior warning indicators have the ability to quickly inspect the condition of a roundsling. Also, prior warning indicators are not as accurate as the subject warning indicator 11 . If the whip end 40 of the warning indicator is visible and the cover 25 is intact, the roundsling can be used for the next lift; if the whip end 40 of the warning indicator is not visible, the sling should be removed from service and inspected. The subject pre-failure warning indicator is the first completely pass/fail inspection system—it is a completely objective test and not subjective.
[0095] It should also be noted that one skilled in the art, after reading this disclosure, may develop variations that are contemplated as being equivalent in scope to the various embodiments specifically set forth in the present disclosure. For example, the termination loops 32 , 34 may be eliminated and the ends of the dedicated strand 20 may be tied directly to the ring 26 . (Alternatively, slip-knots or other means may be used to secure the ends of the strand 20 to the ring 26 .) Although this invention has been described and illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes, modifications and equivalents may be made which clearly fall within the scope of this invention. The present invention is intended to be protected broadly within the spirit and scope of the appended claims. | A pre-failure warning indicator is provided for use with a sling. The pre-failure warning indicator triggers at a point that is predictable within a relatively narrow range, thereby increasing the possibility that a damaged sling is removed from use. The pre-failure warning indicator includes a dedicated strand of material that is placed in close proximity to the load-bearing core yarns of the sling but remains separate and independent from the core yarns; the ends of the dedicated strand are connected via a sacrificial “ring.” A warning fiber having an end that is visible to operators/riggers works in conjunction with the sacrificial strand and the ring. The ring is designed to fail when the sling is subjected to a specifically chosen condition (e.g., excessive weight). The failure of the ring causes the warning fiber to withdraw from the rigger's view thereby warning the rigger that the sling was subjected to the specifically chosen condition and may be damaged. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to hand level control systems for traction vehicles, such as snow blowers, lawn mowers and other walk-behind traction vehicles having a tool or implement operable therewith.
Often it is desirable for the operator of a walk-behind traction vehicle to free one hand while operating a two-handed vehicle, such as a snow blower, lawn mower and the like. In the past this manual freedom has been accomplished by disposing both hand control levers on one handle of the implement, one superimposed on the other, so that operating the one control lever will necessarily operate the other and release of the one will necessarily release the other. In other cases two hand control levers have been positioned adjacent one another on a portion of a U-bar type of handle so that a direct mechanical engagement can be realized between the two levers for effecting a dual control of the implement with one movement of a lever. In such arrangements, however, the appearance of two control levers in a superimposed or side by side relationship on one handle or a portion of one handle is perplexing if not daunting to the average consumer or home-owner operator whose priorities, to be sure, for operating such traction vehicles are simplicity and ease of operation. Besides appearing confusing to the operator, these clustered types of arrangements of control levers, as above described, necessitate a close proximity of parts, including intricate camming mechanisms and pivotal joints such that jamming or deformation of these parts are likely to occur through improper adjustment or use by an irate or inexperienced operator.
OBJECTS AND SUMMARY OF THE INVENTION
The present invention has for its primary object and purpose to provide a hand control lever system for walk-behind traction vehicles, such as snow blowers and lawn mowers and the like, which will afford easy operation of the hand controls without causing confusion to the operator or requiring manual dexterity of a high order. Other ancillary objects of the invention are to provide a hand control system for traction vehicles which has few parts, is durable and offers ready accessibility for adjustment and maintenance of the system.
According to one embodiment of the invention there is provided a first hand control lever on one handle member (the left side handle) of the traction vehicle, which is connected to the traction drive connection and is movable by the operator's left hand between an operable and inoperable position, and a second hand control lever on the other handle bar (the right side handle) which is connected to the tool drive connection and is movable by the operator's right hand between an operable and inoperable position. Also provided is an auxiliary control cable having a cable support and a pivotal cam-slot lever associated with a stop member on the second hand control connection. The control cable is directly responsive to movement of the first hand control lever and acts to latch the second hand contol lever in its operable position in response to the first hand control means being moved to its operable position. In this way the right hand of the operator can be freed for whatever reason as long as his or her left hand grips the left hand control lever and holds it in its operable position; thus, it will be seen that once the traction of the vehicle is implemented (by closing one's grasp on the first hand lever and thereby engaging the drive clutch), the right hand lever may be closed to its operable position (thereby engaging the tool implement, sush as the auger for a snow blower) and that hand may then be subsequently removed for whatever reason so long as the left hand is gripping the first or left hand lever. However, once the left hand lever is released, that is, the traction is stopped, both drives are immediately disconnected by means of the auxiliary control system.
The invention will be better understood as well as further objects and advantages thereof become more apparent from the ensuing detailed description taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view, partially broken away, of the hand control system according to the invention seen from the front of the implement;
FIG. 2 is a schematic perspective view of the auxiliary control cable support used with the invention;
FIG. 3 is a schematic perspective view showing of the pivoted cam-slot lever used with the invention;
FIG. 4 is a schematic plan view, partly broken away, seen from the rear of the implement showing the auxiliary control system in its inoperable position; and
FIG. 5 is a schematic plan view, partly broken away, seen from the rear of the implement, showing the auxiliary control system in its operable position.
DETAILED DESCRIPTION
Referring now to FIG. 1, there is shown generally at 10 a powered traction vehicle, such as a snow blower or like vehicle, such as a lawn mower, a seed spreader, or any power traction vehicle that is designed for walking behind and requires two modes of control, one for the traction drive of the vehicle and the other for implementing the tool drive associated with the vehicle. A frame member 12 is shown connecting a left handle member 14 and a right handle member 16. Each of the handle members terminates in a hand gripping portion, 18 and 20 respectively. A hand control lever 22 is shown pivoted to the left handle grip 18 for movement between a closed operable position and an opened inoperable position, as well know in the art. A spring, not shown, is usually provided for biasing the handle 22 in its opened inoperable position. In like manner a hand control lever 24 is pivoted to the right handle bar member 20.
Connected to the first mentioned hand control lever 22 is a cable 26 rotatably secured in a known manner to a forward portion of the lever 22, as shown. The cable 26 is guided by a guide support member 28 (to be more fully discussed below) to directly connect in a known manner with a connector 30 for the clutch of the wheel drive of the snow blower, as shown. In like manner a cable 32 is rotatably supported at the forward end of the hand lever 24 and is guided through a cam-slot lever support member 34 (to be more fully discussed below) to directly connect with a connector 36 for the auger drive of the snow blower, as shown in FIG. 1. It will be understood that squeezing either hand lever 22 or 24 with respect to its handle bar 18, 20, respectively, will cause the associated cable 26 or 32 to move either the clutch drive or the auger drive into engagement, as is well known in the art.
In accordance with the invention, one end of a auxiliary control cable system 38 is fixedly secured by any suitable means at 40 to the clutch control cable 26; as a consequence, cable 38 is directly responsive to movement of the cable 26. After being guided by guide support member 28, the other end of cable 38 is pivotally connected to a cam-slot lever 42 at one end 44 thereof. The cam slot lever is rotatably supported by the support member 34 and is provided with a latching recess 45 near its other end as well as a slot 47 inclined with respect to the long axis of the lever and a camming surface 49, to be more fully explained below.
As shown in FIG. 2, the support member 28 is made up of a bracket 46 which is attached by conventional means to the frame 12. The bracket 46 secures by suitable means a guide member 48 which has two orthogonally related guide slots 50, 52. Guide slot 50 guides the auxiliary cable member 38 towards the right handle member and guide slot 52 guides cable 26 towards the clutch connector 30.
As shown in FIG. 3, the cam-slot lever support member 34 comprises a bracket 53 which is secured by suitable means to the frame 12 and in turn rotatably supports about a bushing 54 the cam slot lever 42. A torsion spring 56 surrounds the bushing 54 and has one end secured to the bracket 53 and its other end secured to the cam slot lever 42 in a well known manner for causing the cam slot lever to normally rotate away from the cable 32, to be more fully explained below. The bracket 53 is further provided with a pair of ears 58 having aligned apertures 60 for supporting bushings 62 which serve to guide the cable 32 adjacent the slot 47 in the cam-slot lever 42, as well as to position between the bushings 62 an arresting member 64 in the form of a ball-shaped fitting fixedly secured to the cable 32, to be explained more fully below.
Referring now to FIG. 4 and 5, the exact configuration of the cable 38 with respect to the guide support member 28 and the cam-slot lever support member 34 will be explained. Each of the FIGS. 4 and 5 views the invention from the rear of the traction vehicle 10. In FIG. 4 the auxiliary cable 38 is shown in its inoperable position, wherein the cam-slot lever 42 is normally biased by spring 56 out of engagement with the auger control cable 26. The auxiliary cable 38 is seen to be guided from a generally horizontal direction by the guide connecting guide slots 50, 52 in guide member 48 into a generally vertical direction. The vertical guide slot 52 also allows the cable 26 to travel in a generally vertical direction directly to the clutch connector 30. It will be seen in FIG. 4 that the cam-slot lever 42 is out of engagement with the cable 32 because of the action of torsion spring 56 biasing the lever counter clockwise as seen in the drawing. If, however, the cable 38 is caused to pull the cam-slot lever 42 to the left (counter clockwise) as a result of the cable 26 being pulled by its associated hand lever to engage the clutch drive of the traction vehicle (since the two cable 26 and 38 are directly connected with each other), the slot 47 will then ride into and engage the cable 32. When this happens, it will be seen from the drawing that the arresting or stop member 64 affixed to the cable 32 will be disposed below the lever 42. When, however, the cable 32 is pulled by its associated hand lever to thereby engage the auger drive, the stop member 64 will ride up (its movement facilitated by the roundness of the fitting) along the sloped camming surface 49 of the lever 42 and then slip into the curved latching recess 45 where it will be held from return movement should the hand lever associated with the auger drive and its associated cable 32 be released (see FIG. 5). Should, however, the hand lever associated with the traction drive of the vehicle be released (thus bringing to a stop the traction of the vehicle, usually with the aid of a dead-man stop feature, well know in the art), then the cable 38 will be released, allowing the cam-slot lever 42 to rotate clockwise (as seen in the drawing) to thereby free the stop member 64 from the latching recess 47 and allow the cable 32 to be released, thus disengaging the auger drive.
The operation of the hand lever control system according to the invention is as follows. As described above the two hand levers 22, 24 are mounted on opposite handle bars 18, 20, respectively, of the snow blower. Depression of the traction drive lever 22 will engage the traction drive of the snow blower, while at the same time rotating the cam-slot lever 42 via the cable 38 so that the slot 47 will engage the cable 32 associated with the hand control lever 20 for the auger drive. If now the the hand control lever 20 is depressed, the stop member 64 on the cable 32 will cam along the surface 49 of the cam-slot lever 42 and eventually slip into the latching recess 45 to maintain the auger drive as long as the traction drive is hand lever 22 is depressed. This arrangement, of course, allows the operator to free his right hand from the auger drive hand control lever 24 for whatever purpose without interrupting drive to the auger. Should the operator release the traction drive lever 22, however, the cam-slot lever 42 will rotate away from the cable 32 under the action for the torsion spring 56 to thereby release the member 64 and cause the auger drive to be disengaged. It should be understood that the two hand control levers 22, 24 may be depressed in any sequence and still obtain the same results as above described. It should be also understood that the hand control levers may be reversed with respect to each other from that shown in the drawings, so that the traction drive is on the left and the auger drive is on the right. Since most people are right handed and would prefer that hand to be free during operation of the vehicle, the arrangement as above discussed with respect to the drawings is preferred.
The foregoing relates to preferred exemplary embodiment of the present invention, it being understood that other embodiments and variants thereof are possible within the scope of the invention, the latter being defined by the appended claims. | An auxiliary cable control system in a hand lever control system for a walk-behind traction vehicle is directly responsive to movement of a first hand control lever and acts to latch a second hand control lever in its operable position in response to the first hand control means being moved to its operable position, thus freeing one hand of the operator as long as the first hand control lever remains depressed. The auxiliary control cable has a cable support and a pivotal cam-slot lever that cooperates with a stop member associated with the second hand control lever. Once the traction drive hand lever is released, that is, the traction is stopped, both drives are immediately disconnected by means of the auxiliary cable control system. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is related to application Ser. No. 627,304, filed Oct. 30, 1975, for "Method of Recovering Viscous Petroleum from an Underground Formation," application Ser. No. 627,306, filed Oct. 30, 1975, for "Recovering Viscous Petroleum from Thick Tar Sand," application Ser. No. 643,579, filed Dec. 22, 1975, for "System for Recovering Viscous Petroleum from Thick Tar Sand," application Ser. No. 643,580, filed Dec. 22, 1975, for "Method of Recovering Viscous Petroleum from Thick Tar Sand," and application Ser. No. 650,571, filed Jan. 19, 1976, for "Arrangement for Recovering Viscous Petroleum from Thick Tar Sand".
BACKGROUND OF THE INVENTION
This invention relates generally to recovering viscous petroleum from petroleum-containing formations. Throughout the world there are several major deposits of high-viscosity crude petroleum in oil sand not recoverable in their natural state through a well by ordinary production methods. In the United States, the major concentration of such deposits is in Utah, where approximately 26 billion barrels of in-place heavy oil or tar exists. In California, the estimate of in-place heavy oil or viscous crude is 220 million barrels. By far the largest deposits in the world are in the Province of Alberta, Canada, and represent a total in-place resource of almost 1000 billion barrels. The depths range from surface outcroppings to about 2000 feet.
To date, none of these deposits has been produced commercially by an in-situ technology. Only one commercial mining operation exists, and that is in a shallow Athabasca deposit. A second mining project is about 20% completed at the present time. However, there have been many in-situ well-to-well pilots, all of which used some form of thermal recovery after establishing communication between injector and producer. Normally such communication has been established by introducing a pancake fracture. The displacing or drive mechanism has been steam and combustion, such as the project at Gregoire Lake or steam and chemicals such as the early work on Lease 13 of the Athabasca deposit. Another means of developing communication is that proposed for the Peace River project. It is expected to develop well-to-well communication by injecting steam over a period of several years into an aquifer underlying the tar sand deposit at a depth of around 1800 feet Probably the most active in-situ pilot in the oil sands has been that at Cold Lake. This project uses the huff-and-puff single-well method of steam stimulation and has been producing about 4000 barrels of viscous petroleum per day for several years from about 50 wells. This is probably a semi-commercial process, but whether it is a paying proposition is unknown.
The most difficult problem in any in-situ well-to-well viscous petroleum project is establishing and maintaining communication between injector and producer. In shallow deposits, fracturing to the surface has occurred in a number of pilots so that satisfactory drive pressure could not be maintained. In many cases, problems arise from healing of the fracture when the viscous petroleum that had been mobilized through heat cooled as it moved toward the producer. The cool petroleum is essentially immobile, since its viscosity in the Athabasca deposits, for example, is on the order of 100,000 to 1 million cp at reservoir temperature.
As noted, the major problem of the economic recovery from many formations has been establishing and maintaining communication between an injection position and a recovery position in the viscous oil-containing formation. This is primarily due to the character of the formations, where fluids may be extremely low, and in some cases, such as the Athabasca Tar Sands, vitually nil. Thus, the Athabasca Tar Sands, for example, are strip mined where the overburden is limited. In some tar sands, hydraulically fracturing has been used to establish commuication between injectors and producers. This has not met with uniform success. A particularly difficult situation develops in the intermediate overburden depths, which cannot stand fracturing pressure.
Heretofore, many processes have been utilized in attempting to recover viscous petroleum from viscous oil formations of the Athabasca Tar Sands type. The application of heat to such viscous petroleum formations by steam or underground combustion has been attempted. The use of slotted liners positioned in the viscous oil formation as a conduit for hot fluids has also been suggested. However, these methods have not been overly successful because of the difficulty of establishing and maintaining communication between the injector and the producer.
BRIEF DESCRIPTION OF THE INVENTION
The present invention is directed to a method of assisting the recovery of viscous petroleum from a petroleum-containing formation and is particularly useful in those formations where communication between an injector and a producer is difficult to establish and maintain. A substantially vertical passage such as a well or a shaft is made from the earth's surface through the petroleum-containing formation. At least one laterally extending, usually substantially horizontal hole is extended from the vertical passage through at least a portion of the formation. A flow path is formed in the hole and the flow path is isolated from the formation for flow of fluid through the formation into and out of the vertical passage. A hot fluid is circulated through the flow path to reduce the viscosity of the viscous petroleum in the formation adjacent the outside of the flow path to form a potential passageway for flow of petroleum in the formation outside the flow path. A drive fluid is injected into the formation through the passageway to promote flow of petroleum in the formation to a recovery position for recovery from the formation. In preferred form, the hot fluid is steam and the drive fluid is also steam. The hot fluid and the drive fluid may be injected simultaneously under certain conditions. Under other conditions, the hot fluid and the drive fluid are injected intermittently or alternatively. The injectivity of the drive fluid into the formation is controlled by adjusting the flow of hot fluid through the flow path. In one aspect, the petroleum recovery position is a well penetrating the petroleum-containing formation in close proximity to the flow path and the drive fluid is injected into the formation through the vertical passage. In another aspect, the petroleum recovery position is located in the vertical passage and the drive fluid is injected into the formation through a well penetrating the petroleum-containing formation in close proximity to the flow path.
In a more particular form, the method of the invention deals with a method for recovering viscous petroleum from a petroleum-containing formation of the Athabasca type by providing a substantially vertical passage from the earth's surface through the formation and extending at least one substantially horizontal hole from the vertical passage through at least a portion of the formation. A solid-wall, hollow tubular member having a closed outer end is inserted into the horizontal hole and a flow pipe is inserted into the hollow tubular member to a position near the closed end of the tubular member to provide a flow path from the vertical passage through the horizontal hole into and out of the formation through the interior of the flow pipe and the space between the exterior of the flow pipe and the interior of the tubular member. A hot fluid is circulated through the flow path to reduce the viscosity of the viscous petroleum in the formation adjacent the outside of the tubular member to form a potential passageway for flow of petroleum in the formation outside the tubular member. A drive fluid is forced into the formation through the passageway to promote flow of petroleum adjacent the outside of the tubular member to a position for recovery from the formation. As noted, the preferred hot fluid is steam, although other fluids may be used. Steam also is preferred for use as a drive fluid. In some situations, other fluids such as gas or water may be useful drive fluids.
OBJECT OF THE INVENTION
The principal object of the present invention is to maximize recovery of viscous petroleum from a petroleum-containing formation wherein communication between an injector position and a producer position is difficult to establish and maintain by utilizing a hot fluid circulating laterally from a single well in a physically separated flow path through the formation to assist in establishing and maintaining communication for a drive fluid used to promote movement of the petroleum to the producer. Further objects and advantages of the present invention will become apparent when the description is read in view of the accompanying drawings which are made a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG 1 is an elevation view partially in section and illustrates the preferred embodiment of apparatus assembled in accordance with the present invention for use in recovering viscous petroleum from an underground formation;
FIG. 2 is an enlarged view of a portion of the apparatus of FIG. 1;
FIG. 3 is an elevation view partially in section and illustrates an alternative arrangement of apparatus assembled in accordance with the present invention;
FIG. 4 is a plan view and illustrates a potential well layout in accordance with the present invention;
FIG. 5 is an elevation view partially in section and illustrates apparatus used in conducting demonstrations in accordance with the present invention;
FIG. 6 is a perspective view of a block of tar sand flooded in accordance with the present invention showing position of core samples taken after the flood; and
FIG. 7 is a table illustrating the analysis of such cores. Clearly, if one could establish and maintain communication between injector and producer, regardless of the drive fluid or recovery technique employed, it would open up many of these viscous petroleum deposits to a number of potentially successful projects.
DETAILED DESCRIPTION OF THE INVENTION
Refer now to the drawing, and to FIG. 1 in particular, where the preferred embodiment of apparatus assembled in accordance with the invention is illustrated. FIG. 1 shows a substantially vertical passage or shaft and a spaced-apart well, respectively generally indicated by the numerals 10 and 12, which penetrate the earth to a viscous petroleum or tar sand formation 14. For ease in description, vertical passage 10 will be termed a shaft 10. A lateral hole 16 is extended in a substantially horizontal mode from shaft 10 and terminates in relatively close proximity to well 12. A solid-wall, hollow tubular member 18 is inserted through the hole 16. The tubular member is preferably steel and may be made up of one piece or many connecting joints. The outer end of the tubular member is closed to fluid flow by a suitable end plate 21. The inner end of the tubular member is connected to the casing 24 of the shaft 10 by a suitable flange 11. A flow pipe 20 is inserted into the tubular member 18 and terminates at a position near the closed end 21 of the tubular member. A tubing string 23 is connected to the tubular member 18 in the shaft 10 and extends to the surface. The solid-wall, tubular member 18 and the flow pipe 20 provide a continuous, uninterrupted flow path through the viscous petroleum-containing formation into and out of the shaft 10. Tubing strings 23 serves to extend the flow pipe to the surface through the shaft. If desired, a concentric pipe could be connected between the surface and tubular member 18 to carry condensate to the surface. Generally it is preferred to retain this hot fluid in the well.
The shaft 10 is cased by casing string 24. The casing is perforated or slotted, as indicated by the numeral 26. An opening 28 for the tubular member 18 is also provided in the casing. The upper end of the casing 24 is closed by a wellhead indicated schematically as 30. A steam source 32 is connected through valves 34 and 36 and suitable tubing 38 and 40 to tubing string 23 and thence to flow pipe 20 and thence to the flow pipe 20-tubular member 18 annulus. The tubing string 23-casing 24-annulus 42 is also connected to steam source 32 by means of tubing 38 through valves 34 and 44. Thus, by appropriate control of valves 34, 36 and 44, steam may be directed either simultaneously or alternatively into the flow path formed by the flow pipe 20-tubular member 18 annulus via tubing string 23 and/or into the formation 14 via tubing-casing annulus 42 and perforations 26.
The producer well 12 is cased by a suitable casing by a suitable casing string 46. The casing is slotted or perforated, as indicated by the numeral 48. The producer well 12 is located in near proximity to the flow path provided by tubular member 18 and flow pipe 20. The upper end of the casing string 46 is closed by a wellhead 52. A means for lifting pertroleum from the interior of production well 12 is provided. For example, a pump 56 is used to lift petroleum by a suitable sucker rod string 60 through a production flow path 58 to the surface.
In operation, it is usually desirable to first introduce steam into the annulus 42 of shaft 10 to attempt to obtain injection of steam into formation 14 through perforations 26. In most instances, in viscous tar sands, little or no injection is obtained. In accordance with the invention, steam is then flowed through the formation 14 but out of direct contact therewith in the flow path provided by tubing string 23, flow pipe 20 and tubular member 18 by appropriate manipulation of valves 34, 36 and 44. The steam or hot fluid flowing in this flow path heats the viscous petroleum in formation 14 to reduce the viscosity of at least a portion of the petroleum adjacent the outside of the tubular member 18. This provides a potential passage for flow of the drive fluid or steam through the formation via annulus 42 and perforations 26. By suitably controlling the flow in the flow pipe 20-tubular member 18 annulus and the formation 14, a good sweep efficiency can be obtained and oil recovery maximized at recovery well 12. Thus when the steam flowing in the flow path establishes injectivity for the drive fluid into the formation and results in some production of petroleum from the producer steam flow through the flow path is terminated to prevent breakthrough of the drive fluid. If injectivity of the drive fluid becomes undesirably low, then additional steam is flowed through the flow path to reestablish the desired injectivity. In some instances a back flush or other operation may be necessary at well 12 to initiate production. FIG. 2 is an enlarged view of the ends of the flow pipe 20 and the tubular member 18 showing the closed end 21 which provides the circulating flow path through the formation.
FIG. 3 is an elevation view partially in section and illustrates an alternative arrangement of apparatus assembled in accordance with the invention. FIG. 3 shows a substantially vertical passage or shaft and a spaced-apart well, respectively generally indicated by the numerals 110 and 112, which penetrate the earth to a viscous petroleum or tar sand formation 114. For ease in description, vertical passage 110 will be termed a shaft 110. A lateral hole 116 is extended in a substantially horizontal mode from shaft 110 and terminates in relatively close proximity to well 112. A solid-wall, hollow tubular member 118 is inserted through the hole 116. The tubular member is preferably steel and may be made up of one piece or many connecting joints. The outer end of the tubular member is closed to fluid flow by a suitable end plate 121. The inner end of the tubular member is connected through a hole 128 in the casing 124 of the shaft 110 to a surface string of casing 115. A flow pipe 120 is inserted into the tubular member 118 and terminates at a position near the closed end 121 of the tubular member. A tubing string 123 is connected to the tubular member 118 in the shaft 110 and extends to the surface. The solid-wall, tubular member 118 and the flow pipe 120 provide a continuous, uninterrupted flow path through the viscous petroleum-containing formation into and out of the shaft 110. Tubing strings 123 and 115 serve to extend the flow path to the surface through the shaft. Casing string 115 could be eliminated and the condensate pumped to the surface, if desired.
The shaft 110 is cased by casing string 124. The casing is perforated or slotted, as indicated by the numeral 126. An opening 128 for the tubular member 118 is also provided in the casing. The upper end of the casing 124 is closed by a wellhead indicated schematically as 130. A steam source 132 is connected through valve 134 and suitable tubing 138 to tubing string 123 and then to flow pipe 120 and then to flow pipe 120-tubular member 118 annulus and then to the surface via the tubing 123-casing 115 annulus. A means for lifting petroleum is provided in shaft 110. A downhole pump 156 lifts liquid by a suitable sucker rod string 160 through a production flow path 158. By appropriate control of valve 134 and a valve on the return annular conduit (not shown) steam may be directed into the flow path formed by the flow pipe 120-tubular member 118 annulus to heat the viscous petroleum outside tubular member 118.
An injector well 112 is cased by a suitable casing string 146. The casing is slotted or perforated, as indicated by the numeral 148. The injector well 112 is located in near proximity to the flow path provided by tubular member 118 and flow pipe 120. A steam injection tube 145 terminates near the perforations 148 and the upper portion of the steam injection tube passes through the casing string 146 and a wellhead 152. The injection tube 145 is connected to a steam source 147 by means of conduit 151 through valve 153. Thus, steam may be injected through well 112 into the formation 114 and, in accordance with the invention, assist in moving petroleum toward shaft 110 along the outside of the tubular member 118.
In operation, it is usually desirable to first introduce steam into the injection well 112 to attempt to obtain injection of steam into formation 114 through perforations 148. In most instances, in viscous tar sands, little or no injection is obtained. In accordance with the invention, steam is then flowed through the formation 114 but out of direct contact therewith in the flow path provided by tubing string 123, flow pipe 120 and tubular member 118 by appropriate manipulation of valve 134. The steam or hot fluid flowing in this flow path heats the viscous petroleum in formation 114 to reduce the viscosity of at least a portion of the petroleum adjacent the outside of the tubular member 118. This provides a potential passage for flow of the drive fluid or steam through the formation via injector well 112 through perforations 148. By suitably controlling the flow in the flow pipe 120-tubular member 118 annulus and the formation 114, a good sweep efficiency can be obtained an oil recovery maximized at recovery shaft 110.
FIG. 4 is a plan view of a potential field layout using a central producer shaft and a plurality of spaced-apart injector wells. The plan view of FIG. 4 could, for example, be utilized with the well arrangement shown in elevation in FIG. 3. Thus a central producer well indicated generally by 110 is seen intermediate of spaced-apart injector wells indicated generally by the numerals 112E (east), 112N (north), 112W (west) and 112S (south). The arrangement illustrated in FIG. 4 provides a useful layout in field operations.
FIG. 5 is an elevation view partially in section and illustrates apparatus used in conducting demonstrations in accordance with the present invention. As there shown, a sand pack 70 of Athabasca tar sand was encased in a suitable elongated core tube 72. The core tube was provided with suitable end plates 74 and 76 for receiving a hollow tubular member 78. The apparatus is also arranged for steam injection into the face of the sand pack through conduit 80 and for collecting proceeds of the sand pack flood through conduit 82. A steam source 84 is connected to the tubular member 78 and to the sand pack face through tubing 86 and control valve 88. A down-stream control valve 90 controls flow of steam through the central tubular member 78. Thus, assisted recovery operations in accordance with the invention can be demonstrated utilizing the apparatus shown in FIG. 5.
FIG. 6 is a perspective of a block of Athabasca tar sand showing a number of core positions for cores taken longitudinally through the core block. The cores are identified by number and flow plane as indicated. The tar sand block was flooded in accordance with the method of the invention. The cores were taken after the flood and analyzed for residual petroleum. Stration apparatus similar to that shown in FIG. 5. FIG. 7 is a table indicating the residual viscous petroleum weight by core position and plane of the cores of FIG. 6. The original block contained 13.5% by weight of viscous petroleum. As is evident from the table of FIG. 7, a substantail weight percent of a viscous petroleum was recovered when the block was flooded in accordance with the method of the present invention.
Further with respect to FIGS. 5, 6 and 7, in order to demonstrate the method of the present invention, it was necessary as a first step to set up an apparatus containing Athabasca oil sand having a zero effective permeability to steam. To do this, a 1 inch-ID by 12 inches-long quartz tube was used. The tube was packed with Athabasca oil sand containing about 13% weight viscous petroleum and about 4% water. Fittings were attached to both ends of the tube and a conventional steam drive applied to the oil sand at a pressure of 75 psi and a temperature of 320° F. It was found during the early runs that 50% of the petroleum was recovered because of unrealistic permeability to steam, and so the runs did not successfully simulate Athabasca conditions. It was found later that by using a 1/2 inch-diameter solid steel rod, 12 inches long, as a tool for ramming the oil sand very tightly in the tube, the room temperature air permeabilities were reduced to less than 50 millidarcies, a much more realistic value for viscous petroleum-containing formations. In this region of permeability, conventional steam drive did not work and the steam front advanced only about 1 inch into the tube and no farther, since the initally mobilized petroleum blocked off any communication, thereby reducing the effective mobility to zero. These conditions were reproducible on a satisfactory basis.
The method of the invention was then demonstrated using the apparatus shown schematically in FIG. 5. FIG. 5 shows a partially completed demonstration in accordance with the method of the invention. The in-place tubular member 78 has been heated by opening the heating annulus control valve 90 allowing steam to pass through. This immediately provides steam injectivity at the drive end of the tar sand pack 70 and viscous petroleum produced immediately at the producing end. Recoveries in these experiments ranged from 48 to 52% weight of the total petroleum in place. Residual petroleum was determined in every case by exhaustive solvent extraction at the end of each run. In some demonstrations, too much heat was allowed to pass through the tubular member 78, thereby creating an annulus outside the tubular member of very high mobility, allowing premature steam breakthrough and giving rather poorer recoveries, on the order of only 30% of the total petroleum in place.
In order to demonstrate the present method in a laboratory under more realistic field-type conditions, the demonstrations were modified by using large chunks of relatively undistributed Athabasca oil sand. These ranged in weight from one to about four kilograms and appeared to be devoid of cracks. They were randomly shaped and generally roundish or oval. These were encased in epoxy resin so that a total thickness of about 4 inches existed all around the oil sand piece. The placement of the inplace tubular member and injector and producer were very similar to the apparatus shown in FIG. 5. Again, a 1/8 inch stainless-steel tube was used for the in-place tubular member. In order to establish that there was indeed zero effective mobility, a steam drive was always applied to the injector before allowing any heat to pass through the in-place tubular member. Three experiments were run, and in no case was there more than four drops of water produced at the exit from the block, and this slight water production ceased after less than one minute after initiating conventional steam drive. After reaching this static condition with zero injectivity, the heated annulus control valve 90 was cracked slightly, allowing passing of steam into the tubular member 78. Immediately petroleum flowed from the producer end of the core at a high petroleum/water ratio. Care must be exercised in controlling the amount of heat through the in-place tubular member since, in one case, this was not done and the over-all recovery was 30% of the total petroleum in place. Even continued flowing of steam through the block between injector and producer did not allow any further recovery of petroleum in this instance. On breaking open the block, it was found that a very clean oil sand of higher permeability had been created as an annulus close to the in-place pipe. Since the heat in the tubular member was not controlled, good sweep efficiency of the block was not obtained in this case.
The most successful demonstration run was that carried out on a 3.5-kg block of oil sand, initially 13.5% weight petroleum content. Total recovery was 65% of the petroleum originally in place. In all of these experiments, the same pressure and temperature of 75 psi and 320°F respectively were used.
Although, at first glance, the practice of the invention might lead one to expect a very low residual oil content close to the annulus surrounding the in-place tubular member and a high residual oil resulting from poor sweep efficiency in those regions of the sample farthest away from the in-place pipe, this was not the case. In fact, excellent sweep efficiency is obtained when the ratio of hot fluid to drive fluid is controlled so as not to permit early steam breakthrough. In order to evaluate this concern, the encased 3.5-kg block of oil sand at the end of a demonstration was cut through the center at right angles to the in-place tubular member. The oil sand was then cored using a 3/4 inch-diameter core borer and sampled to a depth of 1/2 inch. This was done at 11 locations in each of 6 different planes in the oil sand block. A diagram of the location of these core samples is shown in FIG. 6. A total of 66 samples was taken and each analyzed for residual petroleum content by exhaustive extraction with toluene. The results are shown in FIG. 7. It can be seen that a remarkably uniform sweep of the oil sand sample had taken place. Particularly surprising is the fact that the residual petroleum in those 6 cores taken from the annulus immediately surrounding the in-place tubular member show a residual petroleum content not too different from the cores farthest away from the in-place tubular member.
The demonstrations show that the method of the present invention satisfactorily simulated the zero effective mobility of the Athabasca oil sand deposit. The recovery demonstrations showd that a communication path between injector and producer can be successfully developed; and provided excessive heating of the in-place tubular member is avoided, recoveries up to 65% of the petroleum in place can be achieved. The sweep efficiency is surprisingly high, resulting in an even distribution of residual oil. This means that the reservoir after an assisted-recovery operation conducted in accordance with the invention would be amendable to further recovery techniques such as combustion, chemical floods, etc. Particularly attractive is the fact that injecting drive fluids would be confined to the area of interest between injector and producer, since this would be the only pathway open to them. In other words, it is unlikely that the fluids would be lost to the other parts of the reservoir because of the relative impermeability of the formation on the outer edge of the swept area. | Recovery of viscous petroleum such as from tar sands is assisted using a substantially vertical passage from the earth's surface which penetrates the tar sand and has extending therefrom a lateral hole containing a flow path isolated from the tar sand for circulating a hot fluid to and from the vertical passage to develop a potential flow path into which a drive fluid is injected to promote movement of the petroleum to a production position. | 4 |
BACKGROUND OF THE INVENTION
[0001] The subject invention relates to a scanner device for generating a three dimensional (3D) surface model of arbitrarily shaped objects, such as dental structures, preferably applicable for use in the field of stomatology, dentistry, or orthodontics, and particularly to dental prosthetics manufacturing. More specifically, the subject invention includes an intraoral 3D dental scanning device and methods for imaging and visualizing teeth or gingivae surfaces, including the conformation thereof.
[0002] Three-dimensional (3D) diagnostic and therapeutic modeling of teeth and gingivae have been traditionally obtained by mainstream techniques, such as using replicas obtained from alginate-impressed molds. Such replicas provide gingiva and tooth negative-image molds, which can later be converted into positive models, which may be scanned. However, these mainstream techniques pose problems and disadvantages which are manifold. These problems include: patient discomfort during the process of creating the mold, creation of imperfections and inaccuracies in the resulting mold, and the process can be slow and costly.
[0003] More recently, several state-of-the-art devices have been developed, e.g., panoramic dental X-rays, computerized dental tomographies, and optical scanning devices, that attempt to solve the problems posed by mainstream techniques. Optical scanners are devices which can capture and record information from the surface of an object, and generate that information into an image.
[0004] The use of scanners to determine the surface contour of objects by non-contact optical methods has become increasingly important in many applications including the in vivo scanning of dental structures to create a 3D model. Typically, the 3D surface contour is formed from a cloud of points where the relative position of each point in the cloud represents an estimated position of the scanned object's surface at the given point.
[0005] Such optical scanning devices have been developed and made commercially available for the dental market, and have been described in the patent literature incorporating a variety of technologies and configurations. For example, certain European patents have been identified as describing scanning devices, such as: EP 0825837, entitled, “Modular intra-oral imaging system video camera,” provides a hand-held video camera to capture images of the inner part of the mouth and an optically aligned sensor which converts the captured images into usable data; ES 2383220, entitled “Intraoral dental imaging sensor and X-ray system, using such sensor,” describes an intraoral dental radiological system equipped with a mouth-insertable X-ray imaging sensor having an image-detection matrix to provide electronic signals, and a light source to receive the matrix-generated signals; and ES 2324658 (T3), entitled “Laser-digitalizing system for dental applications” describes a laser digitizer that has a light source with collimation optics to generate a collimated light beam, a scanner optically coupled with the light source.
[0006] Optical scanning devices have also been patented or published in the United States, for example, in U.S. Pat. No. 6,648,640, entitled “INTERACTIVE ORTHODONTIC CARE SYSTEM BASED ON INTRA-ORAL SCANNING OF TEETH”; U.S. Pat. No. 4,837,732, entitled “Method and Apparatus for the Three-Dimensional Registration and Display of Prepared Teeth”; U.S. Pat. No. 4,575,805, entitled “Method And Apparatus For The Fabrication Of Custom-Shaped Implants”; U.S. Pat. No. 5,372,502, entitled “Optical Probe and Method for the Three-Dimensional Surveying of Teeth”; U.S. Pat. No. 5,027,281, entitled “Method and Apparatus for Scanning and Recording of Coordinates Describing Three Dimensional Objects of Complex and Unique Geometry”; U.S. Pat. No. 5,431,562, entitled “Method and Apparatus for Designing and Forming a Custom Orthodontic Appliance and for the Straightening of Teeth therewith”; U.S. Pat. No. 6,592,371, entitled “Method and System for Imaging and Modeling a Three Dimensional Structure”; and U.S. Pat. No. 7,004,754, entitled “Automatic Crown and Gingiva Detection from Three-Dimensional Virtual Model of Teeth”; as well as U.S. Publication No. 2006/0154198, entitled “3D Dental Scanner.”
[0007] These systems and devices previously described all have various disadvantages in their design and use in practice. Commercially available 3D scanner systems have been developed for the dental market typically employ a handheld (by the operator), wand-type scanner in communication with a central (and typically large and bulky) computer/power source. In these systems, the operator moves the scanner over the area to be scanned and collects a series of image frames. The intraoral cavity represents a significant challenge for accurate in vivo 3D imaging of the surface of teeth and tissue. The ability to accurately measure the center of a scanning line is affected by the translucency of teeth, the variety of other reflecting surfaces (amalgam fillings, metal crowns, gum tissue, etc.) and the obscuration due to adjacent surfaces. Further, linear or rotational motion adds to error accumulation and the variation in size and curvature of human jaws makes a “one size fits all” scanner problematic.
[0008] In addition to the inaccuracies that can be introduced, these state-of-the-art devices and systems can be inconvenient to use, and inconvenient for the patient. In some cases, a technician must manually operate the handheld wand using a toothbrush-like motion and the results can depend on the dexterity and skill of the operator. Systems based on photographs taken by the various devices where software interprets and interpolates the photographic information into a final 3D image, can be time-consuming.
[0009] Thus, what is needed in the art is a 3D scanning device, and system, which can address and overcome disadvantages and limitations of the devices and systems which have been previously described and marketed.
[0010] The subject invention addresses and overcomes certain disadvantages of prior systems and devices by providing a completely integrated, unitary device, which is portable, and can be easily held by the patient during use. Thus, the invention provides a dental scanning device without certain flaws and inconveniences of the previously known state-of-the-art systems, capturing accurate 3D images using a fixed-reference system. No handheld wand is required, and no manual operation of the scanning probe is necessary by a technician or a patient, as the device and system is fully automated.
SUMMARY OF THE INVENTION
[0011] The subject invention comprises a 3D scanning device and system especially useful in the field of stomatology, dentistry, or orthodontics, and particularly to dental prosthetics manufacturing. The device and system of the invention is particularly applicable for imaging the surface characteristics of an object, including arbitrarily shaped objects, such as dental structures (e.g., teeth, gingiva, and the like), for generating a three-dimensional (3D) image and surface model of the object or objects. More specifically, the subject invention includes an intraoral 3D dental scanning device and method for imaging and visualizing teeth or gingivae surfaces, including the conformation thereof, useful for generating dental models and the manufacture of dental prosthetics therefrom.
[0012] Thus, the subject invention comprises a unitary, portable scanning device for performing a a three-dimensional scan of an object, wherein the device comprises a scanning probe comprising an extending arm coupled at one end to a mobility mechanism and at another end having a scanning probe head comprising an imaging source for generating an image of an arbitrarily shaped structure. The imaging source can employ optical, X-ray, radioisotope, magnetic, sound, CCD, or CMOS imaging. Optical imaging can include or employ visible, infrared, or ultraviolet light.
[0013] The mobility mechanism provides for extension/retraction, and lateral, movement of the scanning probe from a fixed reference point. The mobility mechanism and at least a part of the extending arm of the scanning probe is encased within a housing body formed as a hollow shell having a chamber for encasing at least a portion of a scanning probe and encasing the mobility mechanism which moves the scanning probe.
[0014] The housing body preferably comprises an opening through which the scanning probe extends for scanning the object.
[0015] The device of the invention can be configured as a table-top scanning device. More preferably, the device is configured as a portable, or hand-held intraoral scanner for scanning dental structures in the mouth of a patient or subject.
[0016] For use as an intraoral scanner, the housing body opening is configured to receive or engage a mouthpiece. The mouthpiece has a top and bottom face separated by side walls to form a hollow bite fixture onto which the subject can bite down upon during a scanning procedure. The bite fixture has distal and proximal ends, wherein the proximal end engages with the opening of the housing body and is open for communicating with the chamber of the housing body. The open proximal end of said mouthpiece receives and allows movement of the scanning probe therewithin during a scanning procedure.
[0017] Preferably, at least one of the top or bottom faces of the bite fixture comprises a transparent or translucent window to allow communication between the optical imaging source and imaging receiver or sensor.
[0018] The scanning device of the invention can comprises a chassis holding a mobility mechanism for moving the extension arm and scanning probe. The scanning probe comprises a scanning probe head holding at least one imaging source or a plurality of imaging sources. Preferably, the mobility mechanism moves the scanning probe automatically in a pre-programmed scanning pattern without further manipulation by an operator. Thus, the scanner device of the subject invention, which employs automatic movement and a pre-programmed scanning pattern of the extension arm and scanner probe, provides for a wand-less scanning probe and scanning procedure.
[0019] Advantageously, the pre-programmed scanning pattern provides movement only along an X-axis and Y-axis, or along a horizontal plane, and does not provide or allow movement of the extension arm or scanner probe head in a non-vertical (Z-axis) direction.
[0020] The subject invention further concerns a method of performing a dental scan, said method comprising the steps of: (1) providing a scanning device as described herein, and (2) performing a scanning procedure on a subject or patient.
[0021] A method of the subject invention can further comprise the step of: printing, milling, or 3D-printing a dental structure using the information obtained from the scanning procedure.
[0022] In addition, the subject invention relates to a system for carrying out a dental scan on a patient, wherein the system comprise a portable scanning device as described herein, and an external device selected form a printer, a milling machine, and a 3D printer. The scanning device can include an integral mouthpiece or bite fixture or can optionally include a separate mouthpiece or bite fixture which matingly engages the housing of the device. a separate mouthpiece, an optional cable for connecting the device to an external printing, milling or 3D printing device, and a carrying case for containing said device, mouthpiece and optional cable.
[0023] The system of the invention can further include a connecting cable for connecting said device to an external printing, milling, or 3D printing device and may optionally include a carrying case for one or more components of the device, such as the housing, bite fixture, connecting cables or external printer or milling device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 shows an embodiment of a device according to the subject invention, illustrating a top or bottom view of the housing body and mouthpiece in an engaged configuration;
[0025] FIG. 2 is an exploded top or bottom perspective view of an embodiment according to the subject invention, illustrating the chassis and scanning probe components housed within the housing body.
[0026] FIGS. 3A-3C show various views of the mouthpiece wherein:
[0027] FIG. 3A is a perspective view of an embodiment of a mouthpiece for the subject device, illustrating the transparent or substantially translucent top or bottom panel thereof, and a circumferential flange positioning stop;
[0028] FIG. 3B is a perspective view of an embodiment of a mouthpiece for the subject device, showing an exploded view of the transparent or substantially translucent top or bottom face of the mouthpiece;
[0029] FIG. 3C is a perspective view of an embodiment of a mouthpiece for the subject device, illustrating the scanning probe within the chamber formed by the mouthpiece.
[0030] FIG. 4 illustrates an embodiment of the device of the invention, hand-held and in use by a scanning subject during a scanning procedure;
[0031] FIG. 5 illustrates another embodiment of a device of the invention, illustrating a mounted embodiment, which can be affixed to a base.
DETAILED DESCRIPTION OF THE INVENTION
[0032] A device of the subject invention comprises, in a preferred embodiment, a housing body that is preferably capable of being held in the hand or hands of a person. By the phrase, “capable of being held in the hand or hands of a person,” is meant that the housing body is configured having a size and weight that can be readily held in one or both hands by a user or scanning subject during a scanning procedure.
[0033] The housing body of the device contains or encases a chassis providing a mobility mechanism for moving, guiding, or directing a scanning probe coupled to the mobility mechanism. By providing a mobility mechanism for operating the movement of the scanning probe in a fixed or pre-programmed pattern relative to the scanning subject, the device and its use can advantageously provide a fixed reference point for the scanning probe, obviating the need for a hand-manipulated wand.
[0034] The scanning probe comprises an arm or stem coupled to the mobility mechanism at a first proximal end of the arm, and having a scanning head positioned at an opposite, distal end of the arm. The scanning head comprises an imaging source affixed thereto or integral therewith, such as an infrared or light-emitting diode (LED) or laser light source, and can comprise a sensor, transducer or receiver for capturing an image generated by the imaging source when projected onto the surface of the object, such as dental structures. The scanning head can further include a camera or a plurality of cameras for photographic or video images which can be converted to three-dimensional images using available computer software or other computer technology.
[0035] Thus the scanning head can comprise one or more imaging components, such as but not limited to an optical imaging source, for generating an imaging source and capturing or storing the generated image, as described and well understood in the art. It would be readily understood that the imaging source can alternatively employ imaging generated by one or more of optical, X-ray, radioisotope, magnetic, sound, charge coupled device (CCD), or complementary metal oxide semiconductor (CMOS) imaging sources as are currently used in the art, or other imaging sources in development. Optical imaging includes, and is not limited to, visible, infrared, or ultraviolet light. Advantageously, the optical imaging source does not require a collimator for focusing the imaging light source and can be provided with or without a collimator. Accordingly, a device of the subject invention can comprise a collimator or can be collimator-free.
[0036] The housing body of the device, which is preferably formed as a molded plastic shell, is provided to enclose or completely encase both the mobility mechanism and at least a portion of the scanning probe (such as the probe arm) when the device is “at rest,” i.e., when in an “off” position or not in scanning mode. The housing body comprises an opening whereby, during its operation, the scanning head of the scanning probe, and typically a portion of the arm of the scanning probe, extends outside the housing body to carry out an imaging process or scan, when “on” or in scanning mode.
[0037] The scanning probe can be partially or completely contained within the housing body when a scan is not being performed, and can be moved outward by the mobility mechanism to project outside the housing body for intraoral scanning of dental structures (e.g., teeth, gingiva, and the like) in a patient.
[0038] In a typical embodiment of the invention, one end of the probe arm is coupled to the mobility mechanism within the housing body, wherein said probe arm extends outside the housing body, and the probe head is also outside the housing body.
[0039] Thus it would be understood that one embodiment of the scanner device of the invention is useful as a table-top scanner of an object.
[0040] In one preferred embodiment for use as an intraoral scanner, the probe head can be protected outside the housing body by a mouthpiece which chambers or encloses the probe head during the scanning operation. It is contemplated that the entire scanning probe can be withdrawn inside the housing body for full protection of the scanning probe, including the probe head, when in an “off” position or not performing a scanning procedure.
[0041] The optional mouthpiece, as further described herein below, used for intraoral scanning can be formed as part of or integral with the housing of the scanning device, or can be a separate component of the device. Preferably, a mouthpiece forming a separate component of the scanning device can matingly engage and be received by the opening in the housing. More preferably, the mouthpiece is formed as a bite fixture which is held in the subject's or patient's mouth during the scanning procedure and can be disengaged from the scanning device and replaced for each user.
[0042] Advantageously, the subject device can be portable, and completely self-contained and hand-held during a scanning operation, meaning that the device does not require a separate hand-held probe wand cabled to an image processor. Hand-held probe wands, and operation thereof by hand, are well known in the industry, but can introduce extraneous linear and rotational motion during hand operation of the wand, which can result in image artefact and increased time for image processing. These disadvantages of a separate, hand-held probe wand can be due to, for example, a requirement for the image processor to continuously or frequently re-calculate reference positioning, which can increase total time of the scanning procedure.
[0043] By contrast, the subject device does not include or require a hand-held wand, i.e., the device is wand-less or wand-free, whereby the scanning probe has a fixed reference position at all stages of the scanning procedure. The scanning probe of the subject invention does not require manipulation by an operator at any time. The movement of the scanning probe of the subject device can preferably be driven by a mobility mechanism operated by a motor, such as an electric or electronic stepping motor. When engaged or turned “on”, the motor-driven mobility mechanism moves the scanning probe automatically in a pre-programmed scanning pattern without further manipulation by an operator.
[0044] In accordance with the subject invention, the device is unitary, whereby the entire imaging unit, including the scanning probe, is controlled and operated by the device, itself, while the mouthpiece is held in a fixed position in the mouth of the subject, thereby providing a fixed reference position for the scanning probe. Thus, the scanning probe, itself, is not hand-held or otherwise manipulated by hand; rather the entire unit is held in a steady or fixed position during the scanning procedure, and the scanning probe, which is integral with the unitary device, is directed by the mobility mechanism to move in a controlled or pre-programmed pattern to carry out a scan. Such pre-programmed pattern is typically an arc pattern, corresponding to the dental arch of a patient or subject on which the scan is performed.
[0045] The housing body, in a preferred embodiment, is ergonomically designed having a size and shape, such as rounded or contoured edges, for being easily held by a patient during use. The housing body is preferably formed by plastic or other light material, molded or otherwise shaped to form a shell structure having a hollow chamber therein. The chamber formed within the housing body shell, which contains the mobility mechanism coupled to, and for movement of, the scanning probe, further encases the electronics and mechanical positioning apparatus for controlling the movement and operation of the scanning probe. For example, the mobility mechanism for moving the scanning probe comprises a chassis, onto which the positioning apparatus is provided, including the operational control mechanism for movement of the probe.
[0046] The positioning apparatus can include an extension arm coupled to the stem or arm of the scanning probe, to extend and retract the scanning probe to and from within the chamber of the housing body. For ease of reference, the movement of the scanning probe is said to move outward, in a distal direction from the center of the housing body, and inward, in a medial or proximal direction toward the center of the housing body. The chassis can further have coupled thereto a lateral rod or gear system providing for lateral (horizontal or side-to-side) movement of the scanning probe.
[0047] These mechanisms and apparatus for movement and positioning of the scanning probe, i.e., for extending/retracting and for lateral movement of the scanning probe are well understood within the mechanical arts. Preferably, the scanning probe is moved only in the in/out and side-to-side directions, and does not move vertically, retaining a constant horizontal plane, within the confines of the mouthpiece, during operation.
[0048] The mechanical positioning mechanism can be controlled by electronics, such as an electronically driven motor, which can direct and control the movement and position of the scanning probe. A preferred embodiment of the device is powered by a motor driven by electricity or by battery-stored electricity, wherein a battery or other power source can also be contained within the housing body. Alternatively, the electric motor can be connected to an external electrical power source by a cable or electrical cord.
[0049] The electronics directing the movement of the scanning probe can be controlled by computer software, provided and stored within or without the housing body, and the software can provide a menu of functions, such as ON/OFF, SCAN, or other desired functions, operated by one or more switches or buttons positioned on the outer top or bottom face of the housing body. Preferably, the device comprises a set of switches or buttons on each of the top and bottom face of the device housing.
[0050] Providing two sets of switches or buttons, one on each of the top and bottom face of the housing body, allows for the device to be operated in dual positions, i.e., upward-facing position and downward-facing position. By “upward-facing” is meant that the probe head and light source are positioned to face upward, toward the top teeth during a dental scan; by “bottom-facing” is meant that the probe head and light source are positioned to face downward, toward the bottom teeth during a dental scan. Therefore, for conducting a complete scan of the top and bottom teeth of a patient, the device can advantageously be positioned in a first direction, e.g., upwardly, to scan the upper teeth, then turned approximately 180° and positioned in the other direction, e.g., downwardly, to scan the bottom teeth. A housing body having switches or buttons on both the top and bottom face can facilitate operation of the device in either upward or downward facing position.
[0051] The housing body can further comprise a connector or port for engaging a cable for communication with a computer or image processor for processing or storing information received from the sensor, transducer or receiver of the scanning probe. Alternatively, the device can comprise a wireless transmitter/receiver for wirelessly communicating with a computer, whereby the wireless transmitter/receiver can be provided integral with the device or housed within the housing body.
[0052] Positioning of the device and scanning probe for optimal intraoral scanning results is facilitated by the mouthpiece or “bite fixture”, which engages the device and provides a protective cover for the scanning probe. Configured for being easily and comfortably held in the patient's mouth during a scanning procedure, the mouthpiece is preferably a generally flat rectangular housing having side walls and top and bottom walls forming and surrounding a generally flat, rectangular hollow chamber.
[0053] The top and bottom walls provide a surface for the patient to bite down onto during the scanning procedure, advantageously providing a fixed position of the teeth during a scanning procedure. This fixed position of the teeth on the mouthpiece provides for and facilitates a fixed reference point relative to the scanning probe, which moves in a pre-programmed pattern during a scanning procedure. Thus, by virtue of the fixed intraoral position of the bite fixture, the scanning probe retains a stable relative position in the mouth of the patient or subject and retains a fixed scanning pattern relative to, and irrespective of, any movement or positioning of the head of the subject or patient.
[0054] This fixed intraoral positioning of the device provides an advantageously comfortable experience for the patient because the scan to be conducted without strict restraint or immobilization of the patient's or subject's head using an external head-restraining device. The fixed intraoral position of the bite fixture can provide for diminished risk of scanning artefact caused by inadvertent head movement of the patient or subject during the scanning procedure, and allows the scanning procedure to be carried out successfully even in the event of slight head movement on the part of the patient or subject.
[0055] The mouthpiece of the device can be configured to engage, and preferably be separable from, the opening provided in the housing body. The mouthpiece is provided as a platform having at least top and bottom faces spaced apart from one another, onto which the patient or scanning subject can bite down onto during a scanning procedure. The top and bottom face are preferably substantially solid planar panels, connected to, but spaced apart from, one another by substantially planar side walls which, together, form or bound the substantially rectangular hollow chamber.
[0056] The mouthpiece advantageously serves to facilitate positioning and stabilization of the “bite” by the patient or scanning subject, so that the teeth or dental arch being scanned are held in a fixed position during the scanning procedure. The mouthpiece can further serve to protect the scanning probe as it extends into the oral cavity during operation of the device during a scanning procedure.
[0057] At least one top or bottom face of the mouthpiece comprises a transparent, or sufficiently translucent window, to allow the scanning light source to penetrate therethrough, and to allow return of light information to the sensor, transducer, camera, or receiver on the scanning probe head to perform a scanning procedure. Generally, the transparent or translucent window is a panel sized to correspond or conform to the entire dental arch being scanned. Different shapes and configurations of the transparent or translucent window are contemplated and are not critical to the invention so long as the configuration provides for scanning the targeted teeth of the patient or subject.
[0058] As stated, the front end of the mouthpiece, facing toward the patient and within the oral cavity during operation or use, can be closed or open, but is preferably closed by a front wall. The opposite end of the front end or wall is open to communicate with the hollow chamber of the housing body. The hollow chamber formed within the mouthpiece receives the scanning probe and provides an area for the scanning probe to enter, extend, retract, and move laterally and perform a scan.
[0059] Various shapes and configurations can be used for the mouthpiece so long as it provides for positioning in the mouth, a bite platform, and allows for movement of the scanning probe therein. A preferred embodiment can comprise a shape conforming generally to the shape of the dental arch. Positioning guides, such as printed, formed or grooved indicia, or contours can be provided on the mouthpiece, but a generally flat wall comprising the scanning widow is preferred in order to reduce optical artefact during the scanning procedure.
[0060] In a preferred embodiment, however, the generally rectangular mouthpiece can include a generally “V”-shaped or “U”-shaped open area which provides room for the patient's tongue to move more freely, facilitating breathing and reducing the likelihood of inducing a feeling of choking or a “gag-response” by the patient.
[0061] As mentioned, it is preferred that the mouthpiece is separable from the housing body, and more preferably, easily engaged to or disengaged from, i.e., easily separable from and affixable to the housing. To facilitate ease of engagement or disengagement from the housing, the opening of the housing for receiving the mouthpiece or bite fixture can be matingly configured to the engagement end of the mouthpiece or bite fixture.
[0062] A separable mouthpiece can facilitate its use under sanitary conditions, either allowing removal of the mouthpiece from the housing body to perform cleaning/sterilization procedures between uses or, when made from cost-effective material, such as an inexpensive plastic, can be provided as a disposable, one-time-use-only mouthpiece that can be affixed to the scanning device for each use, and discarded thereafter.
[0063] It would be understood that the mouthpiece can be formed as an integral part of or unitary with the housing body. While an integral mouthpiece formed as part of the device can include a removable cover or sleeve provided for each patient for maintaining sanitary conditions, this integral mouthpiece embodiment does not readily provide for different sizes of mouthpieces to accommodate different sizes of mouths, such as adult-sized and child-sized mouths. Accordingly, a preferred embodiment comprises a separate and removable mouthpiece, which is not formed permanently integral with the housing body.
[0064] A removable cover or sleeve can be provided for the separable mouthpiece as well, and can be useful for maintaining sanitary conditions or can provide cushioning or a comfortable mouth-feel for the patient or subject. It is preferred that a material used for the bite fixture cover or sleeve does not interfere with communication between the scanning source and sensor or receiver.
[0065] An embodiment of the invention comprising a separable or removable mouthpiece can provide the capability of at least two or more sizes of a mouthpiece. For example, one size of mouthpiece can be provided for adult mouths, and another, smaller size of mouthpiece can be provided for children. Intermediate or larger or smaller sizes can also be provided. Each size of mouthpiece has the same configuration, i.e., is the same size, at its end engaging the housing body, so that multiple sizes of mouthpieces can fit and engage with a single housing body of a device.
[0066] In one preferred embodiment, the mouthpiece comprises at least one flange or annular ridge around its circumference so that it provides a positional “stop” or indicator when properly engaging with the housing body. This flange or annular ridge can further serve as a positional indicator for proper placement of the mouth onto the mouthpiece during a scanning procedure.
[0067] The device, as described can be included as a system for scanning dental structures, wherein the system comprises the components of the device as described, and can further include external, in-line devices which are used in conjunction with the scanning device for providing a dental scan. External devices can receive, process, or utilize the information provided by the dental scan. For example, a system of the subject invention can comprise a printer for printing a photograph from the scan information, a milling machine for constructing a prosthetic dental structure (e.g., a crown or denture) from the scan, or a 3D printer for printing a prosthetic dental structure.
[0068] Methods of using a scanning device of the subject invention are also within the scope of the invention. For example, a method of use can include the steps of (a) providing a scanning device as described and (b) performing a scanning procedure on a subject or patient. The method can further comprise an additional step (c) of printing, milling, or 3D printing a dental structure using the information obtained from the scanning procedure.
[0069] Advantageously, the scanning device of the subject invention can provide a method for scanning teeth and gingivae without the need for imaging powder or imaging gel applied or administered to the teeth or gingivae of the patient or subject. Thus the subject method can be a powder-free or gel-free scanning procedure, which can save time, cost, and reduce discomfort to the patient or subject.
[0070] To describe and illustrate the components of a device of the invention, reference is made to the accompanying drawings, whereby: FIG. 1 shows an embodiment of a device 100 according to the subject invention, illustrating a top or bottom view of the housing body 101 and mouthpiece 102 in an engaged configuration. Reference is made to “either” the top face or bottom face of the device because, in a preferred embodiment, the device is symmetrical wherein the top and bottom faces are identical or at least substantially identical so that the device can be operated in an identical or substantially identical manner when facing upward or downward.
[0071] During operation, the device is positioned, for example, upwardly to perform a scan of an upper dental arch, and the device may then be rotated approximately 180° to face downward for scanning, for example, the lower dental arch. In both instances, a control panel 103 provided on each top and bottom face, provides for easy access and manipulation of the control panel on the “upper” face (facing upward at the time of operation).
[0072] Thus, as shown here, the outer (top or bottom) face comprises a control panel 103 integral with the face wherein the control panel comprises a menu screen 104 for viewing a menu of available operations or functions on menu screen 104 . The operation of the device can be controlled by manipulating one or more buttons or set of buttons provided as part of the control panel. Here, an embodiment is shown having a set of five (5) buttons, specifically, buttons 105 a , 105 b , 105 c , 105 d , and 105 e , for controlling the menu and function or operation of the device.
[0073] Buttons 105 a and 105 b , for example, can manipulate a scrolling function of a menu display, allowing the user to scroll up or down on a displayed menu page; buttons 105 c and 105 d , can control the selection of different pages of the menu, for example, button 105 c providing the operation to return to a previous page of the menu, and button 105 d providing an operation of moving forward to a next page of the offered menu. Button 105 e can be used for initiating the “scan” operation, and can further perform “on/off” functions or the like.
[0074] It would be readily understood that a great variety of styles and designs can be incorporated into the control panel, and the particular style or design is not critical, so long as the device provides user-friendly options for functionality and operation of the device.
[0075] The housing body can be molded or otherwise fabricated using plastic or other appropriate lightweight material, and can be formed as a single unit, or can be formed as sections, example upper and lower halves, which are fitted together to form the single housing body unit.
[0076] Mouthpiece 102 is shown engaged with an opening (not shown) formed in one end of housing body 101 . The embodiment of mouthpiece 102 as shown here, comprises a transparent panel forming a top or bottom face of the mouthpiece. In addition, mouthpiece 102 illustrates a substantially “V”- or “U”-shaped cut-out area 107 formed therein. This is a preferred configuration for a mouthpiece of the invention, conforming generally to the shape of the dental arch, and further advantageously minimizing obstruction of a patient's airway, and gag-response, while permitting the scanning probe to reach the full dental arch during a scanning procedure.
[0077] At an end of the housing body, opposite the mouthpiece, is a connector port 106 , for coupling the device, via a cable, to a computer, image processor, milling machine, printer (e.g., a 3D printer), or the like for transferring information received by the scanning probe to an external device. This connector can alternatively provide for wireless connection, i.e., be configured as a wireless transmitter, for wirelessly transferring image information to an external device. It would be understood that the location of the connector can be at any position on or within the housing body, so long as it fits within the function and design of the device.
[0078] Alternatively, this connector port 107 can be configured as part of a male/female coupling means for coupling the device to a base or stand, providing for hands-free use of the device during a scanning procedure (see, for example, FIG. 5 , and accompanying description, below).
[0079] FIG. 2 is an exploded top or bottom perspective view of an embodiment of scanning device 100 according to the subject invention, illustrating the housing body 101 formed from two halves 101 a and 101 b . This view further illustrates a chassis 201 provided for holding a mobility mechanism coupled to and providing movement for a scanning probe 203 comprising a an arm or stem 204 and a scanning head 205 .
[0080] The mobility mechanism comprises one or more stabilizing bars or rods and a rotating screw mechanism for lateral movement of the scanning probe 202 a and one or more stabilizing bars or rods and rotating screw mechanism 202 b for distal/proximal (in/out) movement of the scanning probe.
[0081] Further shown in FIG. 2 is opening 206 formed or provided at one end of the housing body, such that the mouthpiece can engage the housing body, and the scanning probe can extend from within the housing body into the chamber 207 of the mouthpiece.
[0082] FIGS. 3A-3C show various views of one embodiment of the mouthpiece component of the device of the invention wherein: in FIG. 3A is illustrated mouthpiece 301 comprising a top face 302 and bottom face 303 , spaced apart from one another by side walls 304 and 305 forming a hollow chamber 306 therein.
[0083] Open end 307 engages with the housing body of the device, and provides for communication with the chamber of the housing body and for receiving a scanning probe (not shown) in the formed chamber of the mouthpiece. An intraoral end of the mouthpiece can be open or closed, but is preferably closed by front (intraoral) wall 308 .
[0084] In the embodiment shown, top face 305 comprises, at least in part, a clear or transparent plastic material for allowing a scanning source, such as infrared or laser light, to pass therethrough without interference or distortion of the light source, or the information returning to a sensor, receiver, or transducer provided in or on the scanning probe head.
[0085] Also illustrated in FIG. 3A is a circumferential (or annular, if substantially circular or ovoid shaped) flange or ridge 309 which can provide a positional “stop” for engaging the mouthpiece to the housing body. The flange or ridge 309 can also function as a “stop” for the lips or mouth of the subject.
[0086] In FIG. 3B , the mouthpiece 301 of FIG. 3A is shown in an exploded view, illustrating the clear or transparent top face 302 of mouthpiece 301 , and showing front (intraoral) wall 308 .
[0087] FIG. 3C provides illustration of scanning probe 310 comprising a scanning head 311 inside the mouthpiece chamber 306 , coupled to an arm or stem portion 312 extending from within the housing body. The scanning probe 310 can move distally/proximally (in/out) and laterally in the directions depicted by the arrows. The scanning probe head can comprise one or more imaging sources, such as a light source for generating the image. In one preferred embodiment, the imaging source can comprise a plurality of light sources, e.g., LED laser light. The scanning probe head can preferably comprise at least one light source, more preferably about four to about ten light sources, and typically about six to about eight light sources. These plurality of light sources are well understood in the art to be configured to communicate together to generate a single 3-dimensional image.
[0088] FIGS. 4 and 5 illustrate one embodiment of a device of the subject invention in use. Specifically, FIG. 4 shows a hand-held embodiment, wherein device 401 is held by the subject 402 during operation of the device to conduct a dental scanning procedure. FIG. 5 illustrates an alternative embodiment, mentioned above, whereby the device 501 is coupled to or mounted on a mounting base or stand (not shown) having an extension arm 502 for holding the device in position during a dental scanning procedure.
[0089] Having illustrated and described preferred embodiments of a device of the invention, said device can be used for performing a dental scanning procedure on a subject. In use, the device and mouthpiece are engaged together to form a single unit. The control panel is set to the desired function by the operator of the device and the mouthpiece, engaged with the device, is introduced into the oral cavity of the subject, positioned so that the mouthpiece contacts or positionally conforms to the entire dental arch. The subject preferably bites onto the mouthpiece for securing the position of the dental arch in relation to the mouthpiece and reducing the unnecessary movement of the device in relation to the dental arch during the scanning procedure.
[0090] The operator of the device then presses the “scan” function on the control panel to begin the scanning procedure, whereby the scanning probe automatically moves outward and extends to begin the scanning process at the desired location (e.g., tooth 1, 16, 17 or 32). The scanning probe head moves to sweep in at least two directions: one following the long axis of the scanning probe and its extending arm, and the other being lateral (perpendicular to the long axis of the scanning probe and its extending arm).
[0091] For the intraoral scanning, the scanning probe can comprise one or more of a detection sensor, laser sensors or similar devices integral with the scanning probe, or alternatively and preferably can comprise a camera to capture tooth-by-tooth sweep images from the dental arch and gingivae. These images are automatically generated as exact reproductions of the 3D images, as a result of their fixed and constant reference point in relation to the device or system.
[0092] The scanning probe moves in an arc to scan the entire dental arch of either the top or bottom teeth. If a full scan of all teeth is desired, the device can be removed from the mouth of the subject following a scan of a first (upper or lower) dental arch, rotated approximately 180°, and the process repeated for the other dental arch.
[0093] In a preferred embodiment, the vertical movement of the scanning probe is restricted, i.e., the probe only moves laterally or horizontally (side-to-side) and distally/proximally (out and in), but not vertically (up and down) or rotationally in relation to the mouth or the patient. Thus, the vertical, planar position of the scanning probe is maintained, whereby the scanning probe moves only in a single plane, and does not rise or fall, move up or down, or rotate or tilt during a scanning procedure.
[0094] This maintenance of a planar vertical position for the scanning probe provides a further advantage for the device, whereby the fixed position of the mouth on the mouthpiece and fixed reference point for the scanning probe is not affected by, and does not introduce additional motion artefact to the information generated by the scanning probe head. Vertical movement, tilting or rotational motion of the scanning probe can be a disadvantage of devices employing a hand-held wand comprising the scanning probe or scanning probe head.
[0095] Advantageously, the subject device is wand-less, i.e., it does not comprise a hand-held wand for hand-manipulation of the scanning probe. Instead, the scanning probe is manipulated for movement along a pre-set or pre-programmed arced pattern corresponding to the dental arch, using the chassis-mounted movement apparatus and mobility mechanism within the housing body, facilitating scanning using a fixed position reference point. Thus, the imaging processor is not required to relocate its reference position if the reference point is changed, such as can occur by use of a hand-held wand as the scanning probe. The device of the subject invention is therefore termed a “wand-less” or “wand-free” scanning device.
[0096] The subject device can be provided as a system, including a housing body comprising movement mechanism and scanning probe, and one or more separable mouthpiece. In addition, the system can comprise one or more connecting cable, mounting base and mounting arm, and one or more external device for receiving, processing or expressing information generated during the scanning procedure. For example, the system can include with a scanning device, a computer, image processor, milling machine, 3D printer or the like.
[0097] These components can also be provided in a carrying case which preferably has within the case, areas designated for each component, for easily and advantageously storing, carrying, and organizing the portable device and components therefor.
[0098] A method for performing a dental scan one or more teeth of a subject comprises the steps of (a) providing a scanning device having a fixed reference point for the scanning probe, as described and (b) operating the scanning probe to perform a scanning procedure on a subject or patient. The method can further comprise an added step of (c) printing, milling, or 3D-printing a dental structure using the information obtained from the scanning procedure. Moreover, the method can be carried out without use of a scanning powder or scanning gel; therefore the subject method is advantageously a “powder-free” or “gel-free” scanning method. | A three-dimensional (3D) scanner device for generating a three dimensional (3D) surface model of shaped objects, such as dental structures, applicable for use in the field of dentistry, particularly to dental prosthetics manufacturing. Methods and systems relating to the device are also disclosed. | 8 |
BACKGROUND OF THE INVENTION
[0001] This invention deals generally with off road vehicles and more specifically with all wheel drive vehicles that have both front and rear drive wheels that are also both steered.
[0002] Off road utility vehicles are becoming quite common for recreational and some occupational purposes. During some seasons of the year they are heavily advertised on television, and those commercials almost always show them taking sharp turns and cresting hills at high speeds. That is all very well for the camera, but it is not easily accomplished in the real world without careful design of the vehicle. If the suspension system of such an off road vehicle is not designed to accommodate rough terrain, it is easy to end up with one or more wheels off the ground or with very light loading on some wheels. In fact, even on level ground, the steering on some vehicles can be negatively affected by merely placing a heavy load in the cargo carrying area.
[0003] This problem has been essentially solved by a suspension structure disclosed in U.S. Pat. Nos. 6,629,699; 6,536,545; 6,557,661; and 6,601,665 by Joseph C. Hurlburt, who is also the inventor of the invention described herein. The suspension system includes a “bogey beam” which is a beam parallel to the axis of the vehicle. The bogey beam distributes the vehicle load among all the wheels of the vehicle, even when rough terrain puts individual wheels at different heights. For a four wheeled vehicle, the front axle is mounted on the forward end of the bogey beam and a suspension strut connects the rear end of the bogey beam to the frame. On a six wheel vehicle, instead of the suspension strut the middle axle is attached at the rear end of the bogey beam.
[0004] U.S. patent application Ser. No. 10/766,144 also by Hurlburt, extends the use of a bogey beam to all wheel drive vehicles, those in which the front steering wheels are also driven.
[0005] However, front wheels that are both steered and powered raise new problems. Steering angles of driven axles are limited, and vehicles with full time powered steering axles have difficulty turning sharply. Rather than having the front steering axle properly pull the vehicle around turns, a steered and driven front axle acts as if it were being braked while fighting the turn unless the speed of such steered wheels is increased. This is because the limited steering angle causes the front driven wheels to have a greater turning radius and travel much farther than the non-steered axles. This wastes power, is hard on the drive train, causes severe tire wear, and tears up turf below the tires. These problems are aggravated by sharper turns.
[0006] Since an important goal of utility vehicle is good maneuverability, the steering angle problem may be the reason that prior art utility vehicles have avoided front wheel drive. A limited number of other types of vehicles have attacked the steering angle problem. U.S. patent application Ser. No. 10/766,144 by Hurlburt, suggests automatic disengagement of the steering axle drive during tight turns, and some high end automobiles have added only limited steering to the rear wheels to counteract the problem.
[0007] It would be very beneficial to provide utility vehicles that not only include all wheel drive, but also overcome the problems caused by the limited steering angle of driven front wheels.
SUMMARY OF THE INVENTION
[0008] The present invention solves the problem of limited front wheel steering angles on all wheel drive utility vehicles such as the vehicle disclosed in U.S. patent application Ser. No. 10/766,144 by Hurlburt, the disclosure of which is incorporated herein and made a part of this application. The limitation on maneuverability of an all wheel drive utility vehicle is overcome by adding steering to the rear wheels. With the proper selection of the rear steering angle, the drive to the rear wheels can be maintained at the same speed as the drive to the front wheels, and the turning circle diameter can even be reduced from that of a front wheel drive utility vehicle with standard steering.
[0009] In the preferred embodiment of the present invention the steering angles of the rear wheel are approximately the same as those for the front wheels resulting in an inner rear wheel maximum angle of 45 degrees and an outer rear wheel angle of 26 degrees. This results in a fully powered turning circle diameter of only 10½ feet.
[0010] The present invention provides almost identical travel paths and distances for all the axles of an all wheel drive utility vehicle and thereby allows maintaining full power in turns and improves maneuverability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a perspective side view of a typical six wheel utility vehicle upon which the preferred embodiment of the invention is installed.
[0012] FIG. 2 is a bottom plan view of the frame and drive apparatus of a six wheel utility vehicle provided with the rear wheel steering of the preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] FIG. 1 is a perspective side view of a typical six wheel utility vehicle 10 upon which the preferred embodiment of the invention is installed. Vehicle 10 has all its wheels powered and it is supported above the ground G by front steered and driven wheels 12 mounted on front steering axle 14 , by rear driven wheels 16 mounted on rear drive axle 18 , and by middle driven wheels 20 mounted on middle axle 22 . Vehicle 10 includes an operator compartment 24 , with seats and the typical conventional controls, and a load bed 26 behind operator compartment 24 . Except for the fact that vehicle 10 has all its wheels powered and includes rear wheel steering, which is discussed below, it is quite conventional.
[0014] FIG. 2 is a bottom plan view of the frame and drive apparatus of six wheel utility vehicle 10 with the rear wheel steering of the preferred embodiment of the invention.
[0015] Many parts of the structure of utility vehicle 10 shown in the figures have been previously disclosed, and are more fully described in U.S. patent application Ser. No. 10/766,144 by Hurlburt. However, a brief summary of some of those previously disclosed features follows.
[0016] All the wheels of the utility vehicle 10 are powered. Power is first supplied to rear wheels 16 by an engine (not shown) through transmission 30 and rear axle 18 . Transmission 30 also provides power to middle wheels 20 through universal drive assembly 32 . Universal drive assembly 32 accommodates to variations in the relative positions of rear wheels 16 and middle wheels 20 . As more fully described in U.S. patent application Ser. No. 10/766,144 by Hurlburt, universal drive assembly 32 comprises an assembly of telescoping shafts interconnecting universal joints attached to transmission 30 and middle wheel differential 38 .
[0017] Bogey beam 44 is a suspension structure in which bogey beam 44 is a pivoting, longitudinally oriented beam parallel to the axis of the vehicle. Bogey beam 44 supports front wheel axle 14 at bogey beam forward end 46 and middle wheel axle 22 at bogey beam rear end 48 . Bogey beam 44 permits predictable sharing of the frame load by front wheels 12 and middle wheels 20 while keeping all four of the front and middle wheels in contact with the ground. The load on the rear of the vehicle is conventionally applied to rear axle 18 , usually by shock absorbers of conventional construction at connection points (not shown) on rear axle 18 . Thus, the entire vehicle load is shared by bogey beam pivot point 54 near the front of the vehicle and connection points near the rear.
[0018] Motive power is delivered to front wheels 12 by powering middle axle 22 with universal drive assembly 32 and transferring power from middle axle 22 to the front axle 14 . Middle axle 22 and middle wheel differential 38 are mounted at rear end 48 of bogey beam 44 in a pivotal relationship to bogey beam 44 , and front axle 14 and front differential 56 are similarly mounted in a pivotal relationship to bogey beam 44 at its front end 46 . It is therefore practical to interconnect middle differential 38 to front differential 56 with a simple drive shaft 58 . As shown in FIG. 2 when bogey beam 44 is hollow, drive shaft 58 can be completely enclosed within it. However, a solid bogey beam can also be used and the drive shaft can be mounted outside of and parallel to the bogey beam.
[0019] FIG. 2 shows conventional front steering assembly 60 attached to front wheels 12 . Such a steering assembly is of conventional construction for steered and driven front wheels as is well known in the automotive art. FIG. 2 also shows a typical outline for frame 66 of such a vehicle.
[0020] It is at rear wheels 16 that the present invention deviates from previously disclosed utility vehicles. As shown in FIG. 2 , rear wheels 16 are furnished with fully operating rear steering assembly 70 . Rear steering assembly 70 is of conventional construction, but is controlled to operate in conjunction with front steering assembly 60 . Since the goal of the dual steering of the front and rear wheels is to have the rear wheels follow in the tracks of the front wheels, rear wheels 16 actually steer at angles opposite to that of front wheels 12 . Arrows A at front wheels 12 and arrows B at rear wheels 16 show the direction of the steering angles for a typical turn. Furthermore, to have rear wheels 16 follow in the tracks of front wheels 12 , the steering angles of the two sets of wheels should also be approximately equal for any turn.
[0021] This coordinated control can be accomplished by cable 72 or a linkage (not shown). Cable 72 is perhaps the simplest of many devices that can coordinate rear steering assembly 70 with front steering assembly 60 . Cable 72 is connected to front axle steering arm 74 on one side of front steering assembly 60 and connected 2 to rear axle steering arm 76 on the opposite side of rear steering assembly 70 . Thus, steering the front axle in any direction results in the rear wheels steering in the opposite direction. Cable 72 is typically a sheathed cable so that it can push as well as pull rear steering arm 76 to perform its full function.
[0022] The present invention can also be used on a four wheel vehicle with a bogey beam. Such a vehicle is more fully described in U.S. patent application Ser. No. 10/766,144 by Hurlburt, and actually eliminates middle wheels 20 , so that the steering of rear wheels 16 is not affected.
[0023] The present invention thereby overcomes the limitations of limited front wheel steering angles on all wheel drive utility vehicles by placing both the driven front wheels and the driven rear wheels on the same turning circle.
[0024] It is to be understood that the form of this invention as shown is merely a preferred embodiment. Various changes may be made in the function and arrangement of parts; equivalent means may be substituted for those illustrated and described; and certain features may be used independently from others without departing from the spirit and scope of the invention as defined in the following claims. | A utility vehicle that has a bogey beam suspension for the front steered wheels is also provided with all wheel drive and steered rear wheels for greater maneuverability. The steering of the rear wheels is coordinated with the steering of the front wheels to have the rear wheels follow in the tracks of the front wheels, thereby avoiding the need to disable the front drive on turns. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
Reference is made to commonly-assigned, copending U.S. patent applications:
Ser. No. 09/579,592, pending, filed of even date herewith, of Missell et al., entitled “Ink Jet Printing Process”;
Ser. No. 09/580,184, pending, filed of even date herewith, of Missell et al., entitled “Ink Jet Recording Element”; and
Ser. No. 09/579,635, pending, filed of even date herewith, of Missell et al., entitled “Ink Jet Recording Element”;
the teachings of which are incorporated herein by reference.
FIELD OF THE INVENTION
This invention relates to an ink jet printing method which uses an ink jet recording element which contains certain cellulosic fibers.
BACKGROUND OF THE INVENTION
In a typical ink jet recording or printing system, ink droplets are ejected from a nozzle at high speed towards a recording element or medium to produce an image on the medium. The ink droplets, or recording liquid, generally comprise a recording agent, such as a dye or pigment, and a large amount of solvent. The solvent, or carrier liquid, typically is made up of water, an organic material such as a monohydric alcohol, a polyhydric alcohol or mixtures thereof.
An ink jet recording element typically comprises a support having thereon a base layer for absorbing fluid and an ink-receiving or image-forming layer. The recording element may be porous or non-porous.
Many porous ink jet receivers consist of organic or inorganic particles that form pores by the spacing between the particles. The ink and solvents are pulled into this structure by capillary forces. In order to have enough pore volume or capacity to absorb heavy ink lay downs, these coatings are usually coated to a dry thickness on the order of 40 μm to 60 μm, which can be costly because of the layer thickness.
U.S. Pat. Nos. 5,522,968 and 5,635,297 relate to ink jet receiver elements comprising a support containing cellulose or wood pulp. There is a problem with these elements, however, in that ink jet inks printed on them would tend to bleed through the paper causing paper cockle and low optical density. It is an object of this invention to provide an ink jet printing method which uses an ink jet receiver element which has fast dry times, no paper cockle and high optical density.
SUMMARY OF THE INVENTION
This and other objects are provided by the present invention comprising an ink jet printing method, comprising the steps of:
A) providing an ink jet printer that is responsive to digital data signals;
B) loading the printer with an ink jet recording element comprising a resin-coated paper support having thereon an ink-retaining layer comprising voided cellulosic fibers in a polymeric binder, the ratio of the voided cellulosic fibers to the polymeric binder being from about 90:10 to about 50:50, the length of the voided cellulosic fibers being from about 10 μm to about 50 μm;
C) loading the printer with an ink jet ink composition; and
D) printing on the ink jet recording element using the ink jet ink in response to the digital data signals.
Using the method of the invention, an ink jet receiver element is obtained which has fast dry times and high optical density.
DETAILED DESCRIPTION OF THE INVENTION
The voided cellulosic fibers used in the ink-retaining layer of the ink jet recording element employed in the process of the invention have greatly increased porosity over organic or inorganic particles usually used in porous layers of many ink jet recording elements. In addition, these voided cellulosic fibers have an internal voided structure that allows them to act as “micro-straws” to further assist in absorbing fluids. This voided cellulosic fiber structure provides very fast dry times with very heavy ink lay volumes. In addition, the images obtained using the voided cellulosic fiber layer also have high optical density.
Examples of voided cellulosic fibers which can be used in the invention include Arbocel® alpha cellulose fibers, manufactured by Rettenmaier of Germany. These cellulosic fibers are made of different woods such as beech, maple or pine, preferably beech. The fibers also vary in length from about 10 μm to about 50 μm, with the preferred length of less than about 30 μm. The width of the fibers is about 18 μm.
Any polymeric binder may be used in the ink-retaining layer of the ink jet recording element employed in the process of the invention. In general, good results have been obtained with gelatin, a polyurethane, a vinyl acetate-ethylene copolymer, an ethylene-vinyl chloride copolymer, a vinyl acetate-vinyl chloride-ethylene terpolymer, an acrylic polymer or a polyvinyl alcohol.
In another embodiment of the invention, the ink-retaining layer comprising voided cellulosic fibers may be overcoated with an ink-transporting layer commonly used in the art. In general, good results have been obtained when the ink-transporting layer contains materials such as alumina particles, silica particles or polymer beads, such as methyl methacrylate or styrene. This two-layer system provides more ink absorption capacity, faster dry times, and reduced cost compared to thicker single layers of organic or inorganic particles.
Any resin-coated paper support may be used in the process of the invention, such as, for example, Kodak photo grade Edge Paper®, Kodak Royal® Paper and Kodak D'Lite® Paper.
If desired, in order to improve the adhesion of the fiber layer to the support, the surface of the support may be corona discharge-treated prior to coating.
The layers described above may be coated by conventional coating means onto a support material commonly used in this art. Coating methods may include, but are not limited to, wound wire rod coating, slot coating, slide hopper coating, gravure, curtain coating and the like.
Ink jet inks used to image the recording elements employed in the process of the present invention are well-known in the art. The ink compositions used in ink jet printing typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, and the like. The solvent or carrier liquid can be solely water or can be water mixed with other water-miscible solvents such as polyhydric alcohols. Inks in which organic materials such as polyhydric alcohols are the predominant carrier or solvent liquid may also be used. Particularly useful are mixed solvents of water and polyhydric alcohols. The dyes used in such compositions are typically water-soluble direct or acid type dyes. Such liquid compositions have been described extensively in the prior art including, for example, U.S. Pat. Nos. 4,381,946; 4,239,543 and 4,781,758, the disclosures of which are hereby incorporated by reference.
The following example further illustrates the invention.
EXAMPLE
Element 1 (Fibers, Single Layer) (Invention)
A solution of Arbocel® alpha beech 20 μm fibers and poly(vinyl alcohol) (PVA) at a weight ratio of 85/15 was prepared at 20% solids. This was coated using a metered rod at 100 μm wet laydown, on a corona discharged-treated, resin coated, photo grade paper, Kodak Edge® Paper, and oven dried at 150° F. for 30 minutes, to a dry thickness of 20 μm.
Control Element (Alumina, Single Layer) C-1
A solution of fumed alumina and PVA at a weight ratio of 90/10 was prepared at 20% solids. This was coated and dried similar to Element 1.
Element 2 (Fiber Layer and Alumina Layer) (Invention)
The solutions from Element 1 and C-1 were coated to form a two layer structure. The fiber solution from Element 1 was coated similar to Element 1 using a metered rod at 80 μm wet laydown to form the bottom layer at a dry thickness of about 15 μm. This layer was dried similar to Element 1. Then the alumina solution from C-1 was coated on top of the fiber layer using a metered rod at 80 μm wet laydown to form the top layer at a dry thickness of about 15 μm. This was dried similar to Element 1.
Control Element (Silica, Single Layer) C-2
A solution of silica particles and PVA at a weight ratio of 90/10 was prepared at 20% solids. This was coated and dried similar to Element 1.
Element 3 (Fiber Layer and Silica Layer) (Invention)
The solutions from Element 1 and C-2 were coated to form a two layer structure. The fiber solution from Element 1 was coated similar to Element 1 using a metered rod at 80 μm wet laydown to form the bottom layer at a dry thickness of about 15 μm. This layer was dried similar to Element 1. Then the silica solution from C-2 was coated on top of the fiber layer using a metered rod at 80 μm wet laydown to form the top layer at a dry thickness of about 15 μm. This was dried similar to Element 1.
Control Element (Polymer Beads, Single Layer) C-3
A solution of methyl methacrylate beads (Eastman Kodak Co.), about 160 nm and PVA at a weight ratio of 85/15 was prepared at 15% solids. This was coated and dried similar to Element 1 except that the metered rod at 130 μm wet laydown was used.
Element 4 (Fiber Layer and Polymer Beads) (Invention)
The solutions from Element 1 and C-3 were coated to form a two layer structure. The fiber solution from Element 1 was coated similar to Element 1 using a metered rod at 80 μm wet laydown to form the bottom layer at a dry thickness of about 15 μm. This layer was dried similar to Element 1. Then the polymer bead solution from C-3 was coated on top of the fiber layer using a metered rod at 130 μm wet laydown to form the top layer at a dry thickness of about 15 μm. This was dried similar to Element 1.
Testing
Each element was imaged on an Epson 740 printer using the inks S020189 (Black) and S020191 (Color). A test target was printed with each color (cyan, magenta, yellow, red, green, blue, black) in a long stripe the full length of the paper, taking approximately 6 minutes. As soon as the printing was finished, a sheet of bond copier paper (Hammermill Tidal DP®) was placed over the element and a roller weighing about 1.75 kilograms was rolled over it. The bond paper was pulled off immediately. The dry time was calculated using the distance down the color stripe where no ink transfer occurred and the printing time. The trailing end of the stripe had dried 0 minutes, while the leading edge of the stripe had dried for about 6 minutes. The dry time is taken to be at the point where no ink transfer occurred.
The optical density was read using an X-Rite® densitometer and was the average of all the colors (cyan, magenta, yellow, red, green, blue, black). The results are shown in the following Table:
TABLE
Element
Optical Density
Dry Time (min)
1
2.11
0.0
C-1
1.57
5.0
2
2.04
0.0
C-2
1.59
6.0
3
2.11
0.1
C-3
1.68
5.5
4
1.97
0.15
The above results show that Element 1 employed in the process of the invention had a higher optical density and much better drying time than C-1 using alumina, C-2 using silica and C-3 using polymer beads. Elements 2-4 employed in the process of the invention, a two-layer structure, also had higher optical density and much better drying time than the control elements.
This invention has been described with particular reference to preferred embodiments thereof but it will be understood that modifications can be made within the spirit and scope of the invention. | An ink jet printing method, comprising the steps of:
A) providing an ink jet printer that is responsive to digital data signals;
B) loading the printer with an ink jet recording element comprising a resin-coated paper support having thereon an ink-retaining layer comprising voided cellulosic fibers in a polymeric binder, the ratio of the voided cellulosic fibers to the polymeric binder being from about 90:10 to about 50:50, the length of the voided cellulosic fibers being from about 10 μm to about 50 μm;
C) loading the printer with an ink jet ink composition; and
D) printing on the ink jet recording element using the ink jet ink in response to the digital data signals. | 8 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a process for preparing crosslinked ion exchangers with a homogeneous network structure based on unsaturated aliphatic nitrites in the presence of film-forming protective colloids, where the process carried out is not a seed/feed process.
[0002] Copolymerization of two or more monomers generally gives rise to polymers whose composition changes to some extent as conversion increases. Depending on the type of polymerization, two types of heterogeneity can be distinguished.
[0003] If the lifetime of the active group on the polymer chain is the same as the duration of the polymerization, as in the case of anionic polymerization, the composition changes along the chain. At any given juncture during the polymerization all of the polymer chains have the same overall composition.
[0004] If the lifetime of the active group on the polymer chain is significantly shorter than the overall reaction time, the composition of the polymer chains changes as the conversion proceeds in the polymerization. This second type of heterogeneity is typical of free-radical polymerization reactions in which the lifetime of the growing polymer radicals is in the region of seconds and the polymerization time in the region of hours.
[0005] This heterogeneity is associated with disadvantages for many applications. In the case of adsorber resins and ion exchangers, which are crosslinked bead polymers, non-crosslinked or very weakly crosslinked fractions are highly undesirable. These always arise if there is more than proportional incorporation of crosslinking agent, the concentration of which decreases markedly as the polymerization proceeds. A typical example of this is the acrylonitrile/divinylbenzene combination. Bead polymers and/or weakly acidic ion exchangers prepared from this combination contain considerable amounts of non-crosslinked polymers, which can exude and give products which are mechanically and osmotically unstable. Attempts are made to compensate for the drop in concentration of the crosslinking agent during the polymerization by either using a second crosslinking agent which is incorporated only slowly or feeding further amounts of the crosslinking agent whose concentration drops rapidly (in this case divinylbenzene). The second crosslinking agents used in industry are di- or triallyl compounds, such as 1,7-octadiene or trivinylcyclohexane. These substances react only incompletely and have to be carefully removed so that the resin does not cause difficulties in downstream applications. Feeding further amounts of the crosslinking agent is difficult and requires a sophisticated feed strategy, and there is also a limitation on the selection of the suspension stabilizers. Protective colloids frequently used in bead polymerization, such as gelatins, polyvinyl alcohol, or cellulose derivatives, are film-forming substances which are unsuitable since they inhibit the diffusion of the crosslinking agent into the polymerizing beads (EP-A 98,130).
[0006] There is therefore great interest in any process which does not have the disadvantages described above. Surprisingly, it has been found that unsaturated aliphatic nitrites, such as acrylonitrile, in combination with di- and polyvinyl ethers of alkanediols or of glycols build up a very homogeneous network and give products which do not have the disadvantages described above. It is possible to dispense with feeding of further amounts of the crosslinking agent and with the use of a second crosslinking agent.
[0007] The use of di- or polyvinyl ethers for crosslinking polymers is prior art.
[0008] EP-A 10,265 describes the preparation of synthetic resins based on crosslinked copolymers of mono- and polyvinyl compounds. A substantive feature of the invention is the joint use of two crosslinking agents, as stated in the Abstract: methacrylates of polyhydric alcohols and/or aromatic polyvinyl compounds and unsaturated hydrocarbons which have at least two allyl groups in the molecule and/or polyvinyl ethers of polyhydric alcohols. There is also an indication of the use of acrylonitrile in the bead polymers, but susceptibility to hydrolysis is described in the text as a serious disadvantage of known synthetic resins based on acrylonitrile.
[0009] U.S. Pat. No. 3,586,646 describes the use of divinyl ethers for preparing spongy cation exchangers having groups selected from the class consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, and phosphonic acid groups, in the presence of a porogen (an organic solvent which dissolves the monomer but is a precipitant for the polymer). However, U.S. Pat. No. 3,586,646 does not describe the use of unsaturated nitrites in the bead polymers.
[0010] EP-A 98,130 describes the preparation of crosslinked copolymer beads by a seed/feed process, and describes the copolymer beads themselves and their use as adsorbers or, after introduction or addition of functional groups, as ion-exchange resins. Monomers mentioned for the seed and/or the feed include nitriles of acrylic and/or methacrylic acid, and crosslinking agents mentioned include polyvinyl ethers of glycol, glycerol, pentaerythritol, resorcinol or monothio- or dithio derivatives of glycols. The preparation of the seed/feed particles requires the absence of protective colloids, or a drastic reduction in the amount of these, as they prevent, or dramatically delay, the absorption of the feed component by the seed particles. The particles prepared according to EP-A 98,130 also show multistage swelling behaviour in toluene and birefringence in the form of a maltese cross under polarized light.
[0011] None of the patent applications/patents cited gives any indication as to how monomers and crosslinking agents have to be selected in order to obtain crosslinked bead polymers with a homogeneous network structure, particularly in the presence of film-forming protective colloids.
[0012] The object of the present invention was to prepare ion exchangers, preferably weakly acidic cation exchangers, having a homogeneous network structure and based on unsaturated aliphatic nitrites in the presence of film-forming protective colloids.
SUMMARY OF THE INVENTION
[0013] The present invention achieves this object in providing a process for preparing crosslinked ion exchangers comprising
[0014] (a) polymerizing unsaturated aliphatic nitrites with di- or polyvinyl ethers as crosslinking agents and also with initiators in suspension in the presence of protective colloids, but not by a seed/feed process, to give bead polymers, and
[0015] (b) functionalizing the resultant bead polymers to give ion exchangers.
[0016] If desired, other monovinyl compounds and/or other crosslinking agents and/or porogen may be added to the polymerization reaction mixture.
[0017] The bead polymers prepared by step (a) are likewise provided by the present invention. They have a homogeneous network structure and can be used as adsorber resins.
DETAILED DESCRIPTION OF THE INVENTION
[0018] In step (b) the bead polymers are functionalized by customary methods known to those skilled in the art to give ion exchangers, particularly weakly acidic cation exchangers. To prepare weakly acidic cation exchangers, the bead polymers obtained in step (a) are hydrolysed under alkaline conditions, subjected to ion-exchange if desired, and purified. Alkaline hydrolysis has proven to be a particularly effective and economic practical process. The weakly acidic cation exchangers preferably obtained by the novel process exhibit a particularly high capacity.
[0019] For the purposes of step (a) of the present invention, unsaturated aliphatic nitrites are defined by the general formula (I)
[0020] wherein each of A, B, and C, independently of the others, represents hydrogen, alkyl, or halogen.
[0021] For the purposes of the present invention, the term “alkyl” refers to straight-chain or branched alkyl having from 1 to 8 carbon atoms (preferably from 1 to 4 carbon atoms). For the purposes of the present invention, the term “halogen” refers to chlorine, fluorine, or bromine.
[0022] For the purposes of the present invention, preferred nitriles are acrylonitrile and methacrylonitrile, and the use of acrylonitrile is particularly preferred.
[0023] For the purposes of step (a) of the present invention, suitable divinyl ethers are compounds of the general formula (II)
[0024] wherein
[0025] R represents a radical selected from the group consisting of C n H 2n , (C m H 2m —O) p —C m H 2m , and CH 2 —C 6 H 4 —CH 2 ,
[0026] n is ≧2,
[0027] m is from 2to 8,and
[0028] p is ≧2.
[0029] For the purposes of step (a) of the present invention, suitable polyvinyl ethers are trivinyl ethers of glycerol or trimethylolpropane or tetravinyl ethers of pentaerythritol.
[0030] It is preferable to use divinyl ethers of ethylene glycol, di-, tetra-, or polyethylene glycol or butanediol or polyTHF, or the tri- or tetravinyl ethers. Particular preference is given to the divinyl ethers of butanediol and diethylene glycol.
[0031] If desired, use may also be made of other monovinyl compounds and/or other crosslinking agents.
[0032] For the purposes of the present invention, suitable monomers are styrene and styrene derivatives, acrylic acid, and methacrylic acid and their esters, amides, and anhydrides, vinyl chloride, vinylidene chloride, vinyl acetate, and vinylpyrrolidone.
[0033] For the purposes of the present invention, suitable other crosslinking agents are divinylbenzene, di- and poly(meth)acrylates of glycols, of alkanediols having three or more carbon atoms, glycerol, trimethylolpropane, or pentaerythritol, 1,7-octadiene, and trivinylcyclohexane. Divinylbenzene is preferred. To increase the porosity of the beads use may be made of porogens. Suitable porogens in the novel process are organic solvents in which the monomers are soluble but which are poor solvents and, respectively, swelling agents with respect to the polymer produced. Examples of these compounds are those selected from the group of ketones, such as methyl isobutyl ketone or methyl ethyl ketone, from the group consisting of hydrocarbons, such as hexane, octane, isooctane, and isododecane, or from the group consisting of alcohols having four or more carbon atoms, such as butanols (Farbenfabriken Bayer, DBP 1,045,102 [1957], and DBP 1,113,570 [1957]).
[0034] The preparation of the weakly acidic cation exchangers preferred according to the present invention can be carried out by
[0035] (α) polymerizing unsaturated aliphatic nitrites of the general formula (I) with di- or polyvinyl ethers and, optionally, further crosslinking agents and initiators in suspension in the presence of protective colloids, to give bead polymers,
[0036] (β) subjecting the bead polymer to alkaline hydrolysis (preferably in an autoclave), and
[0037] (γ) subjecting the hydrolyzed bead polymers to ion-exchange from the salt form (preferably Na form) into the H form by dilute mineral acid (preferably 10% strength H 2 SO 4 ), preferably in a column,
[0038] (δ) optionally, purifying the H form of the bead polymers with water in an autoclave and, finally,
[0039] (ε) optionally, classifying the bead polymers into desired particle size ranges in a column.
[0040] The bead polymer may also be screened, if necessary.
[0041] The suspension polymerization according to the invention is carried out in the presence of protective colloids and, if desired, in the presence of dispersing agents. It is advisable to use compounds that are stable in the presence of salts, such as hydroxyethylcellulose or condensation products of naphthalenesulfonic acid with formaldehyde in the presence of the alkali metal or alkaline earth metal salts of hydrohalic acids or of sulfuric acid (particularly preferably of NaCl, Na 2 SO 4 , or CaCl 2 ). The salts reduce the solubility of the monomers in the aqueous phase. To reduce agglomeration, pH buffers made from borate or phosphate may be added. For the purposes of the present invention, suitable free-radical initiators are peroxides, hydroperoxides, peresters, azo initiators and other initiators with half-life times t ½ of 1 hour at from 60 to 140° C. (AKZO Nobel company publication: Initiators for High Polymers). Examples of preferred initiators suitable for the novel process are peroxy compounds, such as dibenzoyl peroxide, dilauroyl peroxide, bis(p-chlorobenzoyl) peroxide, dicyclohexyl peroxydicarobnate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, or tert-amyl peroxy-2-ethylhexane, or else azo compounds, such as 2,2′-azobis(isobutyronitrile) or 2,2′-azobis(2-methylisobutyronitrile). Preferred initiators have half-life times t ½ of 1 hour at from 75 to 110° C. It is particularly preferable to use dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, or azoisobutyronitrile.
[0042] The polymerization is preferably carried out in two stages. The main reaction is first completed at a temperature of from 50 to 80° C. and then completed at an elevated temperature. It is particularly preferable to carry out a polymerization at from 65 to 75° C., followed by an increase of the temperature to 85-100° C.
[0043] To prepare the weakly acidic ion exchangers preferred according to the present invention, the bead polymers are hydrolyzed by aqueous sodium hydroxide in an autoclave. Preference is given to alkaline hydrolysis with aqueous/methanolic sodium hydroxide. Another possibility is hydrolysis at atmospheric pressure by aqueous/methanolic sodium hydroxide. However, acid hydrolysis by mineral acids is also possible, based on the prior art. Reference is made to EP-A 406,648 concerning the conduct of the hydrolysis at superatmospheric pressure. Preference is given to procedure 1, in which the bead polymer forms an initial charge and the aqueous sodium hydroxide is fed. Once the hydrolysis is complete, the resin is washed through, subjected to ion-exchange using 10% strength H 2 SO 4 at 90° C. and then washed until neutral. For purification, the resin is treated with water or, respectively, steam at an elevated temperature. Fine-particle constituents may then be removed in a classifying column.
[0044] The novel bead polymers from step (a) and (α), respectively, have wide application as adsorbers.
[0045] The novel weakly acidic macroporous cation exchangers may be used in the food or drink industry or for drinking water treatment, for example. They are particularly suitable for removing cations/hardness from drinking water (e.g., in household filters) and for decarbonizing drinking water, or else decarbonizing liquids used as food or drink or in preparing food or drink. Other important applications are removal of cations/hardness from sugar solutions or solutions of organic products, e.g., of beet sugar, of cane sugar, or of starch sugar or, respectively, glycerol, gelatin, etc., desalination of water during preparation of ultrahigh-purity water, decarbonization of service water (in the cocurrent process), in association with a strongly acid cation exchanger for the desalination of water for industrial steam generation, as a buffer filter downstream of desalination plants for binding alkali metal ions, in the neutralization of regeneration wastewater from desalination plants, in the sodium form for binding heavy metals, such as copper, nickel or zinc, from solutions at pH>5 in the absence of calcium ions, and of complexing agents.
[0046] The novel weakly acidic macroporous cation exchangers may also be used to remove polar or nonpolar compounds or heavy metals from aqueous or organic solutions from the chemical industry, electronics industry, food or drink industry, waste-disposal industry, or waste-reclamation industry.
[0047] The novel bead polymers and/or ion exchangers may in particular be used
[0048] for removing polar compounds from aqueous or organic solutions,
[0049] for removing polar compounds from process streams from the chemical industry,
[0050] for removing organic components from aqueous solutions or from gases, for example, from acetone or chlorobenzene, or
[0051] for removing heavy metals or precious metals, arsenic, or selenium, from aqueous solutions.
[0052] For the purposes of the present invention, heavy metals or precious metals are the elements of the Periodic Table with serial numbers from 22 to 30, from 42 to 50, and also from 74 to 83.
[0053] The novel ion exchangers and bead polymers, moreover, may be used for purifying or treating water from the chemical industry or electronics industry, or else from the food or drink industry, particularly for preparing ultrahigh-purity water, ultrahigh-purity chemicals or preparing starch or hydrolysis products thereof.
[0054] The novel ion exchangers and bead polymers may moreover be used for purifying wastewater streams from the chemical industry, or else from waste-incineration plants. Another application of the novel adsorbers is the purification of landfill run-off water.
[0055] The novel ion exchangers and bead polymers may also be used for treating drinking water or groundwater. However, the novel bead polymers and/or ion exchangers may also serve as a starting material for other poly(meth)acrylic acid derivatives, by reactions such as:
[0056] reaction with 1-N,N-dimethylamino-3-aminopropane (amine Z) to give acrylamide resins, which products may be partially or completely quaternized and serve for treatment of water or of sugar,
[0057] reaction with polyamines, such as diethylenetriamine or triethylenetetramine, to give highly sulfate-selective resins, or
[0058] reaction with amino sugars (e.g. N-methylglucamine) to give boron-selective resins.
[0059] The novel ion exchangers are prepared in a number of steps and are illustrated using the examples below.
EXAMPLES
Example 1
[0060] The polymerization took place in a 3 liter flat-flange-jointed glass vessel with a wide flat-flange-jointed vessel stirrer, Pt 100 temperature sensor, reflux condenser, 500 ml dropping funnel and thermostat with control unit.
Aqueous phase 1.184 g hydroxyethylcellulose in 126 ml demineralized water 196.8 g sodium chloride (technical) in 592 ml demineralized water 0.414 g Na salt of naphthalenesulfonic acid- formaldehyde condensate (95% strength) in 77 ml demineralized water Organic phase 760 g acrylonitrile 40 g diethylene glycol divinyl ether 2.13 g dibenzoyl peroxide (75% strength)
[0061] The hydroxyethylcellulose is sprinkled into demineralized water and stirred for at least 8 h to prepare the aqueous phase. The sodium chloride solution is an initial charge in the polymerization vessel. The hydroxyethylcellulose solution is added to the sodium chloride solution. The sulfonic acid solution is stirred for 15 min and then added into the polymerization vessel. The entire aqueous phase is stirred for a further 30 min.
[0062] The organic phase is stirred for 15 min at room temperature and then, with the stirrer stopped, added to the aqueous phase. The mixture then stands for 20 min, without stirring, and is then stirred for 20 min at 170 rpm at room temperature.
[0063] The mixture is heated to 72° C. within a period of 90 min with stirring. The start of the reaction can be recognized via a change in the color (from cloudy to milky white). The heat of reaction generated is dissipated via the glass vessel's jacket, which has a connection to the thermostat. Peaks in the reaction are intercepted by adding portions of cold water. The total reaction time at 72° C. is 5 h. The mixture is then heated to 90° C. within a period of 1 h and held for 5 h at this temperature. The mixture is then cooled and mixed with 300 ml of 10% strength aqueous sodium bisulfite solution and stirred for 1 h at 80° C. The resin is then washed through on a 100 mesh screen, using demineralized water.
[0064] Yield: 1180 ml of resin, dry yield: 98.4%
[0065] Effective particle size: 0.278 mm, coefficient of uniformity: 1.625 (determined optoelectronically)
Example 2
[0066] Prior to the alkaline hydrolysis, 500 ml of resin prepared as in Example 1 were transferred into a heatable glass-frit column, followed by annealing at 80° C. for 1 h. The resin was then eluted at 80° C. with 1 bed volume (“BV”) of hot demineralized water over a period of 30 min, followed by another 1 h of annealing. The annealing was repeated 4 times, and the elution was repeated 3 times.
[0067] The resin treated in this way was hydrolyzed in a 3 liter V 4 A autoclave with stirrer and temperature control.
500 ml resin (moist from filtration) 727 ml demineralized water 143 ml 45% strength NaOH (1st part) 655 ml 45% strength NaOH (2nd part) 150 ml demineralized water 670 ml demineralized water
[0068] Resin and water form the initial charge in the autoclave and were heated to 150° C. The 1st part of the NaOH was pumped in within a period of 120 min. The 2nd part of the NaOH was then added within a period of 100 min, rapidly followed by 150 ml of water. Stirring of the mixture at 150° C. continued for 3.5 h. The pressure must be held at not more than 4.5 bar during the pumping-in and the continued stirring. The ammonia produced was released via a glass receiver charged with water. Once the continued stirring had ended, the mixture was cooled to 100° C. and then the pressure released over a period of 40 min. With the valve open, 670 ml of water were pumped in. Finally, the mixture was again stirred for 1 h at 100° C. with the valve open. After cooling to room temperature, the resin was removed and washed through on the screen.
[0069] The resin was then transferred to a heatable column. Conversion to the H form took place at 90° C. with 2 BVs of 10% strength H 2 SO 4 . The first BV was added within a period of 1 h, and the second BV was allowed to stand on the resin for 4 h. The resin was then washed 90° C. with water until neutral.
[0070] Volume of H form: 1050 ml
[0071] Effective particle size: 0.49 mm, uniformity coefficient: 1.67
[0072] Total capacity: 4.76 eq/l
[0073] Volume change: H/Na form (66%), H/Ca form (−2%)
[0074] Swelling water: 49.7%, dry weight: 371 g/l, bulk density: 738 g/l
[0075] For further purification the resin moist from filtration was heated to 150° C. together with the same volume of demineralized water in an autoclave (V 4 A), and stirred at this temperature for 5 h. The water present in the autoclave was removed under pressure through a frit tube and replaced by suction with the same amount of fresh water while the stirrer was stopped. This was followed by heating again to 150° C. and repeating the purification, with stirring. The resin was treated for a total of 3 times at 150° C. with water, for 5 h each time, followed by cooling to room temperature and washing through the resin on a screen.
Example 3
[0076] The resin had the following changes and was polymerized as in Example 1:
[0077] Crosslinking agent: 38 g of diethylene glycol divinyl ether and 29.6 g of divinylbenzene (81% strength)
[0078] Polymerization temperature 1st stage: 70° C.
[0079] Stirrer rotation rate: 160 rpm
[0080] Yield: 1120 ml of resin, dry yield: 90.6%
[0081] Effective particle size: 0.421 mm, uniformity coefficient: 1.585 (determined optoelectronically)
[0082] Hydrolysis took place as in Example 2 with 750 ml of resin moist from filtration.
[0083] Volume of H form: 1420 ml
[0084] Effective particle size: 0.56 mm, uniformity coefficient: 1.48
[0085] Total capacity: 4.62 eq/l
[0086] Volume change: H/Na form (68%), H/Ca form (2%)
[0087] Useful capacity: 1.95 eq/l (cocurrent method with Leverkusen, Germany, mains water, regeneration with 90 g/l of HCl)
Example 4
[0088] The resin had the following changes and was polymerized as in Example 1:
[0089] Crosslinking agent: 32 g of butanediol divinyl ether
[0090] Organic phase with 0.12 g of resorcinol
[0091] Polymerization temperature 1st stage: 70° C.
[0092] Stirrer rotation rate: 160 rpm and after 7 min at 70° C. increased to 180 rpm,
[0093] Yield: 1290 ml of resin, dry yield: 91.2%
[0094] Effective particle size: 0.427 mm, uniformity coefficient: 1.575 (determined optoelectronically)
[0095] Hydrolysis took place as in Example 2 with 500 ml of resin moist from filtration.
[0096] Volume of H form: 1060 ml
[0097] Effective particle size: 0.569 mm, uniformity coefficient: 1.586
[0098] Total capacity: 4.28 eq/l
[0099] Volume change: H/Na form (66%)
[0100] Characterization of the Copolymers
[0101] Copolymers are best defined by way of their copolymerization parameter r i . In a kinetic model, the parameters represent ratios of rate constants for the addition of competing monomers onto a polymer radical.
[0102] The corresponding kinetic equations are:
V
AA
=k
AA
[PA][A]
V
AB
=k
AB
[PA][B]
V
BA
=k
BA
[PB][A]
V
BB
=k
BB
[PB][B]
[0103] In a binary copolymerization of monomer A and monomer B the system is described by two equations:
r A =k AA /k AB and r B =k BB /k BA
[0104] The resulting instantaneous composition of the polymer is:
d [ A ] / d [ B ] = 1 + r A ( [ A ] / [ B ] ) 1 + r B ( [ B ] / [ A ] )
[0105] The above equation is best evaluated in the integrated form according to Meyer-Lowry as a function of the conversion (George Odian, Principles of Polymerization , John Wiley & Sons, 1981, page 464).
[0106] In the case of crosslinking copolymerization with a bifunctional crosslinking agent V instead of monomer B the equations obtained are as follows:
r A =k AA /2 k AV and r V =2 k VV /k VA
[0107] The factor 2 in both equations takes account of the fact that each molecule of crosslinking agent has two double bonds active in polymerization.
[0108] The overall reaction is described by the two rate constants k AA and k VV and the two copolymerization parameters r A and r V . The rate constants k AA and k VV affect the overall reaction rate but not the composition of the copolymer. Since the monomer A is generally present in large excess over the crosslinking agent V, the rate of incorporation of the crosslinking agent is primarily determined by the parameter r A . The effect of the parameter r V is of subordinate importance and can be neglected. In the ideal case the parameter r A has the value 0.5.
[0109] Determination of Copolymerization Parameter r A
[0110] The polymerization was carried out with the composition in the mixing specification of Example 1 with the following changes:
[0111] amount of crosslinking agent: 1, 2 and 4% by weight of diethylene glycol divinyl ether
[0112] amount of hydroxyethylcellulose increased by 35%
[0113] heating to 65° C. (polymerization temperature) within a period of 10 min
[0114] stirrer rotation rate: 230 rpm, to 210-220 rpm after 1 h
[0115] internal standard: toluene (1% based on total amount of monomer)
[0116] At regular intervals samples were taken, introduced into 5 to 10 times the amount of dimethyl sulfoxide (DMSO) and, with stirring, homogenized in an ice bath. The samples comprising DMSO were stirred overnight and then analyzed by gas chromatography to determine the residual monomer composition.
[0117] Fused silica capillary separating column of 30 m length, internal diameter 320 μm, film thickness 0.2 μm
[0118] Injection block temperature: 350° C.
[0119] Temperature phasing: 3 min at 50° C., then to 250° C. at 20 K/min and 5 min at 250° C.
[0120] The retention times for the individual components were:
Acrylonitrile 5.60 min Toluene 6.12 min DMSO 10.79 min Diethylene glycol divinyl ether 10.33 min
[0121] The measurement points up to about 30% polymer conversion were used for evaluation and the parameters matched to the Meyer-Lowry equation. For this, the molar conversion was plotted against the composition of the monomer phase.
[0122] For the copolymerization parameter r A the value obtained was 0.47±0.015.
[0123] A ternary system with one monomer (in this case acrylonitrile, index A) and two crosslinking agents (indices 1 and 2) was fully characterized by the following parameters:
[0124] If the concentration of the crosslinking agents is significantly smaller than that of monomer, the system becomes simpler. The composition of the copolymers is substantially determined by the two parameters r A1 and r A2 , that is to say, the ternary system acrylonitrile/diethylene glycol divinyl ether/divinylbenzene behaves like two separate binary systems acrylonitrile/diethylene glycol divinyl ether and acrylonitrile/divinylbenzene. The two crosslinking agents have practically no effect on each another.
[0125] For acrylonitrile/diethylene glycol divinyl ether, r A1 =0.635±0.015 and for acrylonitrile/divinylbenzene (m-isomer), r A2 =0.05±0.001, and for acrylonitrile/divinylbenzene (p-isomer), r A3 =0.028±0.01.
[0126] Definition of Homogeneous Networks
[0127] The networks of the novel bead polymers and ion exchangers were substantially determined by the copolymerization parameter r A , which is typically 0.5 for the ideal case of a bifunctional crosslinking agent. For homogeneous networks in the sense of the invention, r A is from 0.3 to 0.8, preferably from 0.4 to 0.65 (bifunctional crosslinking agent). Surprisingly, adding aliphatic nitriles in the sense of the present invention gave copolymerization parameters r A which were very close to the ideal value of 0.5, indicating that the networks are very substantially homogeneous.
[0128] Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
[0129] Illustration of the Parameters in Matrices
[0130] The matrices (2×2 for the binary copolymerization of monomer A and crosslinking agent V; 3×3 for the ternary copolymerization of monomer A and crosslinking agents 1 and 2) are intended to illustrate diagrammatically the parameters required for the kinetic definition of the two copolymerization reactions. The copolymerization parameters ri (binary) and rij (ternary) represent the relative rate constants for the addition of 2, 3 or more monomers to a growing polymer radical. The reactivity (rate constant) of this polymer radical with a monomer is—according to a simplifying assumption—determined exclusively by the monomer last incorporated (in our case acrylonitrile or a crosslinking agent). In the case of binary copolymerization 2 polymer radicals are present to each of which 2 monomers (in the present case acrylonitrile and the crosslinking agent) can add, i.e. there are 4 rate constants (2×2). In ternary copolymerization (in the present case acrylonitrile plus crosslinking agents 1 and 2) 3 polymer radicals are present which can react with 3 monomers (acrylonitrile plus crosslinking agents 1 an 2), i.e. 9 rate constants (3×3) are involved in this case. The addition of a monomer to its polymer radical, e.g. acrylonitrile to the polymer radical with a terminal acrylonitrile group, does not produce any change in composition, but determines the overall rate of polymerization. High ki values (binary) and kii values (ternary) signify rapid polymerization and low ki and kii values signify slow polymerization. | The present invention relates to a process for preparing crosslinked ion exchangers with a homogeneous network structure based on unsaturated aliphatic nitrites in the presence of film-forming protective colloids. | 1 |
TECHNICAL FIELD
This invention relates to chelators that form a mixture enriched for a single stereoisomeric species upon coordination to a metal center.
BACKGROUND OF THE INVENTION
The current interest in the radiolabeling of biologically important molecules (proteins, antibodies, and peptides) with 99m Tc stems from the desire to develop a target specific diagnostic radiopharmaceutical. 1-10 The advantages of using 99m Tc in diagnostic nuclear medicine are well known 11-15 and a number of techniques have been developed for the 99m Tc labeling of biologically important molecules. 16-20 One obvious approach is to coordinate a 99m Tc metal directly with the targeting molecule. This approach is known as the direct labeling method and it involves the use of a reducing agent to convert disulfide linkages into free thiolates, which then bind to the 99m Tc metal. A major disadvantage of this method is the lack of control over the coordination of the 99m Tc metal and the stability of the resulting metal complex. In addition, the lack of suitable or accessible coordination sites in some proteins and peptides exclude direct labeling as a viable technique. Two common alternatives to direct labeling are the final step labeling method and the pre-formed chelate approach. Both techniques involve the use of a bifunctional chelator, which provides the site of 99m Tc coordination. The difference between the two approaches lies in the order in which the 99m Tc complex is formed. In the final step labeling method, complexation occurs after the chelator has been attached onto the targeting molecule. With the pre-formed chelate method, the 99m Tc complex is initially prepared and purified before being attached to the targeting molecule. In both techniques, the bifunctional chelator must coordinate to 99m Tc to form a complex that is stable in vivo and the chelator must have an active moiety that can react with a functional group on the targeting molecule.
A number of bifunctional chelators have been used in the labeling of proteins, peptides and monoclonal antibodies. 2,9,10,17,21-28 Depending on the chelator, the labeling of biologically important molecules with bifunctional chelators often results in the formation of multiple species and/or isomeric complexes. An example is the 99m Tc labeling of molecules using the hydrazinonicotinamide (HYNIC) system. Since the HYNIC group can only occupy one or two sites of Tc coordination, co-ligand are required to complete the coordination sites. Glucoheptonate 29-30 , tris(hydroxymethyl)methylglycine (tricine) 25 , ethylenediamine-N, N′-diacetic acid (EDDA) 9 , water soluble phosphines 25 [trisodium triphenylphosphine-3,3′,3″-trisulfonate (TPPTS); disodium triphenylphosphine-3,3′disulfonate (TPPDS); and sodium triphenylphosphine-3-monosulfonate (TPPMS)] and polyamino polycarboxylates 9 have all been used as co-ligand in the HYNIC system. It has been clearly shown the Tc-99m labeling of molecules via the HYNIC/co-ligand system produces multiple species, which is due to the different coordination modalities of the hydrazine moiety and the co-ligands. The number of species, the type, the stability and the properties of the species vary greatly from one co-ligand to another. In the labeling of chemotatic peptide using the HYNIC system, the nature of the co-ligand also greatly affects the biodistribution of the labeled peptide. 31
Another example of a bifunctional chelator producing multiple species is dithiosemicarbazone (DTS) system. It has been shown that the DTS bifunctional chelator produces at least four complexes with technetium. 32 Two of the complexes are known to be charged; hence they have different biodistribution from the uncharged species.
As in the development of a pharmaceutical based on organic molecules, the stereochemistry or isomerism of a metal complex is also very important in the development of a radiopharmaceutical or metallodrug. It is well known that isomers can often have different lipophilicities, biodistribution and biological activities. An example of this is the 99m Tc complex of 3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime ( 99m Tc-d,1-HMPAO or Ceretec), which is a cerebral perfusion imaging agent. 14,33-35 Though 99m Tc-d,1-HMPAO is active, it has been shown that the meso analogs of the 99m Tc HM-PAO 14,36 complex and the 99m Tc complex of 3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime 14,37 (PnAO) does not possess the properties necessary for use as a cerebral perfusion imaging agent.
A type of Tc and Re coordination modality common in Tc and Re radiopharmaceuticals is the coordination of a tetradentate N 4−x S x chelator to a metal oxo moiety to form a square pyramidal or octahedral metal oxo complex. A host of bifunctional chelators have been developed based on the tetradentate N 4−x S x coordination motif. Examples include N 4 propylene amine oxime 38 , N 3 S triamide thiols 9, 39-43 , N 2 S 2 diamide dithiols 9, 44-46 , N 2 S 2 monoamide monoaminedithiols 47-49 and N 2 S 2 diamine dithiols 50-55 . Functionalization of the chelator backbone enable these chelators to be attached to biologically interesting molecules. The labeling of these bifinctional chelators with TcO 3+ or ReO 3+ often produce isomers or epimers. 39-43, 46-55 The isomers or epimers (syn and anti) arise from the configuration of the metal oxo group relative to the functional group on the chelator backbone. It has been clearly shown that the biodistribution and biological activity of the syn and anti isomers are often different. 39-43, 46, 56 The Tc complex of mercaptoacetylglycylglycylglycine (MAG 3 ), a renal imaging agent, exists in the syn and anti isomers. The biological activities of the syn and anti isomers are known to be different. 39,40 The syn and anti isomers of the Tc complex of 2,3-bis(mercaptoacetamide)propanoate (map) was also shown to have different biological activity. 46 It was reported that in humans, 58% of the syn isomers was excreted at 30 minutes as compared to only 19% of the anti isomer. Another example of the isomers exhibiting a difference in biological behaviour is the 99m Tc labeled diamino dithiol piperidine conjugate, which were investigated as a brain perfusion imaging agents. It was shown that the two isomeric complexes exhibit widely disparate brain uptake. 55 At 2 minute post-administration in rats, uptake of the anti isomer in the brain was 1.08% dose/g, while the uptake of the syn isomer was 2.34% dose/g. The brain/blood ratio at 2 minute post-administration was 2.09 for the anti isomer and 5.91 for the syn isomer.
The peptide dimethylglycine-serine-cysteine-glycine is a bifunctional chelator that can be use to label biologically important molecules. 61,62 It has been shown that dimethylglycine-serine-cysteine-glycine coordinates to TcO 3+ and ReO 3+ via a monoamine diamide monothiol coordination modality. 61 The resulting Tc and Re complexes exist as two isomers; the serine CH 2 OH side chain is in the syn and anti conformations with respect to the metal oxo bond. The presence of the syn and anti isomers are very evident from the NMR spectral data. In the 1 H NMR spectrum of the Re complex, there were two pairs of singlets associated with the nonequivalent methyl groups in the dimethylglycine residue. Each pair of singlets corresponded to either the syn or anti isomers. The 1 H and 13 C NMR spectral data for the Re oxo complex of dimethylglycine-sercine-cysteine-glycine-NH 2 (RP294) were obtained. The presence of the two isomers are clearly evident from the NMR data. In the coordination of dimethylglycine-isoleucine-cysteine-glycine (RP349) to ReO 3+ , two isomers (syn and anti) were also observed. The 99m Tc labeling of RP294 and RP349 produced syn and anti isomers; two peaks were observed in the HPLC using the radiometric detector. The 99m Tc labeling of biotin with dimethylglycine-lysine-cysteine-NH 2 (RP332) also produced syn and anti isomers; two peaks were observed in the HPLC. These results are consistent with the coordination of other tetradentate N 4−x S x chelators to TcO 3+ and ReO 3+ . 9,39-55
The labeling of biologically important molecules via a bifinctional chelator can result in the formation of isomers or multiple species, which can have significant impact on the biological properties of the radiopharmaceutical. For receptor-based radiopharmaceuticals, the target uptake is largely dependent on the receptor binding affinity of the targeting molecule and the blood clearance of the labeled molecule, which is determined by the physical properties of both the targeting molecule and the metal chelate. Hence, the presence of isomers for the metal chelate can have significant impact on the radiopharmaceutical. Therefore, in the development of a radiopharmaceutical or metallodrug, it is necessary to separate the isomers and evaluate the biological activities of each individual isomer. It would therefore be desirable to develop chelators that predominately form only a single stereoisomeric species upon coordination to a metal center.
SUMMARY OF THE INVENTION
Chelators and chelator-targeting molecule conjugates are provided that form a mixture enriched for a single stereoisomeric species upon coordination to a metal center.
According to an aspect of the invention, there is provided a chirally pure compound of the formula I:
wherein
R 1 is a linear or branched, saturated or unsaturated C 1-4 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents selected from halogen, hydroxyl, amino, carboxyl, C 1-4 alkyl, aryl and C(O)R 10 ;
R 2 is H or a substituent defined by R 1 ;
R 1 and R 2 may together form a 5- to 8-membered saturated or unsaturated heterocyclic ring optionally substituted by one or more substituents selected from halogen, hydroxyl, amino, carboxyl, oxo, C 1-4 alkyl, aryl and C(O)R 10 ;
R 3 , R 4 and R 5 are selected independently from H; carboxyl; C 1-4 alkyl; C 1-4 alkyl substituted with a substituent selected from hydroxyl, amino, sulfhydryl, halogen, carboxyl, C 1-4 alkoxycarbonyl and aminocarbonyl; an alpha carbon side chain of a D- or L-amino acid other than proline; and C(O)R 10 ;
R 6 is an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring;
or R 6 is
wherein R 11 , R 12 and R 13 are independently selected from H, linear or branched, saturated or unsaturated C 1-6 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring; with the proviso that a least one of R 11 , R 12 and R 13 is not H;
or R 6 is
wherein R 14 and R 15 are independently selected from H, linear or branched, saturated or unsaturated C 1-6 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring; with the proviso that a least one of R 14 and R 15 is not H;
or R 6 is
wherein X is selected from O or S and R 16 is selected from linear or branched, saturated or unsaturated C 1-6 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, and an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring;
R 7 and R 8 are selected independently from H; carboxyl; amino; C 1-4 alkyl; C 1-4 alkyl substituted by a substituent selected from hydroxyl, carboxyl and amino; and C(O)R 10 ;
R 9 is selected from H and a sulfur protecting group; and
R 10 is selected from hydroxyl, alkoxy, an amino acid residue, a linking group and a targeting molecule.
According to another aspect of the invention, there is provided a chirally pure compound of the formula II:
wherein
R a is selected from H and a sulfur protecting group;
R b , R c R d , R f and R g are selected independently from H; carboxyl; C 1-4 alkyl; C 1-4 alkyl substituted with a substituent selected from hydroxyl, amino, sulfhydryl, halogen, carboxyl, C 1-4 alkoxycarbonyl and aminocarbonyl; an alpha carbon side chain of a D- or L-amino acid other than proline; and C(O)R h ;
R e is an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring;
or R e is
wherein R i , R j and R k are independently selected from H, linear or branched, saturated or unsaturated C 1-6 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring; with the proviso that a least one of R i , R j and R k is not H;
or R e is
wherein R l and R m are independently selected from H, linear or branched, saturated or unsaturated C 1-6 alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring; with the proviso that a least one of R l and R m is not H;
or R e is
wherein X is selected from O or S and R n is selected from linear or branched, saturated or unsaturated C 1-6 -alkyl chain that is optionally interrupted by one or two heteroatoms selected from N, O and S; and is optionally substituted by one or more substituents; alkoxycarbonyl, aminocarbonyl, alkoxy, and an optionally subsituted 3- to 6-membered heterocylic or carbocylic ring; and
R h is selected from hydroxyl, alkoxy, an amino acid residue, a linking group and a targeting molecule.
According to another aspect of the invention, the chelator-targeting molecule conjugates are provided in combination with a diagnostically useful metal or an oxide or nitride thereof.
According to another aspect of the present invention, there is provided a method of imaging a site of diagnostic interest, comprising the step of administering a diagnostically effective amount of a composition comprising a chelator-targeting molecule conjugate which is complexed to a diagnostically useful metal or an oxide or nitride thereof.
DETAILED DESCRIPTION OF THE INVENTION
In the coordination of dimethylglycine-t-butylglycine-cysteine-glycine [SEQ ID NO:1] to TcO 3+ and ReO 3+ , an single isomer was observed. A single pair of singlets associated with the methyl groups in the dimethylglycine residue was observed. The 1 H and 13 C NMR spectral data for the Re oxo complex of dimethylglycine-L-t-butylglycine-L-cysteine-glycine [SEQ ID NO:2]. The 99m Tc labeling of dimethylglycine-L-t-butylglycine-L-cysteine-glycine [SEQ ID NO:2] (RP455) and of dimethylglycine-D-t-butylglycine-L-cysteine-glycine [SEQ ID NO:3] (RP505) produced a single peak as observed in the HPLC using the radiometric detector. This was an unexpected result and is in contrast with what is observed in the Tc and Re oxo complexes of other tetradentate N 4−x S x chelators, 9, 39-55 which exist as the syn and anti isomers.
The presence of a sterically bulky group in the side chain of the peptidic chelator cause the formation of a single isomeric metal complex. In the cases of dimethylglycine-lysine-cysteine and dimethylglycine-serine-cysteine-glycine, [SEQ ID NO:6] there are insufficient bulk to cause one isomer to be preferred over another; hence the ratio of the syn and anti isomers is approximately 1:1. In the case of dimethylglycine-isoleucine-cysteine, a more sterically bulky CH(CH 3 )—CH 2 —CH 3 group was introduced into the peptidic backbone. This additional bulk caused the ratio of the syn and anti isomers to be 3:1; hence, one isomer was more favored over the other. In the case of dimethylglycine-t-butylglycine-cysteine-glycine, [SEQ ID NO:1] the incorporation of the C(CH 3 ) 3 group introduced sufficient bulk into the peptide to cause one of the isomer to be completely favored over the other; hence, a single isomeric metal complex was observed.
Molecular modeling using Quanta Charm of the Re complexes of these peptides is in agreement with the experimental results. Molecular modeling of the Re complex of dimethyglycine-L-serine-L-cysteine-glycine [SEQ ID NO:4] show the two isomers possessing thermodynamic potential energies of −67.02 and −68.37 kcal/mole. There is only a small difference in the energy of the two isomers. There is no preferred isomer for the Re complex and both the syn and anti isomers are observed at an approximate ratio of 1:1. Molecular modeling of the Re complex of dimethylglycine-lysine-cysteine shows a difference between in the thermodynamic potential energies of the two isomers to be approximately 1 kcal/mole. There is only again a small difference in the energy of the two isomers; hence both the syn and anti isomers should be observed.
In the case of dimethylglycine-L-isoleucine-L-cysteine-glycine, [SEQ ID NO:5] a more bulky side chain is incorporated into the peptidic backbone. Molecular modeling of the Re complex of the dimethylglycine-isoleucine-cysteine-glycine [SEQ ID NO:12] show one of the isomer having a potential energy that is approximately 3 kcal/mole lower than the energy of the other isomer. There is a now a greater difference in the energies and there is a slight preference for one isomer over the other. Hence, the ratio of the two isomers is 3:1.
In the case of dimethylglycine-L-t-butylglycine-L-cysteine-glycine, [SEQ ID NO:2] molecular modeling of the Re complex shows the difference in the potential energies of the two isomers to be approximately 6.5 kcal/mole. With the Re complex of dimethylglycine-D-t-butylglycine-L-cysteine-glycine, [SEQ ID NO:3] the difference in the energies of the two isomers is about 8.5 kcal/mole. One isomer is significantly preferred over the other; hence, only a single isomer is observed for the Re and Tc complexes. Molecular modeling of the Re complex of mercaptoacetyl-t-butylglycine-glycine-glycine shows that the syn and anti isomers of the complex with a energy difference of 7.4. The metal complexes of mercaptoacetyl-t-butylglycine-glycine-glycine preferred one isomer over the other and should exist as a single isomer.
Artificial amino acids with bulky side chains can be prepared according to known literature methods. 63-67 For example, both L- and D-amino acid derivatives can be prepared starting directly from the commercially available L- or D-serine, respectively. 67 Using this method, alkyl, phenyl and other bulky groups can be incorporated into serine to produce β-hydroxy-α-amino acids. 67 Hence, artificial amino acids with bulky side chains can be incorporated into peptidic chelators, which would produce a single species and an single isomeric metal complex.
The advantage of having a bifunctional chelator that forms a single isomeric metal complex is that in the labeling of biologically important molecule, there is only a single radiolabeled species. Hence, there is no need to isolate and evaluate the biological activity and toxicity of multiple compounds. It is also easier to formulate a radiopharmaceutical kit that consistently produces a single radiolabeled compound than one that produces a series of radiolabeled compounds. In the labeling of a biologically important molecule with a chelator that results in multiple species, there is a necessity to formulate the kit such that the labeling consistently produce the same set of compounds in the same ratio. This is eliminated with the use of a chelator that produces a single metal complex. Quality control of a radiopharmaceutical is also simplified by the use of a chelator that result in a single species as it is much easier to develop a quality control protocol that identifies a single well characterized compound than one that have to identify the presence and quantity of multiple compounds.
An addition benefit from the incorporation of different side chain groups into the peptidic chelator backbone to cause a single isomer is that the lipophilicity of the resulting metal complexes is altered by the addition of the different groups. The log D of the 99m Tc complex of dimethylglycine-t-butylglycine-cysteine-glycine [SEQ ID NO:1] is −1.3, compared to −2.3 for the 99m Tc complex of dimethylglycine-serine-cysteine-glycine.[SEQ ID NO:6]
The terms defining the variables R 1 -R 10 , R a -R n and X as used hereinabove in formula (I) have the following meanings:
“alkyl” refers to a straight or branched C 1 -C 8 chain and includes lower C 1 -C 4 alkyl;
“alkoxy” refers to straight or branched C 1 -C 8 alkoxy and includes lower C 1 -C 4 alkoxy;
“thiol” refers to a sulfhydryl group that may be substituted with an alkyl group to form a thioether;
“sulfur protecting group” refers to a chemical group that is bonded to a sulfur atom and inhibits oxidation of sulfur and includes groups that are cleaved upon chelation of the metal. Suitable sulfur protecting groups include known alkyl, aryl, acyl, alkanoyl, aryloyl, mercaptoacyl and organothio groups.
“Linking group” refers to a chemical group that serves to couple the targeting molecule to the chelator while not adversely affecting either the targetting function of the peptide or the metal binding function of the chelator. Suitable linking groups include alkyl chains; alkyl chains optionally substituted with one or more substituents and in which one or more carbon atoms are optionally replaced with nitrogen, oxygen or sulfur atoms. Other suitable linking groups include those having the formula A 1 —A 2 —A 3 wherein A 1 and A 3 are independently selected from N, O and S; and A 2 includes alkyl optionally substituted with one or more substituents and in which one or more carbon atoms are optionally replaced with nitrogen, oxygen or sulfur atoms; aryl optionally substituted with one or more substituents; and heteroaryl optionally substituted with one or more substituents. Still other suitable lining groups include amino acids and amino acid chains functionalized with one or more reactive groups for coupling to the glycopeptide and/or chelator. In one embodiment, the linking group is a peptide of 1 to 5 amino acids and includes, for example, chains of 1 or more synthetic amino acid residues such as β-Alanine residues. In another embodiment, the linking group is NH-alkyl-NH.
“Targeting molecule” refers to a molecule that can selectively deliver a chelated radionuclide or MRI contrasting agent to a desired location in a mammal. Preferred targeting molecules selectively target cellular receptors, transport systems, enzymes, glycoproteins and processes such as fluid pooling. Examples of targeting molecules suitable for coupling to the chelator include, but are not limited to, steroids, proteins, peptides, antibodies, nucleotides and saccharides. Preferred targeting molecules include proteins and peptides, particularly those capable of binding with specificity to cell surface receptors characteristic of a particular pathology. For instance, disease states associated with over-expression of particular protein receptors can be imaged by labeling that protein or a receptor binding fragment thereof coupled to a chelator of invention. Most preferably targeting molecules are peptides capable of specifically binding to target sites and have three or more amino acid residues. The targeting moiety can be synthesised either on a solid support or in solution and is coupled to the next portion of the chelator-targeting moiety conjugates using known chemistry.
Chelator conjugates of the invention may be prepared by various methods depending upon the chelator chosen. The peptide portion of the conjugate if present is most conveniently prepared by techniques generally established in the art of peptide synthesis, such as the solid-phase approach. Solid-phase synthesis involves the stepwise addition of amino acid residues to a growing peptide chain that is linked to an insoluble support or matrix, such as polystyrene. The C-terminus residue of the peptide is first anchored to a commercially available support with its amino group protected with an N-protecting agent such as a t-butyloxycarbonyl group (tBoc) or a fluorenylmethoxycarbonyl (FMOC) group. The amino protecting group is removed with suitable deprotecting agents such as TFA in the case of tBOC or piperidine for FMOC and the next amino acid residue (in N-protected form) is added with a coupling agent such as dicyclocarboimide (DCC). Upon formation of a peptide bond, the reagents are washed from the support. After addition of the final residue, the peptide is cleaved from the support with a suitable reagent such as trifluoroacetic acid (TFA) or hydrogen fluoride (HF).
Conjugates may further incorporate a linking group component that serves to couple the peptide to the chelator while not adversely affecting either the targetting function of the peptide or the metal binding function of the chelator.
In accordance with one aspect of the invention, chelator conjugates incorporate a diagnostically useful metal capable of forming a complex. Suitable metals include radionuclides such as technetium and rhenium in their various forms such as 99m TcO 3+ , 99m TcO 2 + , ReO 3+ and ReO 2 + . Incorporation of the metal within the conjugate can be achieved by various methods common in the art of coordination chemistry. When the metal is technetium-99m, the following general procedure may be used to form a technetium complex. A peptide-chelator conjugate solution is formed initially by dissolving the conjugate in aqueous alcohol such as ethanol. The solution is then degassed to remove oxygen then thiol protecting groups are removed with a suitable reagent, for example with sodium hydroxide and then neutralized with an organic acid such as acetic acid (pH 6.0-6.5). In the labelling step, a stoichiometric excess of sodium pertechnetate, obtained from a molybdenum generator, is added to a solution of the conjugate with an amount of a reducing agent such as stannous chloride sufficient to reduce technetium and heated. The labelled conjugate may be separated from contaminants 99m TcO 4 − and colloidal 99m TcO 2 chromatographically, for example with a C-18 Sep Pak cartridge.
In an alternative method, labelling can be accomplished by a transchelation reaction. The technetium source is a solution of technetium complexed with labile ligands facilitating ligand exchange with the selected chelator. Suitable ligands for transchelation include tartarate, citrate and heptagluconate. In this instance the preferred reducing reagent is sodium dithionite. It will be appreciated that the conjugate may be labelled using the techniques described above, or alternatively the chelator itself may be labelled and subsequently coupled to the peptide to form the conjugate; a process referred to as the “prelabelled ligand” method.
Another approach for labelling conjugates of the present invention involves techniques described in a co-pending U.S. application Ser. No. 08/152,680 filed Nov. 16, 1993, incorporated herein by reference. Briefly, the chelator conjugates are immobilized on a solid-phase support through a linkage that is cleaved upon metal chelation. This is achieved when the chelator is coupled to a functional group of the support by one of the complexing atoms. Preferably, a complexing sulfur atom is coupled to the support which is functionalized with a sulfur protecting group such as maleimide.
When labelled with a diagnostically useful metal, chelator conjugates of the present invention can be used to detect sites of inflammation by procedures established in the art of diagnostic imaging. A conjugate labelled with a radionuclide metal such as technetium-99m may be administered to a mammal by intravenous injection in a pharmaceutically acceptable solution such as isotonic saline. The amount of labelled conjugate appropriate for administration is dependent upon the distribution profile of the chosen conjugate in the sense that a rapidly cleared conjugate may be administered in higher doses than one that clears less rapidly. Unit doses acceptable for imaging inflammation are in the range of about 5-40 mCi for a 70 kg individual. In vivo distribution and localization is tracked by standard scintigraphic techniques at an appropriate time subsequent to administration; typically between 30 minutes and 180 minutes depending upon the rate of accumulation at the target site with respect to the rate of clearance at non-target tissue.
List of Abbreviations
Abbreviation
Description
Acm
acetoamidomethyl
Ar
argon
Arg
arginine
Boc
tert-butyloxycarbonyl
Cys
cysteine
DIEA
diisopropylethylamine
Dimethylgly
N,N-dimethylglycine
DMF
N,N-dimethylformamide
ES-MS
Electron Spray Mass Spectrometry
Fmoc
9-fluorenylmethyloxycarbonyl
Gly
glycine
HBTU
2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyl-uronium
hexafluorophosphate
HOBT
1-hydroxybenzotriazole
HPLC
high performance liquid chromatography
Ile
isoleucine
Leu
leucine
Lys
lysine
mL
millilitre(s)
mmol
millimole(s)
mol
mole(s)
Mott
4-methoxytrityl
NaOH
sodium hydroxide
NMP
N-methylpyrrolidone
Phe
phenylalanine
Pmc
2,2,5,7,8-pentamethylchroman-6-sulfonyl
R t
retention time
sasrin
2-methoxy-4-alkoxybenzyl alcohol (super acid
sensitive resin)
Ser
serine
t-Bu
tert-butyl
TFA
trifluoroacetic acid
Thr
threonine
Trt
trityl
Tyr
tyrosine
Y ε -R
protection group R is attached to the peptide chain via
the atom, Y, on the amino acid side chain (Y is N, O
or S and R is Acm, Boc, Mott, t-Bu or Trt)
Experimental Section
Materials. N-methylpyrrolidone, N,N-dimethylformamide, 100 mmol 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyl-uronium hexafluorophosphate/0.5M 1-hydroxybenzotriazole DMF, 2.0M diisopropylethylamine/NMP, dichloromethane and trifluoroacetic acid were purchased from Applied Biosystems Inc. Triethylamine and tert-butyl methyl ether were purchased from Aldrich Chemical Inc. Fmoc amino acid derivatives and Fmoc-Gly sasrin resin was purchased from Bachem Bioscience Inc. All chemicals were used as received. [ReO 2 (en) 2 ]Cl was prepared according to literature methods. 57,58
Instrumentation. NMR spectra were recorded on a Bruker AC-300 and on a Bruker DRX-500 NMR spectrometer and are reported as δ in ppm from external TMS. Mass spectra (electrospray) were obtained on a Sciex API#3 mass spectrometer in the positive ion detection mode. HPLC analyses and purifications were made on a Beckman System Nouveau Gold chromatographic system with a Waters 4 mm radial pak C-18 column. During analytical HPLC analysis, the mobile phase was changed from 100% 0.1% aqueous trifluoroacetic acid to 100% acetonitrile containing 0.1% trifluoroacetic acid over 20 minutes at a flow rate of 2 mL/min. All HPLC analyses were monitored with a UV detector set at 214 and 254 nm. Solid phase peptide syntheses were performed on an ABI Peptide Synthesizer model 433A using FastMoc chemistry and preloaded Fmoc amino acid sasrin resin. 59,60 Molecular modeling of the Re complexes was performed using Quanta Charm version 3.3. 63 HPLC analyses of the 99m Tc samples were made on a Beckman System Gold chromatographic system with a Vydac 4.6 mm radial pak C-18 column. The mobile phase was changed from 100% water containing 0.1% trifluoroacetic acid to 70% acetonitrile containing 0.1% trifluoroacetic acid over 25 minutes at a flow rate of 1 mL/min. The HPLC analyses of the 99m Tc samples were monitored with a UV detector set at 215 nm and a radiometric gamma detector.
Synthesis of Peptides. Peptides of various amino acid sequences were prepared via a solid phase peptide synthesis method on an automated peptide synthesizer using FastMoc 1.0 mmole chemistry. 59,60 Preloaded Fmoc amino acid sasrin resin and Fmoc amino acid derivatives were used. Prior to the addition of each amino acid residue to the N-terminus of the peptide chain, the FMOC group was removed with 20% piperidine in NMP. Each Fmoc amino acid residue was activated with 0.50 M HBTU/HOBt/DMF, in the presence of 2.0M DIEA/NMP. The C-terminus of the completed peptide was attached to the resin via the sasrin linker. The peptidyl resin was washed with dichloromethane and dried under vacuum for 20-24 hours. The peptide was cleaved off the resin by stirring the peptidyl resin in 95% aqueous trifluoroacetic acid for 3-4 hours. The sasrin resin was filtered and the filtrate was added dropwise to tert-butyl methyl ether at 0° C. The peptide precipitate out of the ether. The precipitate was collected by centrifugation and dissolved in minimal amount of water. The aqueous peptide solution was lyophilized to yield the product. The product was analyzed by mass spectrometry and by HPLC. The product was purified by HPLC. This method was used to prepare the following peptides
1)RP349: Dimethylgly-L-Ile-L-Cys(S ε -Acm)-Gly [SEQ ID NO:7]
2)RP332: Dimethylgly-L-lysine(N ε -Biotin)-L-Cys(S ε -Acm)
3)RP455: Dimethylgly-L-t-Butylgly-L-Cys(S ε -Acm)-Gly [SEQ ID NO:8]
4)RP505: Dimethylgly-D-t-Butylgly-L-Cys(S ε -Acm)-Gly [SEQ ID NO:9]
5)RP502: Dimnethylgly-L-t-Butylgly-L-Cys(S ε -Acm)-Gly-Thr-Lys-Pro-Pro-Arg [SEQ ID NO:10]
Synthesis of Re Oxo Complex of Dimethylglycine-L-t-butylgly-L-Cys-Gly: [SEQ ID NO:2] To remove the acm protecting group, dimethylgly-L-t-butylgly-L-Cys-(S ε -Acm)-Gly [SEQ ID NO:8] (84.0 mg, 0.187 mmoles) was dissolved in 2 mL of 30% acetic acid. Mercury(II) acetate (91.6 mg, 0.287 mmoles) was added to the solution and the solution was stirred under Ar at room temperature for 18 hours. H 2 S gas was then bubbled through the solution for 5 minutes, causing black HgS to precipitate. The precipitate was removed by centrifugation, and the filtrate was frozen and lyophilized overnight. [ReO 2 (en) 2 ]Cl (88.6 mg, 0.237 mmoles) was dissolved in 3 mL of distilled water and added to the lyophilized deprotected peptide. The solutions was a light green colour. The pH of the solution was adjusted to 6 using 1M NaOH. The solution was refluxed under Ar for 2 hours, during which time the solution changed from green to red. The solution was frozen and lyophilized overnight, yielding a red solid. Purification of the product was done by HPLC. Mass spectrum (electrospray): m/z=577 ([MH] + , [C 15 H 27 N 4 O 6 Re 1 S 1 ]. HPLC retention time: 9.52 min. 1 H NMR and 13 C NMR (500 MHz, D 2 O) spectral data are shown in Table 3 and 4. Log D (pH: 7.4): −1.3.
Synthesis of Re Oxo Complex of Dimethylgly-D-t-butylgly-L-Cys-Gly: [SEQ ID NO:3] The procedure for the synthesis of the Re oxo complex of dimethylgly-D-t-butylgly-L-Cys-Gly was the same as the one described for the synthesis of the Re complex of Dimethylgly-L-t-butylgly-L-Cys-Gly. [SEQ ID NO:2] Mass spectrum (electrospray): m/z=([MH] + , [C 15 H 26 N 4 O 6 Re 1 S 1 ]. HPLC retention time: 9.62 min. 1 H NMR (300 MHz, D 2 O): 2.89 (s, methyl 1 H in the dimethylglycine residue), 3.65 (s, methyl 1 H in the dimethylglycine residue).
Synthesis of Re Oxo Complex of Dimethylgly-L-t-Butylgly-L-Cys-Gly-Thr-Lys-Pro-Pro-Arg: The procedure for the synthesis of the Re oxo complex Dimethylgly-L-t-Butylgly-L-Cys-Gly-Thr-Lys-Pro-Pro-Arg [SEQ ID NO:11] was the same as the one described for the synthesis of the Re complex of dimethylgly-L-t-butylgly-L-Cys-Gly. [SEQ ID NO:2] Mass spectrum (electrospray): m/z=1155 ([MH] + , [C 41 H 71 N 13 O 12 Re 1 S 1 ] + ). HPLC retention time: 8.82 min. 1 H NMR (500 MHz, D 2 O): 2.63 (s, methyl 1 H in the dimethylglycine residue), 3.56 (s, methyl 1 H in the dimethylglycine residue).
Synthesis of Re Oxo Complex of Dimethylgly-L-Ile-L-Cys-Gly: [SEQ ID NO:5] The procedure for the synthesis of the Re oxo complex Dimethylgly-L-ile-L-cys-gly [SEQ ID NO:5] was the same as the one described for the synthesis of the Re complex of dimethylgly-L-t-butylgly-L-cys-gly. [SEQ ID NO:2] Mass spectrum (electrospray): m/z=577 ([MH] + , [C 41 H 71 N 13 O 12 Re 1 S 1 ] + ), m/z=598 ([MH] + ], [C 41 H 71 N 13 O 12 Re 1 S 1 ] + ). HPLC retention time: 9.50 min. 1 H NMR (300 MHz, D 2 O): 2.60 (s, methyl 1 H in the dimethylglycine residue of isomer A), 2.76 (s, methyl 1 H in the dimethylglycine residue of isomer B), 3.68 (s, methyl 1 H in the dimethylglycine residue of isomer A), 3.72 (s, methyl 1 H in the dimethylglycine residue of isomer B).
Synthesis of the 99m Tc complex. The peptide (0.2-0.5 μmoles) was dissolved in 200 μL of saline. Na[ 99m TcO 4 ] (10 mCi) was added to the solution, followed by tin(II) chloride (7.5×10 3 μg, 39 μmoles), sodium gluconate (1.3×10 3 μg, 5.8 μmoles), and 20 μL of 0.1M NaOH. The solution was left at room temperature for 1 hour or heated at 100° C. for 15 minutes. In the synthesis of the 99m Tc complex, the acetoamidomethyl protection group was displaced from the cysteine residue in RP414. The 99m Tc complex was analyzed by HPLC. The 99m Tc complexes of RP455, RP505 and RP502 was co-injected with the corresponding Re complexes. The HPLC retention times of the 99m Tc peptidic complexes are as follows:
1) 99m Tc complex of RP349 (Dimethylgly-L-Ile-L-Cys-Gly) [SEQ ID NO:5]: HPLC retention time: 99m Tc(RP349) R t =19.41, 21.53 min (radiometric gamma detector).
2) 99m Tc complex of RP332 (Dimethylgly-L-lysine(N ε -Biotin)-L-Cys): HPLC retention time: 99m Tc(RP332) R t =11.54, 11.97 min (radiometric gamma detector).
3) 99m Tc complex of RP455 (Dimethylgly-L-t-Butylgly-L-Cys-Gly) [SEQ ID NO:2]: HPLC retention time: ReO(RP455) R t =21.18 min (UV detector set at 215 nm); 99m Tc(RP445) R t =21.49 min (radiometric gamma detector).
4) 99m Tc complex of RP505 (Dimethylgly-D-t-Butylgly-L-Cys-Gly) [SEQ ID NO:3]: HPLC retention time: ReO(RP505) R t =18.16 min (UV detector set at 215 nm); 99m Tc(RP505) R t =18.89 min (radiometric gamma detector).
5) 99m Tc complex of RP502 (Dimethylgly-L-t-Butylgly-L-Cys(S ε -Acm)-Gly-Thr-Lys-Pro-Pro-Arg) [SEQ ID NO:10]: HPLC retention time: ReO(RP502) R t =19.76 min (UV detector set at 215 mn); 99m Tc(RP502) R t =20.10 min (radiometric gamma detector).
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Gly Ile Cys Gly | The labeling of biologically important molecules via a bifunctional chelator can result in the formation of isomers or multiple species, which can have significant impact on the biological properties of the radiopharmaceutical. For receptor-based radiopharmaceuticals, the target uptake is largely dependent on the receptor binding affinity of the targeting molecule and the blood clearance of the labeled molecule, which is determined by the physical properties of both the targeting molecule and the metal chelate. Hence, the presence of isomers for the metal chelate can have significant impact on the radiopharmaceutical. Therefore, in the development of a radiopharmaceutical or metallodrug, it is necessary to separate the isomers and evaluate the biological activities of each individual isomer. It would therefore be desirable to develop chelators that predominately form only a single stereoisomeric species upon coordination to a metal center. Disclosed herein are chelators that form a mixture enriched for a single stereoisomeric species upon coordination to a metal center. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims priority to U.S. provisional patent application 61/631,952, filed Jan. 12, 2012, pursuant to 35 USC 119(e).
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] No federal government funds were used in researching or developing this invention.
NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT
[0003] Not applicable.
SEQUENCE LISTING INCLUDED AND INCORPORATED BY REFERENCE HEREIN
[0004] Not applicable.
BACKGROUND
[0005] 1. Field of the Invention
[0006] Conventional scarves can be bulky in nature due to excessive material used for design. In order to close a conventional scarf for warmth it must be wrapped around neck multiple times and knotted, pinned or otherwise secured. In addition to sacrificing convenience of dressing and undressing, conventional configurations are also limited in their warming efficiency, as gaps tend to open between the loops of cloth, and gaps are raised between the skin and the garment where the material has bunched.
[0007] Conventional scarves also do not fit well in standard pockets or purses, often requiring bunching or folding which requires ample space and often results in a wrinkled garment.
[0008] Scarves of the “neck warmer” or “gaiter” variety are manufactured to be tubular in their design and shape, requiring the individual wearer to pull garment over his/her head creating friction and static charge. In addition to the inconvenience of pulling a garment over the head, the act of removal often musses the hair and makeup of the wearer, and accumulates makeup stains on the garment.
[0009] In regards to scarf/hat combinations, typically garment designs that can be worn as both are joined together as a hooded scarf made of multiple layers and angles of fabric. With these types of prior art constructions, a hooded portion would be placed on the head and a shawl style scarf would be wrapped around the back, shoulders and neck; fastened in front by tying a knot. These garments can shift while being worn and are unable to be worn with a coat because of all the bulky material required for design.
[0010] What is needed is a type of apparel comprising two or more magnetic fasteners, specifically shaped and sized so as to allow for a plurality of methods of use as a fitted scarf, wrap and/or headpiece.
[0011] 2. Background of the Invention
[0012] The current state of knowledge is as follows.
[0013] A neck and head garment of concave ellipse shape with a hidden magnet positioned at each end; thus providing an efficient and quick means for attaching and detaching garment. The garment's design, size, shape and magnetic closure system enables individual to wear as a hat with open top or scarf with design versatility. The addition of the magnetic closure system allows the utility of magnetically attaching any metal accessory such as a broach, barrette, or decorative pin to garment without the need of pinning
BRIEF SUMMARY OF THE INVENTION
[0014] The novel components of this work are the specific shaping and sizing of the garment, which configuration allows for a snug fit without bunching or hanging fabric, as well as the use of magnetic fasteners which provides for an ease of securing and removing the garment without the need for knotting, pinning or other less convenient means of securement.
[0015] In a preferred embodiment is provided the A garment comprising one or more layers of material cut in a concave ellipsoid shape, further comprising one or more pairs of clasp magnets secured within the garment such that the magnets overlap and bond when the garment is worn as a scarf or head piece.
[0016] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets are stitched between layers of fabric.
[0017] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets are adhered between layers of fabric or to the exterior of fabric using an adhesive.
[0018] In another preferred embodiment, the disclosed garment, further comprising wherein the adhesive is from the group comprising: cryanoacrylate, polyurethane, basting glue or thermoplastic adhesive.
[0019] In another preferred embodiment, the disclosed garment, further comprising wherein fitted pockets are located on the garment for removable placement of the clasp magnets.
[0020] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets are circular.
[0021] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets have a diameter between 8 mm and 24 mm and a depth between 1.5 mm and 1 cm.
[0022] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets have a diameter between 12 mm and 20 mm and a depth of approximately 3 mm.
[0023] In another preferred embodiment, the disclosed garment, further comprising wherein the garment measures between 6″ and 10″ from the apex to the center of the plane between the ends, and the distance between the ends measures between 22″ and 26″.
[0024] In another preferred embodiment, the disclosed garment, further comprising wherein the garment measures between 8″ and 9″ from the apex to the center of the plane between the ends, and the distance between the ends measures between 23″ and 24″.
[0025] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets are taken from the group comprising: metallic, ceramic (ferrite), injection-molded, flexible and alnico.
[0026] In another preferred embodiment, the disclosed garment, further comprising wherein the clasp magnets are neodymium magnets.
[0027] In another preferred embodiment, the disclosed garment, further comprising one or more metallic and/or magnetized accessories magnetically secured to the outer surface of the garment via the magnetic pull of the underlying clasp magnet.
[0028] In another preferred embodiment, the disclosed garment, one or more weighting elements.
[0029] In another preferred embodiment, the disclosed garment, further comprising heating wires within the layers of fabric attached to a power source.
[0030] In another preferred embodiment, garment comprising: one or more layers of material cut in a concave ellipsoid shape; one or more pairs of circular neodymium clasp magnets, each magnet measuring approximately 12 mm to 20 mm in diameter and approximately 3 mm in depth and secured within the garment such that the magnets overlap and bond when the garment is worn as a scarf or head piece; and optionally comprising weighting elements, heating wires attached to a power source and/or one or more metallic and/or magnetized accessories magnetically secured to the outer surface of the garment via the magnetic pull of the underlying clasp magnet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] FIG. 1 is a line drawing of a concave ellipsoid shape, with dotted lines evidencing the placement of magnets and two lines marking dimensions.
[0032] FIG. 2 is a line drawing evidencing the concave ellipsoid shape folded over with the magnets overlapping.
[0033] FIG. 3 is a line drawing of the garment worn as a scarf.
[0034] FIG. 4 is a line drawing of the garment worn as a scarf with a metallic decorative barrette secured to the outer magnet.
[0035] FIG. 5 is a photo drawing of the garment worn on a live model as a scarf.
[0036] FIG. 6 is a photo drawing of the garment worn on a live model as a head piece.
DETAILED DESCRIPTION OF THE INVENTION
[0037] Definitions
[0038] The following definitions are provided as an aid to understanding the detailed description of the present invention.
[0039] The phrase “concave ellipse” shall mean a boomerang, or lune-like shape comprising rounded or curved ends, as opposed to sharply pointed ends, as exemplified in FIG. 1 .
[0040] The word “magnet” shall an object creating its own persistent magnetic field and comprising positive and negative poles, each of which is attracted to another object.
[0041] The word “weighting element” means an object comprised within the present invention with a purpose of weighting the garment to avoid displacement of the garment due to wind or movement of the wearer.
[0042] Garment Shape
[0043] One object of the invention is to provide an improved scarf shape that follows the natural shape of the neck for comfort, warmth, and style. One preferred shape is a concave ellipse, which allows the garment to lay flat against the skin around the neck and dropping to the upper chest in front, at which point the garment overlaps itself and allows for the embedded or attached magnets to overlap and bond.
[0044] The concave ellipsoid shape, employed as a scarf, results in a garment that fits snugly around the wearer's neck without using multiple loops and without creating bunches in the fabric. The same shape may be sized up or down to fit the neck circumference of the wearer.
[0045] This same shape, employed as a head wrap, allows for a single wrap over the ears, providing a greater depth of material covering the back of the head, with the point of magnetic attachment at either the temple or forehead, or the lower back of the head above the neckline. Again, the garment may be sized up or down to fit varying head circumference.
[0046] The concave ellipsoid shape further allows for the wearer to employ a decorative flourish by twisting or turning the garment one or more times prior to securing the magnets. This method of decorative use is enhanced by the use of different or differently colored materials for the front and back of the garment.
[0047] Further, the disclosed shape and configuration allows the wearer to don the garment as a scarf and leave it in place while putting on and/or removing an overlaying jacket or coat.
[0048] In a preferred embodiment, the distance from apex to the center of the line between the ends, marked on FIG. 1 as line A, is between 6″ and 10″, and the distance from end to end, marked on FIG. 1 as line B, is between 22″ and 26″.
[0049] In a more preferred embodiment, the distance from apex to the center of the line between the ends, marked on FIG. 1 as line A, is between 8″ and 9″, and the distance from end to end, marked on FIG. 1 as line B, is between 23″ and 24″.
[0050] Magnetic Clasps or Fasteners
[0051] The present invention comprises a magnetic clasping mechanism. Such mechanism allows the wearer to secure or release the garment with one hand. As opposed to the currently available methods of securing scarf-like garments, such as knotting or pinning, a magnetic system provides convenience and time savings to all users, and provides an especially significant improvement for individuals suffering from joint pain such as arthritis.
[0052] The use of magnets as devices for securing moving parts is known. Examples include magnetized jewelry clasps, electronic cable connections, cabinet door hardware, eyeglass components, etc.
[0053] In the present inventions, magnets would generally be sewn within the fabric of the garment, and therefore hidden. For example, a flat magnet of any shape would be circumnavigated by stitching between two folds of material for stabilization near one end of a lune-shaped garment. A magnet of identical dimensions would be similarly secured at the same position on the opposite end of the garment. The positioning of the magnets would be such that the magnets would meet at a point of garment overlap, such that the opposite poles of the magnets would attract one another and form a bond at the point of attachment.
[0054] Variations of this placement method would exist for different types of material. For example, a scarf garment comprising an upper layer of faux or natural fur and a fabric lining could similarly be secured between the two layers, either by stitching or adhesive.
[0055] Shapes of magnets comprised within the invention may be chosen from the group including, without limitation: circular, square, rectangular, or triangular.
[0056] As an alternative to the permanent fixation of magnets within the garment, sealable pockets, using velcro, a fabric overlap or similar design, could be placed on the underside of the garment into which removable magnets could be placed.
[0057] The magnets themselves may be chosen from a variety of types, including but not limited to magnetic metals from the group comprising iron, aluminum, cobalt, nickel or rare earth metals. Alternatively, the magnets may be chosen from the group comprising any commercially available composite or synthetic magnets such as ceramics (ferrite), alnico, injection-molded magnets or flexible magnets.
[0058] A neodymium (or “neo”) magnet (also known as NdFeB, NIB, or Neo magnet), the most widely-used type of permanent rare earth magnet, is made from an alloy of neodymium, iron and boron to form the Nd2Fe14B tetragonal crystalline structure. Neo magnets are known for superior strength of magnetic field when compared to other commercially available magnets of similar dimension.
[0059] Ceramic, or ferrite, magnets are made of a sintered composite of powdered iron oxide and barium/strontium carbonate ceramic. Given the low cost of the materials and manufacturing methods, inexpensive magnets of various shapes can be easily mass-produced. The resulting magnets are non-corroding but brittle and must be treated like other ceramics.
[0060] Alnico magnets are made by casting or sintering a combination of aluminum, nickel and cobalt with iron and small amounts of other elements added to enhance the properties of the magnet. Sintering offers superior mechanical characteristics, whereas casting delivers higher magnetic fields and allows for the design of intricate shapes Alnico magnets resist corrosion and have physical properties more forgiving than ferrite, but not quite as desirable as a metal.
[0061] Injection-molded magnets are a composite of various types of resin and magnetic powders, allowing parts of complex shapes to be manufactured by injection molding. The physical and magnetic properties of the product depend on the raw materials, but are generally lower in magnetic strength and resemble plastics in their physical properties.
[0062] Flexible magnets are similar to injection-molded magnets, using a flexible resin or binder such as vinyl, and produced in flat strips, shapes or sheets. These magnets are lower in magnetic strength but can be very flexible, depending on the binder used.
[0063] In a preferred embodiment, the invention comprises two flat, circular magnets, each with a diameter between 8 mm and 24 mm and a depth between 1.5 mm and 1 cm.
[0064] In a more preferred embodiment, the invention comprises two flat, circular magnets, each with a diameter between 12 mm and 20 mm and a depth of approximately 3 mm.
[0065] In another preferred embodiment, the invention comprises more than one pair of magnets to provide multiple points of attachment.
[0066] In a more preferred embodiment, the invention comprises two pairs of magnets providing two separate points of attachment.
[0067] In another embodiment, one or both of the magnets in a given pair are adhered to the exterior surface of the garment instead of sewn or otherwise secured within the garment, using one or more appropriate commercially available adhesives from the group comprising, without limitation, cyanoacrylates, basting glue, fabric stiffener, polyurethane, polyester resin, polyols, acrylic polymers, polychloroprene or similar contact adhesive, thermoplastic adhesives, acrylic glue, or epoxy resin.
[0068] The presence of magnet clasps within or on the garment further provides a point of attachment for metallic or magnetized accessories, again without requiring sewing or pinning In a preferred embodiment, one or more metallic or magnetized decorative accessories, such as broaches or barrettes, are secured to the outer surface of the garment over an outer magnetic clasp after the garment has been donned.
[0069] In another preferred embodiment, functional accessories comprising metal or magnets may be attached to the outer surface of the garment over an outer magnetic clasp via the magnetic pull of the underlying clasp magnet. Such accessories or devices could include, without limitation, time pieces, GPS devices, compasses or eyeglasses.
[0070] Other Features
[0071] Traditional scarves have a tendency to shift due to wind or movement of the wearer. This problem is especially acute for people wearing the garment while participating in sports or physical activities, such as skiing.
[0072] In a preferred embodiment, the present invention comprises one or more weighting elements to prevent shifting or repositioning of the garment once it is in place, whether from wind or from movement of the wearer. By way of example and not limitation, such weighting elements could be sewn or adhered within the fabric layers of the garments by methods disclosed herein related to magnets (e.g., sewing or by adhesives).
[0073] In another preferred embodiment, the weighting elements could comprise materials from the group including, without limitation, sand or metallic beads.
[0074] Apparel comprising heating elements, often in the form of metallic wires or threads, is known. Self-heated socks, most noticeably, have long been marketed to hunters and skiers.
[0075] In another preferred embodiment, the present invention comprises one or more heating elements connected to a power source. In another preferred embodiment, the heating elements comprise a plurality of metallic wires or threads. In more preferred embodiment, the heating elements are attached to a commercially available battery power source, from the group including, but not limited to, a AAA, AA, C, D, LR44 or 9-volt.
[0076] Detailed Figures Descriptions
[0077] Referring now to the Figures, FIG. 1 is a line drawing evidencing an open garment 110 cut in the concave ellipsoid shape, with a magnet 120 sewn within each end, with each magnet's evidenced by a circular broken line. Line 140 measures the distance between the apex and the center of the plane between the two ends, and line 150 measures the distance between the two ends.
[0078] Referring now to the Figures, FIG. 2 is a line drawing evidencing garment 110 cut in the concave ellipsoid shape but resting in the overlap position, with the position of the overlapping magnets 120 evidenced by a circular broken line.
[0079] Referring now to the Figures, FIG. 3 is a line drawing of garment 110 being worn as a scarf, wrapped around the neck and shoulders of the wearer, with a decorative, magnetized broach 130 affixed over magnets 120 (not shown).
[0080] Referring now to the Figures, FIG. 4 is a line drawing of garment 110 being worn as a head piece, wrapped around the head of the wearer with magnets 120 (not shown) affixing over the wearer's temple, with decorative broach 130 affixed over the magnets.
[0081] The references recited herein are incorporated herein in their entirety, particularly as they relate to teaching the level of ordinary skill in this art and for any disclosure necessary for the commoner understanding of the subject matter of the claimed invention. It will be clear to a person of ordinary skill in the art that the above embodiments may be altered or that insubstantial changes may be made without departing from the scope of the invention. Accordingly, the scope of the invention is determined by the scope of the following claims and their equitable Equivalents. | This invention relates to a type of apparel specifically shaped and sized to allow for a plurality of uses as a scarf, wrap, or headpiece, further comprising one or more pairs of magnetic fasteners to secure the garment in a predetermined configuration. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of Japanese Patent Application No. 2010-015629 filed on Jan. 27, 2010 and U.S. Provisional Application Ser. No. 61/282,665 filed on Mar. 15, 2010, the entire disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present disclosure relates to an evaluation device and an evaluation method for a substrate mounting apparatus used for holding a target substrate such as a silicon wafer in a semiconductor manufacturing process and controlling a temperature of the target substrate. More particularly, the present disclosure relates to a device and a method for easily evaluating a function, especially, a temperature control function, of a substrate mounting apparatus when a target substrate is heated from the outside in a plasma process or the like.
BACKGROUND OF THE INVENTION
In a semiconductor manufacture field, there has often been used a plasma processing apparatus which performs an etching process or a film forming process by applying plasma to a target substrate (hereinafter, referred to as “substrate”) such as a silicon wafer. Since such a plasma process has been performed under a depressurized pressure, a vacuum chuck cannot be used to hold the substrate. Thus, there has generally been used a substrate mounting apparatus such as a mechanical clamp or an electrostatic chuck using electrostatic force.
The electrostatic chuck may include a substrate mounting surface made of an insulator having therein an embedded sheet electrode. If a high potential is applied to the sheet electrode, Coulomb force or Johnsen-Rahbek force is generated by static electricity distributed in the insulator and polarized and electrified charges in the substrate. Accordingly, the substrate can be held onto the substrate mounting surface by the Coulomb force or the Johnsen-Rahbek force.
A basic function of the electrostatic chuck is to adsorptively hold the substrate, but recently, the electrostatic chuck has generally been used for controlling a temperature of the silicon wafer during a process. By way of example, the electrostatic chuck may be used for cooling the silicon wafer by flowing an inert gas such as helium between the silicon wafer and the electrostatic chuck, or the electrostatic chuck may be used for heating the silicon wafer in combination with a heater. This is because the temperature of the substrate is closely related with a rate of an etching process or a film forming process and a quality of a processing result.
For this reason, in evaluation of the electrostatic chuck, there has been considered the temperature control function of the silicon wafer and uniformity of temperature distribution during a film forming process and an etching process onto the silicon wafer as very important evaluation factors in addition to a mechanical characteristic, a decrease of particles, improvement in purity, plasma resistance, and chemical resistance.
Generally, the temperature of the substrate during a plasma process may depend on heat inputted to the substrate or a mounting table from the outside. Therefore, the temperature control function of the substrate mounting apparatus may be influenced by heat from the outside.
Therefore, performance evaluation for the electrostatic chuck used in the plasma processing apparatus needs to consider heat inputted to the substrate or the mounting table from plasma. If a thermal condition in the performance evaluation is different from a thermal condition in an actual plasma process, results of the performance evaluation may be greatly different from results of the actual plasma process.
If characteristics of the electrostatic chuck are measured by using the plasma processing apparatus under the same condition as a process such as an actual etching process, the performance evaluation can be conducted accurately. However, it costs a lot to use a high-priced and complicated plasma processing apparatus for this evaluation. Further, there is a problem in that it takes a lot of effort and time required for the evaluation.
For this reason, disclosed in Patent Document 1 are an evaluation device and an evaluation method for an electrostatic chuck. In Patent Document 1, performance of an electrostatic chuck is evaluated by providing the electrostatic chuck in an evacuable airtight chamber and heating a substrate by a lamp heater positioned above the electrostatic chuck to simulate a thermal condition in a plasma processing apparatus.
Meanwhile, disclosed in Patent Document 2 are an evaluation device and an evaluation method for simply evaluating a substrate mounting apparatus by simulating a thermal status corresponding to an actual plasma processing apparatus.
Patent Document 1: Japanese Patent Laid-open Publication No. 2006-86301
Patent Document 2: Japanese Patent Laid-open Publication No. 2008-108938
As disclosed in Patent Document 1, the evaluation method for the electrostatic chuck is conducted in the evaluation device which simulates the thermal condition by using the lamp heater (halogen lamp) as an external heating source instead of plasma. Accordingly, the performance for the electrostatic chuck can be simply evaluated.
However, upon review of this method, the present inventor has found that it is difficult to simulate the thermal condition using plasma by the evaluation method for the electrostatic chuck disclosed in Patent Document 1.
The reason for that is a difference in a heat transfer mechanism between heat transfer from plasma and heat transfer from a conventional heating lamp or heater. Generally, it is deemed that the heat transfer from plasma of high temperature is mainly caused by contact heat transfer by molecules excited into plasma.
Meanwhile, the heat transfer from the heating lamp occurs in such a way that resonance absorption of an infrared light irradiated from a heating source occurs on a substrate, and such energy brings about motion (vibration) of molecules, and, thus, friction between vibrated materials generates heat.
Here, the infrared light irradiated from the heating lamp may mainly include a near infrared ray (about 0.78 μm to about 2 μm) and an infrared ray (about 2 μm to about 4 μm). A silicon wafer serving as the substrate mostly transmits the infrared ray (infrared light) of a wavelength in the range of from about 1 μm to about 5 μm. For this reason, the silicon wafer is hardly heated by an infrared lamp, and the infrared light penetrates the silicon wafer and entirely heats a surface (mounting surface) of the electrostatic chuck underneath the silicon wafer.
Here, in a microscopic view, there exist freaks on surfaces of the electrostatic chuck and the silicon wafer. For this reason, contact surfaces between the electrostatic chuck and the silicon wafer have some areas where the surfaces are in close contact with each other and some areas where a gap exists between the surfaces. In this status, the irradiation light (infrared light) from the infrared lamp mostly penetrates the silicon wafer. Accordingly, only the surface of the electrostatic chuck is heated at the areas where the gap exists between the surfaces, whereas the contact surface of the silicon wafer with the electrostatic chuck is heated at the areas where the surfaces are in close contact with each other. Consequently, the heat is sufficiently transferred to the silicon wafer at the areas where the surfaces are in close contact with each other. Meanwhile, the heat is not sufficiently transferred into the silicon wafer at the areas where the gap exists between the surfaces (where the surfaces are not in close contact with each other).
Meanwhile, in an actual process using plasma, it is deemed that heat is mainly transferred by contact heat transfer of molecules when molecules exited into plasma of high temperature when the molecules are brought into contact with the silicon wafer. For this reason, the entire surface of the silicon wafer can be uniformly heated.
Therefore, it is deemed that a thermal status of the electrostatic chuck and the silicon wafer in the simulation device using the infrared light is different from that in the actual plasma processing apparatus.
In order to solve this problem, disclosed in Patent Document 2 is the evaluation device for evaluating the performance of the substrate mounting apparatus by using the infrared heater as the heating source. In this evaluation device, to simulate the thermal status corresponding to the actual plasma processing apparatus, the thermal status of the plasma processing apparatus can be simply simulated by using a substrate made of silicon carbide which absorbs the infrared light instead of a substrate made of silicon.
However, the evaluation device disclosed in Patent Document 2 needs to additionally include the infrared heater or the lamp as the heating source like the evaluation device disclosed in Patent Document 1. For this reason, there is a problem in that the evaluation device becomes larger and expensive.
Further, since the heating source such as the infrared heater is positioned above the substrate, when temperature distribution of an entire substrate is measured by, for example, a non-contact radiation thermometer, the measurement may be influenced by the heating source such as the infrared heater. Meanwhile, it may be possible to use a temperature probe as a thermocouple element, but it is very difficult to arrange temperature probes as thermocouple elements on the entire substrate. If the temperature probes as thermocouple elements are arranged, areas where they are positioned have thermal characteristics that are different from other areas. For this reason, if a multiple number of such areas having thermal characteristics different from the other areas exist on the substrate for evaluation, a thermal status thereof becomes different from an actual thermal status. Accordingly, there is a problem in that performance evaluation of the electrostatic chuck cannot be simply conducted on its entire surface with high precision according to the technologies disclosed in Patent Documents 1 and 2.
Meanwhile, when a temperature control function of an electrostatic chuck serving as a substrate mounting table is evaluated, it is not necessary to uniformly evaluate an entire surface of a substrate mounting surface. According to research by the present inventor until now, it has been found that it is possible to specify some areas which should not be excluded from evaluation of characteristics of the electrostatic chuck. By way of example, there is formed a flow path for coolant used for a temperature control in the electrostatic chuck and the coolant flows into and out from the flow path. For this reason, it is difficult to control temperatures at an inlet and outlet of the coolant flow path as compared to temperatures in the other areas. Further, an area near a high voltage power supply unit where the coolant flow path cannot be formed or an area near lift pins for moving the substrate up and down have the same problem. Furthermore, an outer periphery in a circumferential direction of the substrate has a plasma density distribution problem or electric field distribution problem and needs more delicate temperature control than any other areas.
In the conventional methods, it is possible to measure and evaluate temperature characteristics on the entire surface of the substrate mounting table at a time, but it is very difficult to uniformly heat the entire substrate. Further, it costs a lot to conduct the measurement and evaluation.
With regard to this problem, the present inventor has conceived that a self-heating type evaluation substrate can be used as a dedicated substrate (hereinafter, referred to as “evaluation substrate”) to evaluate characteristics of a substrate mounting apparatus such as an electrostatic chuck. According to this, it is possible to evaluate performance of an electrostatic chuck made of, for example, silicon which transmits the infrared light. Further, if the self-heating type evaluation substrate is used, the heating source such as the infrared heater is not needed, and, thus, a non-contact thermometer can be provided thereabove. With this configuration, it is possible to measure temperature distribution of an entire surface of the evaluation substrate with high accuracy. The present inventor has derived the present disclosure in view of the foregoing description.
Accordingly, the present disclosure provides an evaluation device and an evaluation method for a substrate mounting apparatus capable of simply evaluating a temperature control function of the substrate mounting apparatus under preset evaluation conditions or circumstances, and an evaluation substrate used for the same.
BRIEF SUMMARY OF THE INVENTION
In accordance with one aspect of the present disclosure, there is provided an evaluation device for a substrate mounting apparatus which holds a target substrate mounted on a mounting surface and controls a temperature of the target substrate. The evaluation device includes an evacuable airtight chamber in which the substrate mounting apparatus is provided; an evaluation substrate which is mounted on the mounting surface instead of the target substrate and includes a self-heating resistance heater; and a temperature measurement unit which measures a temperature of the evaluation substrate.
In the evaluation device, the resistance heater may be provided within the evaluation substrate and/or on all or a part of a surface of the evaluation substrate.
In the evaluation device, the evaluation substrate may have substantially same size and shape as the target substrate.
In the evaluation device, the evaluation substrate may have an enough size to measure temperatures of measurement target areas on the mounting surface.
In the evaluation device, the temperature measurement unit may be a temperature probe as a thermocouple element.
In the evaluation device, temperature probe as a thermocouple element may be provided in an opening formed in the resistance heater so as to be brought into contact with the evaluation substrate.
In the evaluation device, the temperature measurement unit may be a non-contact thermometer which is not in contact with the evaluation substrate.
In the evaluation device, the resistance heater may have therein an opening through which infrared light of the evaluation substrate radiated.
In the evaluation device, the non-contact thermometer may be provided outside the airtight chamber so as to receive the infrared light via an observation window provided in the airtight chamber.
In the evaluation device, the substrate mounting apparatus may be an electrostatic chuck.
In accordance with another aspect of the present disclosure, there is provided an evaluation substrate used in an evaluation device for a substrate mounting apparatus which holds a target substrate mounted on a mounting surface and controls a temperature of the target substrate. The evaluation substrate includes a resistance heater which increases a temperature of the evaluation substrate to a required level in a substantially uniform manner; and a temperature measurement unit which measures a temperature of the evaluation substrate.
In the evaluation substrate, the evaluation substrate may have substantially same size and shape as the target substrate.
In the evaluation substrate, the evaluation substrate may have an enough size to measure temperatures of measurement target areas on the mounting surface.
In the evaluation substrate, the resistance heater may be provided on all or a part of a surface of the evaluation substrate.
In the evaluation substrate, the temperature measurement unit may be a temperature probe as a thermocouple element.
In the evaluation substrate, the temperature probe as a thermocouple element may be provided in an opening formed in the resistance heater so as to be brought into contact with the evaluation substrate.
In the evaluation substrate, the temperature measurement unit may be a thermometer which is not in contact with the evaluation substrate.
In the evaluation substrate, an opening through which infrared light of the evaluation substrate are radiated may be formed in the resistance heater provided on the evaluation substrate.
In accordance with still another aspect of the present disclosure, there is provided an evaluation method for a substrate mounting apparatus includes providing the substrate mounting apparatus which holds a target substrate mounted on a mounting surface and includes a temperature control unit for controlling a temperature of the target substrate in a depressurizable airtight chamber; mounting an evaluation substrate having a self-heating resistance heater on the substrate mounting apparatus; measuring temperature distribution of the evaluation substrate by adjusting a temperature of the evaluation substrate to a required level by the temperature control unit and the resistance heater; and evaluating a function of the substrate mounting apparatus based on the temperature distribution of the evaluation substrate.
In the evaluation method, the evaluation substrate may be self-heated by the resistance heater provided within the evaluation substrate and/or on all or a part of a surface of the evaluation substrate.
In the evaluation method, the function of the substrate mounting apparatus may be evaluated by using the evaluation substrate having substantially same size and shape as the target substrate.
In the evaluation method, characteristics of measurement target areas on the mounting surface may be evaluated by using the evaluation substrate having an enough size to measure temperatures of the measurement target areas.
In the evaluation method, the temperature distribution of the evaluation substrate may be measured by a temperature probe as a thermocouple element.
In the evaluation method, the temperature probe as a thermocouple element may be provided so as to be brought into contact with the evaluation substrate.
In the evaluation method, the temperature distribution of the evaluation substrate may be measured by a thermometer which is not in contact with the evaluation substrate.
In the evaluation method, an opening may be formed in the resistance heater, and the temperature distribution of the evaluation substrate may be measured by using an opening through which infrared light is radiated from the evaluation substrate.
In the evaluation method, the temperature distribution of the evaluation substrate may be measured via an observation window provided in the airtight chamber by a unit outside the airtight chamber.
In the evaluation method, the substrate mounting apparatus may be an electrostatic chuck.
In accordance with the present disclosure, it is possible to provide an evaluation device and an evaluation method for a substrate mounting apparatus capable of simply evaluating a temperature control function of the substrate mounting apparatus depending on evaluation conditions or circumstances and an evaluation substrate used for the same.
BRIEF DESCRIPTION OF THE DRAWINGS
Non-limiting and non-exhaustive embodiments will be described in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be intended to limit its scope, the disclosure will be described with specificity and detail through use of the accompanying drawings, in which:
FIG. 1 is a schematic cross-sectional view of an evaluation device for a substrate mounting apparatus in accordance with an embodiment of the present disclosure;
FIGS. 2A and 2B show a chip-type evaluation substrate in accordance with an embodiment of the present disclosure;
FIGS. 3A and 3B show a chip-type evaluation substrate in accordance with an embodiment of the present disclosure;
FIG. 4 shows an evaluation device for a substrate mounting apparatus in case of measuring a temperature of an evaluation substrate by a radiation thermometer;
FIG. 5 shows an evaluation device for a substrate mounting apparatus in case of measuring a temperature of an evaluation substrate by a radiation thermometer;
FIG. 6 is a plane view of an evaluation substrate in which a resistance heater is positioned so as to surround a temperature probe as a thermocouple element;
FIG. 7 is a plane view of an evaluation substrate in which temperature probes as thermocouple elements are provided inside clip-shaped resistance heaters;
FIG. 8 is a plane view of an evaluation substrate in accordance with another embodiment of the present disclosure, and the evaluation substrate is capable of evaluating an outer periphery of a wafer in a circumferential direction thereof;
FIG. 9 is a plane view of an evaluation substrate in which openings are formed inside the clip-shaped resistance heaters;
FIG. 10 is a plane view of an evaluation substrate in which temperature probes as thermocouple elements are removed and openings are formed;
FIG. 11 is a plane view of an evaluation substrate in which a ring-shaped resistance heater is provided at an outer periphery in a circumferential direction and a plurality of openings is formed in the resistance heater; and
FIG. 12 is a plane view of an evaluation substrate in which a spiral-shaped resistance heater is provided and a plurality of openings is formed in the resistance heater.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings, but the present disclosure is not limited thereto. FIG. 1 is a schematic cross-sectional view of an evaluation device for a substrate mounting apparatus in accordance with an embodiment of the present disclosure. This evaluation device may include an airtight chamber 1 ; a vacuum pump 6 which evacuates the inside of the chamber 1 ; an electrostatic chuck 2 provided in the chamber 1 ; an evaluation substrate 4 mounted on a mounting surface 3 of the electrostatic chuck 2 ; a self-heating type resistance heater 5 (see FIGS. 2A and 2B ) provided on the evaluation substrate 4 ; an AC power supply 13 which supplies a power to the resistance heater 5 ; temperature probes 14 as thermocouple elements buried in the evaluation substrate 4 ; and a thermocouple main body 15 connected thereto.
A type of the electrostatic chuck 2 as an evaluation target in the present disclosure is not specially limited. By way of example, an insulation body 7 may be any one of a ceramic body formed by thermal spraying or sintering or insulating resin body such as a polyimide film. An electrode 8 may be formed into any one of a film shape, a plate shape, and a spiral coil shape as long as a voltage can be applied substantially uniformly onto an entire surface of a target substrate.
The electrostatic chuck 2 may have a configuration in which the electrode 8 is buried in the insulation body 7 constituting the mounting surface 3 , and the insulation body 7 is fixed on a cooling plate 9 . In the cooling plate 9 , a coolant path is formed and coolant flows therein through an inlet line and an outlet line. Further, the electrode 8 is supplied with a high voltage from a DC power supply 10 .
Provided at a ceiling of the chamber 1 is a heat insulating plate 12 via an insulating post 11 in order to prevent overheating of the ceiling. Here, the heat insulating plate 12 can be omitted depending on an upper limit of a temperature increased by the resistance heater 5 . The resistance heater 5 is supplied with a power from the AC power supply 13 outside the chamber 1 , so that the evaluation substrate 4 is self-heated. The power is controlled by a controller (not shown) to an appropriate value.
Further, desirably, the cooling plate 9 and the insulation body 7 may adhere to each other as one body in order to improve heat conductivity and the cooling plate 9 may be made of a material of high heat conductivity.
Meanwhile, a cooling medium such as a He gas can be introduced between the evaluation substrate 4 and the insulation body 7 in order to directly cool the evaluation substrate. Alternatively, a heater may be provided in the cooling plate 9 and the cooling plate 9 may be used as not a heat sink but a heat source.
Desirably, by evacuating the inside of the camber 1 by the vacuum pump, the chamber 1 may have a vacuum level lower than several Torr, and specifically equal to a vacuum level of various kinds of plasma processing apparatuses. However, any vacuum level is possible as long as the evaluation substrate 4 is maintained in a thermally isolated state from its surroundings. If air flow and convection do not occur, the chamber 1 may be in the atmospheric atmosphere.
Herein, a feature of the prevent disclosure is that the resistance heater 5 (see FIGS. 2A and 2B ) is provided on the evaluation substrate 4 . Since the resistance heater 5 is provided on the evaluation substrate 4 , heat can be transferred directly to the evaluation substrate 4 . For this reason, a material, which is not heated due to transmission of infrared lights from an infrared lamp or an infrared heater, can be heated. Further, since the evaluation substrate 4 is self-heated, an external heating source such as an infrared heater or a lamp is unnecessary.
Hereinafter, there will be explained a size of the evaluation substrate 4 including the resistance heater 5 . The present inventor found out that when performance evaluation for the electrostatic chuck 2 is conducted, temperature distribution on its entire surface needs not be measured at a time. That is because it is possible to specify areas to be measured after evaluation of a temperature control function of the electrostatic chuck 2 is completed. By way of example, areas corresponding to an inlet and an outlet of the coolant path or a high voltage power supply unit, areas near lift pins, and an outer periphery of the target substrate in a circumferential direction thereof are important places for the evaluation.
In view of the foregoing, desirably, the evaluation substrate 4 may be large enough such that temperatures can be measured at areas to be evaluated, and such an evaluation substrate 4 will be referred to as “chip-type evaluation substrate” herein. It is easy to uniformly heat the entire chip-type evaluation substrate 4 including the resistance heater 5 . Depending on an arrangement of the resistance heater 5 , the evaluation substrate 4 may have the same size and shape as an actual target substrate such as a silicon wafer of about 300φ.
Hereinafter, there will be explained a principle of measurement of a heat flow rate by using the evaluation substrate 4 of the present disclosure. The evaluation substrate 4 is maintained in a thermally isolated state from the outside. By way of example, the vacuum chamber 1 may have a vacuum level in the range of from about 1 Pa to about 100 Pa and a current may flow into the resistance heater 5 . A power applied to the resistance heater 5 may be in the range of from about 1 kW/m 2 to about 100 kW/m 2 , and, desirably, in the range of from about 20 kW/m 2 to about 40 kW/m 2 . By way of example, if a silicon evaluation substrate having a size of about 300φ heated from the normal temperature to about 100°C., it is desirable to apply a power in the range of from about 2 kW to about 4 kW.
In this case, if the applied voltage is about 100 V, resistance is in the range of from about 2Ω to about 5Ω, and if the applied voltage is about 200 V, resistance is in the range of from about 10Ω to about 20Ω.When such a power is applied to the resistance heater 5 , an hourly change in temperature of the evaluation substrate 4 is set as a reference temperature characteristic.
Subsequently, the evaluation substrate 4 is mounted on the electrostatic chuck 2 , the same power is applied to the resistance heater 5 , and a temperature of the evaluation substrate 4 which is temperature-controlled by the electrostatic chuck 2 is measured every hour. This is the same as a measurement of a heat loss (calories lost by the evaluation substrate 4 ) at a contact area between the electrostatic chuck 2 and the evaluation substrate 4 . Further, by comparing the measured heat loss value with a theoretical heat loss value, a function of the electrostatic chuck 2 is evaluated.
Herein, the temperature of the evaluation substrate 4 can be measured directly by, for example, the temperature probe 14 as a thermocouple element. Alternatively, the temperature of the evaluation substrate 4 can be measured by, for example, a radiation thermometer as a non-contact temperature measuring device. Hereinafter, there will be explained each temperature measuring method in case of using the chip-type evaluation substrate 4 and in case of using the evaluation substrate having the same size and shape as the target substrate.
FIGS. 2A and 2B show the chip-type evaluation substrate 4 in accordance with an embodiment of the present disclosure. The evaluation substrate 4 may evaluate characteristics of the electrostatic chuck 2 at each area. FIG. 2A is a perspective view of the evaluation substrate 4 , and FIG. 2B is a cross-sectional view thereof. As depicted in FIGS. 2A and 2B , the resistance heater 5 is provided on a surface of the evaluation substrate 4 via an adhesion layer such as an adhesive. Alternatively, the resistance heater 5 may be provided on the evaluation substrate 4 by heat-pressing adhesion, vapor deposition, thermal spraying, coating, and printing other than by using the adhesive.
Herein, it is illustrated that the resistance heater is provided on the surface, i.e., a base 41 , of the evaluation substrate 4 , but the resistance heater 5 may be provided within the base 41 . By way of example, the resistance heater 5 may be embedded in the base 41 . Further, the resistance heater 5 may be buried when the evaluation substrate 4 is fabricated.
A material of the resistance heater 5 is not specifically limited, but in general, any material such as a metal heating wire, graphite, or conductive ceramic can be used as long as it generates heat when a current flows. Further, any shape or any arrangement of the resistance heater 5 is possible as long as the entire evaluation substrate 4 can be uniformly heated.
As depicted in FIGS. 2A and 2B , a plurality of the temperature probes 14 as thermocouple elements is connected to the resistance heater 5 . An electromotive power from the temperature probes 14 as thermocouple elements is transmitted to the external thermocouple main body 15 via a connection terminal provided at an inner wall of the chamber 1 , and, thus, a temperature of the evaluation substrate 4 is measured.
Front ends of the temperature probes 14 as thermocouple elements are closely connected and fixed to the evaluation substrate 4 by an adhesive or the like. It is important that a total amount of the adhesive covering the front ends is uniform and there is no gap in a contact interface and also, air bubbles are not entered therein.
A temperature of the evaluation substrate 4 may be measured by a non-contact thermometer such as a radiation thermometer instead of the temperature probes 14 as thermocouple elements. FIGS. 3A and 3B show the chip-type evaluation substrate 4 in accordance with an embodiment of the present disclosure. As depicted in FIGS. 3A and 3B , the temperature probes 14 as thermocouple elements in the resistance heater 5 of the evaluation substrate 4 illustrated in FIGS. 2A and 2B are removed. A surface of the base 41 can be seen through openings 42 to which the temperature probes 14 as thermocouple elements were attached.
With this configuration, it is possible to measure infrared light radiated through the openings 42 of the resistance heater 5 and the temperature of the evaluation substrate 4 can be measured by measuring the infrared light.
Hereinafter, there will be explained a temperature measurement method of the evaluation substrate 4 using a radiation thermometer. As described above, various materials may be considered for a material of the evaluation substrate 4 . In this case, emissivity may be varied depending on a material of the evaluation substrate 4 and a displayed temperature of the radiation thermometer may be affected accordingly. Therefore, for example, a thermostat furnace may be used and a difference between a temperature of the thermostat furnace (i.e., a temperature of the evaluation substrate 4 ) and the displayed temperature of the radiation thermometer may be corrected in advance. By making such a correction in advance, a temperature of the evaluation substrate 4 can be measured with high accuracy regardless of a material of the evaluation substrate 4 .
FIG. 4 shows an evaluation device for a substrate mounting apparatus in case that a temperature of the evaluation substrate 4 is measured by a radiation thermometer. As depicted in FIG. 4 , the radiation thermometer 16 may be provided in the airtight chamber 1 .
In the evaluation device depicted in FIG. 4 , the radiation thermometer 16 is provided at the heat insulating plate 12 via the insulating post 11 in the airtight chamber 1 in order to prevent overheating of the ceiling. With this radiation thermometer 16 , it is possible to measure a temperature by using infrared light radiated from the openings 42 of the evaluation substrate 4 . Further, in the present embodiment, temperature distribution of the entire surface of the evaluation substrate 4 is measured by a single radiation thermometer 16 . However, the present disclosure is not limited thereto, and, by way of example, another radiation thermometer 16 may be further provided in order to measure a temperature of the outer periphery of the evaluation substrate 4 .
FIG. 5 illustrates an evaluation device in which the radiation thermometer 16 is provided outside the airtight chamber 1 . When the radiation thermometer 16 is provided outside the airtight chamber 1 , an observation window 18 may be provided at an upper part of the chamber 1 and a hole may be formed at a position corresponding to the observation window 18 in the heat insulating plate 12 . With this observation window 18 , it is possible to measure the infrared light radiated through the openings 42 of the evaluation substrate 4 , and, thus, a temperature of the evaluation substrate 4 can be measured. Since the radiation thermometer 16 is provided outside the airtight chamber 1 , a design of the evaluation device becomes easier.
Hereinafter, there will be explained the evaluation substrate 4 having the same size and shape as the target substrate. FIG. 6 is a plane view of an evaluation substrate 4 - 1 , and the evaluation substrate 4 - 1 may include a base 41 as a silicon wafer which is used in an actual plasma process; a temperature probe 14 as a thermocouple element embedded in a central portion of the base 41 ; and a resistance heater 5 positioned so as to surround the temperature probe 14 as a thermocouple element.
As described above, a power supply unit for supplying a high voltage to the electrode 8 is positioned at a central area of the electrostatic chuck 2 , and, thus, a coolant path cannot be formed. For this reason, evaluation of a temperature at the central area is very important and the evaluation substrate 4 - 1 is used therefor.
FIG. 7 is a plane view of an evaluation substrate 4 - 2 , and the evaluation substrate 4 - 2 may include a base 41 as a silicon wafer; clip-shaped resistance heating bodies 5 provided at eight (8) areas on the outer periphery in the circumferential direction; and temperature probes 14 as thermocouple elements provided in the resistance heating bodies 5 . As described above, during a plasma process, the outer periphery of the wafer in the circumferential direction has a problem with non-uniformity in plasma density distribution or electric field distribution. For this reason, the outer periphery is a very important area in evaluation of functions of the electrostatic chuck 2 . Accordingly, with the evaluation substrate 4 - 2 , it is possible to evaluate the outer periphery of the wafer in the circumferential direction as well as the central area thereof.
FIG. 8 is a modification example of FIG. 7 and shows a plane view of an evaluation substrate 4 - 3 in accordance with another embodiment of the present disclosure. The evaluation substrate 4 - 3 can measure a temperature of the central area and the circumferential periphery of the wafer. In the evaluation substrate 4 - 2 illustrated in FIG. 7 , the areas surrounded by the resistance heating bodies 5 are heated and temperatures of the areas are measured by the temperature probes 14 as thermocouple elements, whereas in the evaluation substrate 4 - 3 illustrated in FIG. 8 , temperatures of the outer periphery in the circumferential direction and the central area can be measured while the entire wafer is uniformly heated.
Hereinafter, there will be explained a case where a temperature of the evaluation substrate 4 is measured by using the radiation thermometer 16 . FIG. 9 is a plane view of an evaluation substrate 4 - 4 , and the evaluation substrate 4 - 4 may include a base 41 as a silicon wafer; clip-shaped resistance heating bodies 5 provided at eight (8) areas in the outer periphery in the circumferential direction; and openings 42 provided in the resistance heating bodies 5 . By measuring infrared light radiated through the openings 42 by the radiation thermometer 16 , a temperature of the outer periphery of the evaluation substrate 4 in the circumferential direction can be measured.
FIG. 10 is a plane view of an evaluation substrate 4 - 5 in which temperature probes 14 as thermocouple elements provided in the evaluation substrate 4 - 3 shown in FIG. 8 are removed and the openings 42 are opened. By measuring infrared light radiated through the openings 42 by the radiation thermometer 16 , temperatures of the outer periphery in the circumferential direction and the central area in the evaluation substrate 4 can be measured.
FIG. 11 is a plane view of an evaluation substrate 4 - 6 , and the evaluation substrate 4 - 6 may include a base 41 as a silicon wafer; a ring-shaped resistance heater 5 provided in the outer periphery in its circumferential direction; and a plurality of the openings 42 formed in the resistance heater 5 . Further, FIG. 12 is a plane view of an evaluation substrate 4 - 7 , and the evaluation substrate 4 - 7 may include a base 41 as a silicon wafer; a spiral-shaped resistance heater 5 provided in order to uniformly heat the entire base 41 ; and a plurality of the openings 42 formed in the resistance heater 5 . With the evaluation substrate 4 - 6 , a temperature of the outer periphery in the circumferential direction can be measured by measuring infrared light radiated through the openings 42 . Furthermore, with the evaluation substrate 4 - 7 , temperature distribution of the entire wafer can be measured. | There are provided an evaluation device and an evaluation method for a substrate mounting apparatus capable of simply evaluating a temperature control function of the substrate mounting apparatus depending on evaluation conditions or circumstances and an evaluation substrate used for the same. The substrate mounting apparatus holds a target substrate mounted on a mounting surface and controls a temperature of the target substrate. The evaluation device includes an evacuable airtight chamber in which the substrate mounting apparatus is provided; an evaluation substrate which is mounted on the mounting surface instead of the target substrate and includes a self-heating resistance heater; and a temperature measurement unit which measures a temperature of the evaluation substrate. | 7 |
FIELD OF THE INVENTION
This invention relates to a process for the preparation of certain cellulose derivatives.
DESCRIPTION OF THE PRIOR ART
The conversion of insoluble cellulose or cellulose-containing materials into derivatives soluble in either aqueous or non-aqueous media has been of prime interest to industry for many years. Several methods are available for the preparation of water soluble cellulose derivates, including various alkyl ether derivatives, such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc., as exemplified by U.S. Pat. Nos. 2,278,612; 2,517,577; 2,140,568; 2,009,015; 2,160,782; 3,064,313; 3,280,026; 3,498,971; 3,567,360; and 3,574,188.
Water soluble cellulose products have applications in numerous areas, including foods, textiles, paints, cosmetics and pharmaceuticals. The utility of these products in many of these applications relies on their ability to confer high viscosities to aqueous media. However, it has been shown that the viscosifying properties of these cellulose alkyl ether derivatives are inadequate for certain applications, such as in mobility control applications in enhanced oil recovery. These shortcomings derive, among other things, from the methods employed in the manufacturing processes. In order to obtain water soluble products, relatively high degrees of substitution are required. As a consequence, these processes often rely on strongly alkaline or otherwise extreme reaction conditions to achieve adequate activation of the intractable cellulose for subsequent chemical derivatizations. These conditions commonly lead to partial or substantial degradation of the resulting products. Various attempts have been made to overcome these problems by employing alternative methods of derivatization, such as graft copolymerization (U.S. Pat. Nos. 3,359,224; 3,366,582; 3,838,077; etc.). Turunen et al in PCT Intern. Appl. No. WO 83 02,278, 1983 have described a method for solubilizing cellulose by a process which involves x-ray irradiation, impregnation with ammonia and urea, evaporation of the ammonia, and finally heating of the mixture to obtain an alkali-soluble cellulose carbamate derivative. However, these methods have met with only limited success for certain applications.
In general, the method employed in the preparation of such alkylether derivatives of cellulose can be classified as non-selective, in that the reagents used (e.g. haloalkyl acids, alkylene oxides, etc.) exhibit essentially no differential reactivity towards cellulose hydroxyl groups at different positions of the anhydroglucose repeat unit, resulting in a random distribution of substituents.
It is therefore desirable to have available derivatization methods, which are selective for only one of the hydroxyl functions, yet sufficiently simple and efficient to be applicable to industrial scale use. Selective modifications are advantageous in that they permit a greater control over the physical properties of the product and avoid some of the side reactions which are commonly associated with non-selective methods, such as formation of polymeric side chains. Substantial efforts have, for example, been directed at developing methods for the selective oxidation of primary and secondary hydroxyl groups. The introduction of carbonyl groups into polysaccharides constitutes one of the most important synthetic tasks, because it affords reactive intermediates which are amenable to further modifications, such as reductive amination, epimerization via reduction, and conversion into branched derivatives. Selective oxidations are furthermore of interest in the evaluation of the stability of oxidized polysaccharides in various industrial processes, such as in the bleaching and aging of cellulose-containing materials.
There is, at present, no generally applicable method available for selectively converting the C-6 hydroxyl functions of polysaccharides to the corresponding aldehydes or carboxylic acids. Most oxidation procedures result in the formation of mixtures of aldehyde and acid residues and degradation products. Considerable efforts have, for example, been directed at the oxidation of cellulose using nitrogen dioxide either in the gas phase or dissolved in carbon tetrachloride. It has been shown that the predominant reaction is the conversion of D-glucose to D-glucuronic acid residues. However, this is accompanied by some oxidation of secondary hydroxyl functions. Quantitative oxidations at C-6 can furthermore not be accomplished without concomitant depolymerization.
K. Brederick, Tetrahydron Lett. 695, 1967, observed that oxidation of cellulose with dimethyl sulphoxide (DMSO)/acetic anhydride (Ac 2 O) yielded mixtures of 2-oxy, 3-oxy, and 2,3-oxy cellulose products. This method was then used by C. Bosso, J. Defaye, A. Gadelle, C. C. Wong and C. Pederson, J. Chem. Soc., Perkin Trans., 1, 1579, 1982 for the selective oxidation of 6-0-trityl cellulose to afford the corresponding 2-oxy-cellulose derivative. Further developments were achieved by the same group following the discovery of the DMSO/paraformaldehyde solvent system for cellulose. They found that 3-oxy-cellulose could be obtained in yields of 60-70% without prior C-6 protection of the native polymer, using the DMSO/Ac 2 O oxidation system in combination with the DMSO/paraformaldehyde (PF) solvent. Detailed studies of the oxidation products showed that formaldehyde substitution occurs initially at the C-6 and C-2 positions of amylose and with increasing concentration also at C-3. While oxidation of unprotected cellulose with DMSO/Ac 2 O/PF proceeds exclusively at position C-3, it was found that in the case of amylose some 10% oxidation at C-2 had also occurred at similar overall levels of oxidations (degree of oxidation, d.o., 0.6-0.7). For 6-0-trityl cellulose, they found a greater proportion of 2-oxy (56%) than 3-oxy (36%) products. On the other hand, oxidation occurred exclusively at C-2 for 6-0-tritylamylose, but 56% at C-2 and 30% at C-3 in the case of 6-0-acetyl amylose (d.o. 0.7). These data indicate that the selectivity of C-2 oxidation is not related to the bulkiness of the C-6 substituent. It can be concluded from the work of Defaye et al that the selective oxidation of C-3 positions of unprotected amylose and cellulose is due to the reversible covalent formation of hydroxymethyl and poly(oxymethylene)ol groups at positions C-2 and C-6. Selectively oxidized cellulose derivatives are important precursors for the preparation of amino-deoxy-cellulose derivatives, which are of interest for a variety of applications, including flocculating and metal chelating agents, in enzyme immobilization, etc., as evidenced by U.S.S.R. Pat. No. 473,724 (1975, B. N. Gobunov, P. A. Protopopov, A. P. Khardin). N. Polukhina, L. S. Gal'braikh, and Z. A. Rogovin, Vysokomolekul, Soedin, B11, 270, 1969 and N. Kholmuradov, Yu, S. Kozlova, L. S. Gal'braikh, and Z. A. Rogorin, Vysokomolekul, Soedin, 8, 1089, 1966, have reacted 2,3-anhydro derivatives of cellulose with ammonia to obtain mixed polysaccharide products with 2-amino-2-deoxy-and 3-amino-3-deoxy-substituents. A total of four types of aminosugars were identified in these products, of which two were 3-amino-3-deoxy altrose and 2-amino-2-deoxy glucose.
T. Teshirogi, H. Yamamoto, M. Sakamoto and H. Tonami, Sen-I Gakkaishi, 36, T502, 1980 have recently reported a method for preparing 2-amino-2-deoxy-cellulose having a degree of substitution (d.s.) of 0.37. Their method is based on selective oxidation of 6-0-triphenylmethyl cellulose to 2-oxo-6-0-triphenylmethylcellulose, conversion into the oxime by hydroxylamine hydrochloride, reduction with lithium aluminum hydride, and finally detritylation with acid. However, this method has a number of disadvantages, in that (i) the overall chemical yields are low, (ii) it involves five chemical steps, of which two are connected with the introduction of stable amine functions and another two steps involve acid treatment of the polymer; (iii) reduction of the oxime intermediate leads to side reactions, such as loss of amine functions due to some formation of keto functions, and polymer degradation arising from the destruction of excess reducing agent; and (iv) the applicability of the method has been demonstrated for only one type of cellulose starting material.
M. Yalpani, L. D. Hall, J. Defaye and A. Gadelle, Can. J. Chem., 62, 260, 1984, have recently reported the preparation of 3-amino-3-deoxy-cellulose with d.s. 0.3 using regenerated cellulose as starting material. In both of these methods, the yields of aminodeoxy-cellulose were unsatisfactory, and only the more chemically reactive cellulose starting materials were employed.
SUMMARY OF THE INVENTION
This invention therefore seeks (a) to develop procedures for the preparation of new types of water soluble cellulose derivatives by selective attachment of carbohydrate residues; (b) to use mild reaction conditions in order to retain the molecular integrity of the final products; (c) to develop procedures which can utilize low cost raw materials, such as wood pulp, for the preparation of these water soluble products; and (d) to develop procedures which allow the preparation of cellulose products with high degrees of substitution, and with the potential for a wide range of structural variations of parameters such as the length, type, and conformation of the branch residue, as well as their net charge.
Accordingly, the invention provides a process for preparing n-amino-n-deoxy cellulose where n is 2 or 3 and has the same value at each occurrence in one molecule, the process comprising (i) when n is 2 selectively oxidizing cellulose by (a) reacting it with triphenylmethyl chloride; then (b) reacting the product from (a) with acetic anhydride and dimethylsulfoxide, then (c) subjecting the product from (b) to reductive amination; (ii) when n is 3 (a) reacting cellulose with dimethylsulfoxide and paraformaldehyde then (b) reacting the product from (a) with acetic anhydride and dimethylsulfoxide and then (c) subjecting the product from (b) to reductive amination.
In one aspect the invention provides a process for producing a branched water soluble cellulose derivative having at least part of the carbon atoms at position 2 or at position 3 substituted by an amino carbohydrate group, the process comprising subjecting 2-oxy cellulose or 3-oxy cellulose to reductive amination using an amino sugar and a reducing agent able to reduce the imine group in the presence of carbonyl groups.
In another aspect the invention provides a process for producing a branched water soluble cellulose derivative having at least part of a carbon atoms at position 2 or position 3 substituted by an amino carbohydrate group, the process comprising converting a 2-amino-2-deoxy or 3-amino-3-deoxy cellulose to the branched product by reductive alkylation with an aldehyde or carbonyl containing carbohydrate and a reducing agent able to reduce the imine group in the presence of carbonyl.
According to the invention selective oxidations of cellulose hydroxyl functions at either C-2 or C-3 are accomplished using acetic anhydride and dimethyl sulfoxide as the oxidant and either 6-0-triphenyl methyl cellulose or unprotected cellulose, respectively. In the latter case, the cellulose starting material can be derived from a variety of sources and pretreatments, for example, regenerated cellulose or cellulose obtained from wood pulp. For the preparation of 6-0-triphenyl-methyl cellulose regerenated cellulose is preferred. For the preparation of C-2 or C-3 aminated cellulose derivatives from the corresponding oxy-cellulose derivatives, any ammonium salt or primary or secondary amine-containing reagent can be employed. Ammonium acetate, ammonium chloride, hydrazine, or ethylenediamine are preferred. Any reducing agent which reduces imines in the presence of carbonyl functions can be used. Sodium cyanoborohydride is preferred.
Any aqueous or polar organic solvent or mixtures thereof can be employed, with water (at neutral pH) or aqueous alcohol, ethyl alcohol, methyl sulphoxide or dimethyl formamide being preferred. The reaction temperatures can vary between 20°-90° C., but should preferably not exceed 60° C. Similarly, the conversion of the oxycellulose or aminocellulose derivatives into branched derivatives can be performed using reductive amination and reductive alkylation, respectively. In the former case, any amino sugar, such as glucosamine, galactosamine, maltosamine, streptomycin, etc., or products obtained by amination of carbohydrates may be employed.
For the reductive alkylation of amino cellulose derivatives any aldose or ketose, or other carbonyl-containing saccharide may be employed, with aldoses and ketoses being preferred.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following examples illustrate the invention:
EXAMPLE 1
2-Amino-2-Deoxy-Cellulose
Alpha cellulose fibres (15.0 g, approximately 99.5% pure) were converted to the 6-0-triphenylmethyl cellulose derivative using triphenylmethyl chloride (61.0 g) according to known methods (J.W. Green, Methods in Carbohydrate Chemistry, Vol. III, R.L. Whistler, ed., Academic Press, 1963, p. 327), following a pretreatment with pyridine for 18 h. Samples (2.0 g) of the 6-0-triphenylmethyl cellulose derivative dissolved in dimethyl sulphoxide (100 mL) were treated with acetic anhydride (20 mL) and the mixture was stirred for 90 h. The 2-oxy-cellulose product was filtered, washed with water (1 L) and methanol (0.6 L), and dried (1.8 g). A portion of this material (1.0 g) was subsequently treated with ammonium acetate (3.0 g) and sodium cyanoborohydride (2.2 g) in water at room temperature for 45 h. The 2-amino-2-deoxy-6-0-triphenylmethyl cellulose products thus obtained after exhaustive washing with water (1 L) and methanol (0.2 L) and drying, had nitrogen contents varying between 0.81-1.11%, corresponding to degrees of substitution of 0.2-0.3. Treatment of this product with dilute (1 M) hydrochloric acid in acetone resulted in the removal of the 6-0-protecting function.
EXAMPLE 2
2-Amino-2-Deoxy-Cellulose
A sample of α-cellulose fibres (5.0 g) was dispersed in (50%) aqueous pyridine at 95° C. for 18 h, filtered, resuspended dry pyridine at 95° C. for 3 h, filtered and resuspended in dry pyridine at 95° C. for 18 h, filtered, washed with N,N-dimethyl formamide (DMF, 100 mL) and then resuspended in DMF. This suspension was treated with N,N-dimethylaminopyridine (0.58 g, 3 mmol), triphenylmethylchloride (18.85 g, 68 mmol), and triethylamine (15 mL) at 30° C. for 24 h. The product was filtered, washed with methanol (1 L), and dried. This material was oxidized, and subsequently reductively aminated, using ammonium acetate, as described in Example 1. The resulting 2-amino-2-deoxy-6-0-triphenylmethyl cellulose derivatives had nitrogen contents of 0.70-0.77%.
EXAMPLE 3
3-Amino-3-Deoxy-Cellulose
A sample (50.0 g) of a 2% aqueous suspension of microfibrillated cellulose was suspended in methyl sulphoxide (DMSO, 100 mL) at 100° C. for 2 h, filtered, and resuspended in DMSO (150 mL) for 10 h, heated to 90° C., filtered and resuspended in DMSO (150 mL). This material was then treated with acetic anhydride (15 mL) at 80° C. for 48 h. The brown suspension was filtered, washed with water, resuspended in water (50 mL) and treated with ammonium acetate (1.5 g) and sodium cyanoborohydride (2.2 g) at room temperature for 45 h. The product, 2-amino-2-deoxy-cellulose, was isolated after filtration and washing, and had N contents of 0.45-1.50%.
EXAMPLE 4
3-Amino-3-Deoxy-Cellulose
A suspension of Acetakraft pulp (11.1 g) in DMSO (900 mL) was treated with paraformaldehyde (24.0 g) at 90° C. for 3 h with stirring. Another portion (11.0 g) of paraformaldehyde was added and the temperature raised to 125° C. for 1 h, and then to 135° C. for 1 h, resulting in almost complete dissolution of the cellulose material. The slightly turbid suspension was cooled, and then treated with acetic anyhydride (80 mL) in the dark for 20 h. Water was added to the resulting oxidized material, and the suspension was filtered, washed with water (1 L), methanol (0.6 L), and diethyl ether (0.4 L), yielding a white, fluffy material (10.5 g). Samples (1.0 g) of this material were treated with NH 4 OAc (3.6 g) and NaCNBH 3 (2.2 g) in DMSO (100 mL) at room temperature for 7 days. The resulting brown solutions were dialyzed for 4 days yielding white gels, which were lyophilized. The 3-amino-3-deoxy-cellulose products thus obtained had N-contents of 1.07-1.09%.
EXAMPLE 5
3-Amino-3-Deoxy-Cellulose
A sample (1.5 g) of 3-oxy-cellulose derived from Acetakraft as described in Example 4, was treated with paraformaldehyde (8.9 g) in DMSO (100 mL) at 100° C. for 2 h, cooled and then reoxidized with acetic anhydride for 18 h at room temperature. The product was isolated and reductively aminated as described in Example 4, yielding, after purification by dialysis, a 3-amino-3-deoxy-cellulose product with a N-content of 4.77%.
EXAMPLE 6
3-Amino-3-Deoxy-Cellulose
A sample of regenerated cellulose (5.0 g) in DMSO (200 mL) was treated with paraformaldehyde (10.2 g) at 90° C. for 3 h, then at 125° C. for 1 h, and finally at 135° C. for 1 h. The resulting clear solution was cooled to room temperature, and treated with acetic anhydride for 20 h in the dark. The oxycellulose product was precipitated with water, filtered, washed with water (0.4 L), methanol (0.2 L), and ether (0.2 L) yielding a light yellow powder (4.8 g). Samples (1.0 g) of this material were reductively aminated as described in Example 4 yielding, after dialysis, 3-amino-3-deoxy-cellulose derivatives with N-contents of up to 6.38%, corresponding to a d.s. of ca. 0.9.
EXAMPLE 7
3-Amino-3-Deoxy-Cellulose
A sample of regenerated cellulose (2.2 g) in DMSO (100 mL) was treated with paraformaldehyde (6.1 g) at 110° C. for 1 h. The reaction mixture was cooled to room temperature and treated with acetic anhydride (35 mL) in the dark for 18 h. The resulting white suspension was treated with methanol (100 mL), filtered, washed with methanol (0.4 L), and dried. Reductive amination of this material with NH 4 OAc (3.5 g) and NaCNBH 3 (2.0 g) at room temperature for 3 days gave 3-amino-3-deoxy-cellulose with N contents of 2.34-2.8%.
EXAMPLE 8
3-Amino-3-Deoxy-Cellulose
Samples of α-cellulose fibres (5.0 g) were solvent pretreated for several hours with either dimethyl sulphoxide, methanol, or acetic acid at either room temperature or up to 70° C. and then oxidized and reductively aminated as described in Example 4. The resulting 3-amino-3-deoxy-cellulose products had N-contents between 0.80-1.05%.
EXAMPLE 9
3-N-(2-Amino-2-Deoxy-glucose)-3-Deoxy-Cellulose
A sample of 3-oxy-cellulose (1.5 g), derived from Acetakraft as described in Example 4, in DMSO (100 mL) was treated with a DMSO solution containing glucosamine hydrochloride, (3.6 g), and NaCNBH 3 (2.0 g) at room temperature for 7 days. The water soluble product (1.3 g) was obtained after dialysis and precipitation, and had a N-content of 4.12%.
EXAMPLE 10
3-N-(2-Amino-2-Deoxy-glucose)-3-Deoxy-Cellulose
A sample of 3-amino-3-deoxy-cellulose (1.0 g) with N-content of 2.8% obtained from Example 7, was treated with D-glucose (1.4 g), and NaCNBH 3 (1.8 g) in DMSO (100 mL) at room temperature for 4 days, yielding, after dialysis, a water soluble product with N-content of 1.50%.
EXAMPLE 11
2-N-(2-Amino-2-Deoxyglucose)-2-Deoxy-Cellulose
A solution of 2-oxy-6-0-triphenylmethylcellulose (1.0 g, 2.56 mmol), obtained from Example 2, in DMSO (25 mL) was treated with a DMSO solution of glucosamine hydrochloride (1.3 g, 6 mmol) and NaCNBH 3 (0.8 g, 13 mmol) containing solid Na 2 CO 3 (0.74 g, 7 mmol) at room temperature for 30 h.
After removal of the solids, the product was precipitated with iso-propanol, treated first with methanolic-hydrochloric acid (pH 5), and then with methanol (until neutral), and dried to yield 0.7 g of the water soluble branched cellulose derivative with N content of 6.32%.
The reductive amination could alternatively be conducted in aqueous solution resulting in products with N-contents of up to 1.62%.
EXAMPLE 12
3-N-(2-Amino-2-Deoxy-glucose)-3-Deoxy-Cellulose
A sample of 3-oxycellulose (2.8 g) in DMSO (150 mL) obtained from Example 8 was treated with a DMSO solution containing glucosamine hydrochloride, (6.7 g 31 mmol), NaCNBH 3 (2.2 g, 35 mmol) and pyridine (2 mL, 25 mmol). The reaction mixture was warmed to 50° C. and stirred for 24 h. The resulting orange solution was precipitated with iso-propanol (0.5 L); the precipitate was filtered, washed with iso-propanol (0.4 L), and dried in vacuo at 45° C. The yellow product had a N-content of 1.30%.
EXAMPLE 13
3-N-(1-Amino-1-Deoxy-Lactit-1-yl)-3-Deoxy-Cellulose
A sample of 3-amino-3-deoxy-cellulose (1.5 g, 0.9 mmol) obtained from Example 6, with a N-content of 2.17%, dispersed in water (125 mL) was treated with β-lactose (4.6 g, 13.4 mmol) and NaCNBH 3 (1.0 g, 16 mmol) at room temperature for 50 h. The resulting water soluble product (3.4 g) had a N-content of 1.51%.
The process of the invention, for the preparation of the 2- and 3-aminocellulose as well as the branched 2- and 3-deoxycellulose derivatives, are efficient and inexpensive. The selectively modified products thus obtained are of use for a variety of applications either by themselves or as chemical intermediates for new types of cellulose products. The reaction conditions are mild and avoid polymer degradation which is common with many other chemical methods. The derived products are of greater utility as they retain more of the macromolecular properties of the native cellulose.
The process allows for a considerable degree of structural variation for the branched derivatives, with parameters such as branch length, conformation and type being readily modified. Similarly, the branched products can be designed to be neutral, or to carry anionic or cationic charge by simple choice of the carbohydrate residue to be attached as side chain, or by facile chemical modifications such as oxidation, etc.
It should also be noted the use of N,N-dimethylamine-pyridine as catalyst (see Example 2) provides improved yields of the triphenylmethyl derivative. Further if the reaction with DMSO and acetic anhydride is carried out with exclusion of light and at relatively high temperatures (as exemplified) then substantially higher oxidation levels (about 30 to 40%) are achieved without side reactions such as discoloration. Note also the invention permits the use of wood pulp as starting material, which is widely available and inexpensive.
Aminocellulose derivatives are useful as cationic polymers for applications as flocculating agents, inexpensive metal-chelating derivatives, and for certain bio-medical applications.
The branched cellulose derivatives constitute new types of water soluble derivatives which will find a wide range of uses in all the areas where water soluble polymers are presently employed, e.g. as thickening and suspending agents, etc. | A process for preparing n-amino-n-deoxy cellulose where n is 2 or 3 and has the same value at each occurrence in one molecule. When n is 2 cellulose is selectively oxidized by (a) reacting it with triphenylmethyl chloride; then (b) reacting the product from (a) with acetic anhydride and dimethylsulfoxide. The product from (b) is then subjected to reductive amination. When n is 3 cellulose is reacted with dimethylsulfoxide and paraformaldehyde. The product from (a) is then reacted with acetic anhydride and dimethylsulfoxide and the product from (b) then subjected to reductive amination. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of Ser. No. 11/282,910 filed on Nov. 18, 2005 which is a divisional application of U.S. patent Ser. No. 10/440,036, filed May 16, 2003, which claims priority to U.S. patent application Ser. No. 09/909,667, filed Jul. 20, 2001, which claims priority to U.S. Provisional Application No. 60/219,853 filed Jul. 21, 2000, the entirety of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to methods and devices for correcting bone abnormalities and involves the use of a surgical mesh bag which is inserted into a prepared cavity in bone. The bag is inflated using bone replacement material to expand and fill the cavity.
[0003] U.S. Pat. Nos. 5,549,679 and 5,571,189 to Kuslich, describe a device and method for stabilizing the spinal segment with an expandable, porous fabric implant for insertion into the interior of a reamed out disc which is packed with material to facilitate bony fusion. In the present invention, a similar bag is used to correct bone abnormalities including, but not limited to, bone tumors and cysts, tibial plateau fractures, avascular necrosis of the femoral head and compression fractures of the spine.
[0004] U.S. Pat. Nos. 5,108,404 and 4,969,888 to Scholten et al., describe a system for fixing osteoporotic bone using an inflatable balloon which compacts the bone to form a cavity into which bone cement is injected after the balloon is withdrawn. The invention requires the use of fluoroscopy to monitor the injection and to help guard against cement leakage through fissures in bone. Unfortunately, such leakage is known to occur in spite of these precautions. Since such leakage may cause serious injury, including paralysis, an improved device and method is needed.
[0005] U.S. Pat. No. 5,972,015 to Scribner et al., describes a system of deploying a catheter tube into the interior of a vertebra and expanding a specially configured nonporous balloon therewithin to compact cancellous bone to form a cavity. The Scribner patent approach utilizes a non-porous balloon which is inflated within the bone to cause compression. The cavity thus formed, may then be filled with bone cement. Unfortunately, the bag used by Scribner may be ruptured during expansion to compact cancellous bone due to sharp projections found within the cavity to be expanded. Filling the cavity eventually formed could allow leakage of bone cement out of the bone against vessels or nerves which may cause undesirable complications.
[0006] The present invention involves an improvement of all of the previous techniques and avoids complications that could occur with the system of U.S. Pat. No. 5,972,015.
[0007] All U.S. patents, applications and all other published documents mentioned anywhere in this application are incorporated herein by reference in their entirety.
[0008] The art described in this section is not intended to constitute an admission that any patent, publication or other information referred to herein is “prior art” with respect to this invention, unless specifically designated as such. In addition, this section should not be construed to mean that a search has been made or that no other pertinent information as defined in 37 C.F.R. § 1.56(a) exists.
SUMMARY OF THE INVENTION
[0009] The invention provides a method of correcting numerous bone abnormalities including bone tumors and cysts, avascular necrosis of the femoral head, tibial plateau fractures and compression fractures of the spine. The abnormality may be corrected by first accessing and boring into the damaged tissue or bone and reaming out the damaged and/or diseased area using any of the presently accepted procedures, or the damaged area may be prepared by expanding a bag within the damaged bone to compact cancellous bone. After removal and/or compaction of the damaged tissue the bone must be stabilized.
[0010] In cases in which the bone is to be compacted, the methods and devices of this invention employ a catheter tube attached to an inflatable porous fabric bag as described in U.S. Pat. Nos. 5,549,679 and 5,571,189 to Kuslich, the disclosures of which are incorporated herein by reference. Those bags may be inflated with less fear of puncture and leakage of the inflation medium than thin walled rubber balloons. They may also be used over a Scribner balloon to protect the balloon from breakage and eventually seepage.
[0011] The devices of U.S. Pat. Nos. 5,549,679 and 5,571,189 to Kuslich, additionally provide the surgeon with the advantage of safely skipping the first balloon inflation steps of Scribner and Scholten, by expanding the bag through introduction of fill material, such as a bone repair medium thereby correcting the bony defect and deformity and stabilizing it in one step of the procedure.
[0012] As indicated above, the damaged bone may be removed by any conventional reamer. Examples of reamers are described in U.S. Pat. No. 5,015,255; U.S. patent application Ser. No. 09/782,176, to Kuslich et al., entitled “Expandable Reamer” and filed Feb. 13, 2001; and U.S. patent application Ser. No. 09/827,202 to Peterson et al., entitled “Circumferential Resecting Reamer Tool,” filed Apr. 5, 2001, the disclosure of which has been expressly recited herein at the end of this application. Other examples of reamers are known and may be used. After the damaged bone or tissue has been removed, bone repair medium may then be inserted into the cavity thus formed, via a catheter and expandable fabric bag as described in U.S. Pat. Nos. 5,549,679 and 5,571,189.
[0013] Alternatively, either a smaller than desired cavity may be formed into the bone to be enlarged by compaction or the cavity may be formed only by compaction through introduction of fill material into the bag. In either case, the bag may be positioned over the inflation balloon which is then inflated within the bone site to provide the degree of compaction required. The bag may then be filled with fill material, such as bone repair medium while the balloon remains in place within the bag. Alternatively, the balloon may be removed from the bag prior to filing the bag.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] A detailed description of the invention is hereafter described with specific reference being made to the drawings in which:
[0015] FIG. 1 is a side elevational view of a vertebra that is fractured and in need of repair;
[0016] FIG. 2 is a side view of the vertebra of FIG. 1 being reamed out with a reaming tool from the anterior approach;
[0017] FIG. 3 is a top view of the vertebra of FIG. 1 showing the reamer forming a pair of cavities within the vertebra from the anterior approach;
[0018] FIG. 4 is a side elevational view of the vertebra of FIG. 2 showing placement of an expandable fabric bag of the invention;
[0019] FIG. 5 is a top elevational view of the vertebra of FIG. 3 showing a second of two expandable fabric bags of the invention being positioned;
[0020] FIG. 6 is a side view of a vertebra being reamed from a posterior approach;
[0021] FIG. 7 is a top view of the vertebra of FIG. 6 with a bag in place and a second cavity being reamed;
[0022] FIG. 8 is a side elevational view of the vertebra of FIG. 6 with an expandable fabric bag of the invention in place;
[0023] FIG. 9 is a top view of the vertebra of FIG. 7 with one bag inflated and the second bag being deployed;
[0024] FIG. 10 is a side elevational view showing the vertebra cavity being expanded with an expandable fabric bag about an inflation device in cross-section;
[0025] FIG. 11 shows the bag system of FIG. 10 with the vertebra in phantom to show the bag system;
[0026] FIG. 12 is a view similar to FIG. 10 showing a different approach to the interior of the vertebra;
[0027] FIG. 13 is a view similar to FIG. 11 showing the approach of FIG. 12 ;
[0028] FIG. 14 shows the bag of FIG. 12 in a closed, filled and expanded position;
[0029] FIG. 15 is a top view of the bag system of FIG. 12 being inflated through a catheter tube;
[0030] FIG. 16 shows a femoral head with avascular necrosis;
[0031] FIG. 17 shows the femoral head of FIG. 16 being reamed out;
[0032] FIG. 18 shows placement of a bag system of the invention within the cavity in the femoral head;
[0033] FIG. 19 is a side elevational view of a tibial plateau fracture;
[0034] FIG. 20 is a side view of the fracture of FIG. 19 with a cavity being formed with a reamer; and
[0035] FIG. 21 shows the tibial plateau fracture repaired with an expanded inflatable fabric bag in place.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] In the following detailed description, similar reference numerals are used to depict like elements in the various figures.
[0037] FIG. 1 shows a typical vertebra 10 having compression fractures 12 that is in need of repair. As indicated above the damaged portion of the vertebra 10 may be reamed out, compacted, or otherwise repaired. For example, FIG. 2 shows a reamer 14 entering the vertebra 10 anteriorly to make an opening 15 and cavity 16 . Alternatively, multiple cavities 16 may be formed such as is shown in FIG. 3 .
[0038] As previously mentioned, the damaged portion of the vertebra 10 may be compacted in addition to or instead of being reamed out. In FIG. 4 , a delivery tube or catheter 20 is seen in the process of delivering an expandable fabric bag 22 into the vertebra 10 or into a cavity 16 present therein. As indicated, the cavity 16 may have been created through reaming, compaction by the bag 22 or other device, or by other means. Once the bag 22 is positioned within the vertebra 10 , the bag 22 may be inflated or expanded to the limits of the cavity 16 thus formed through insertion or injection of fill material 19 into the interior 21 of the bag 22 .
[0039] FIG. 5 shows a single filled expandable fabric bag 22 in place with a second expandable bag which is being inserted and expanded within the cavity 16 .
[0040] FIGS. 6-9 illustrate a procedure in which the opening 15 and cavity 16 are created posteriorly. Regardless of the direction through which the vertebra 10 is operated on, in all forms, the cavity 16 which is formed is then filled with acceptable bone replacement material.
[0041] Bone replacement material 19 may be one or more of the following, or any other biocompatible material judged to have the desired physiologic response:
[0042] A) Demineralized bone material, morselized bone graft, cortical, cancellous, or cortico-cancellous, including autograft, allograft, or xenograft;
[0043] B) Any bone graft substitute or combination of bone graft substitutes, or combinations of bone graft and bone graft substitutes, or bone inducing substances, including but not limited to: Tricalcium phosphates, Tricalcium sulfates, Tricalcium carbonates, hydroxyapatite, bone morphogenic protein, calcified and/or decalcified bone derivative; and
[0044] C) Bone cements, such as ceramic and polymethylmethacrylate bone cements.
[0045] The bone replacement material is inserted into the bag 22 via a needle, catheter 20 or other type of fill tool. The bone replacement material expands the bag to the limits of the cavity 16 .
[0046] The inventive bag 22 may be a small fabric bag, from about one to about four cm in diameter, being roughly spherical in shape, although other elliptical shapes and other geometric shapes may be used. The bag is pliable and malleable before its interior space 21 is filled with the contents to be described. The material of the bag 22 may be configured to take on the shape of the cavity in which the bag is placed. While in this initial condition, the bag may be passed, uninflated, through a relatively small tube or portal, perhaps about three mm to about one cm in diameter.
[0047] The bag 22 , such as may best be seen in FIG. 9 , is constructed in a special and novel way. The bag 22 may be constructed of a fabric 23 . Fabric 23 may be woven, knitted, braided or form-molded to a density that will allow ingress and egress of fluids and solutions and will allow the ingrowth and through-growth of blood vessels and fibrous tissue and bony trabeculae, but the fabric porosity is tight enough to retain small particles of enclosed material, such as ground up bone graft, or bone graft substitute such as hydroxyapatite or other osteoconductive biocompatible materials known to promote bone formation. The fabric 23 defines a plurality of pores 25 . Generally, the pores 25 of the fabric 23 will have a diameter of about 0.25 mm or less to about 5.0 mm. The size is selected to allow tissue ingrowth while containing the material packed into the bag. If bone cement or other material is used which will not experience bone ingrowth, the pores 25 may be much tighter to prevent egress of the media from within the bag 22 out into the cavity 16 . This prevents leakage that could impinge upon nerves, blood vessels or the like if allowed to exit the bone.
[0048] One or more of the pores 25 may be used as a fill opening 27 , wherein the fabric 23 may be manipulated to enlarge a pore to a diameter potentially greater than 5 mm but no more than about 1 cm. Preferably, the fill opening 27 is less than about 5 mm in diameter. Such a pore/fill opening 27 is sufficiently large to allow a catheter, needle, fill tube or other device for inserting or injecting fill material to pass through the fabric 23 and into the interior 21 of the bag 22 without damaging the integrity of the bag 22 .
[0049] When the bag 22 is fully filled with fill material, the bag will form a self-retaining shape which substantially fills the cavity 16 . Once sufficiently full, the fill tool used to place fill material into the bag interior 21 is removed from the opening 27 . Where the opening 27 is not a pore 25 but rather a separate and distinct opening in the bag 22 , the opening 27 may have a set diameter which requires sealing such as by tying, fastening, welding, gluing or other means of closing the opening 27 after the bag has been filled. Where the opening 27 is a pore 25 , upon removal of the catheter or fill tool from the opening 27 the fabric 23 will contract to reduce the diameter of the opening 27 to be substantially similar to that of the other pores 25 .
[0050] The size and density of the pores determine the ease or difficulty with which materials may pass through the mesh. For instance, very small pores (<0.5 mm) would prohibit passage of all but the smallest particles and liquids. The pore size and density could be controlled in the manufacturing process, such that the final product would be matched to the needs of the surgeon. For example, if methylmethacrylate bone cement were to be used, the pore size would need to be very small, such as about less than 0.5 mm to about 1.0 mm, whereas, when bone graft or biocompatible ceramic granules are used, pore sizes ranging from about 1.0 mm to about 5.0 mm or more may be allowed. The fact that the fabric 23 is properly porous would allow it to restrict potentially dangerous flow of the fill material outside the confines of the bag.
[0051] The fabric is light, biocompatible, flexible and easily handled, and has very good tensile strength, and thus is unlikely to rip or tear during insertion and inflation. When the device is inflated, the device expands to fill a previously excavated cavity 16 .
[0052] The use of the term “fabric” herein is meant to include the usual definition of that term and to include any material that functions like a fabric, that is, the “fabric” of the invention must have a plurality of pores 25 through which material and fluid flow is allowed under the terms as described, and the “fabric” must be flexible enough to allow it to be collapsed and inserted into an opening smaller than the inflated bag size.
[0053] The bag 22 need not be woven and may be molded or otherwise formed as is well known in the art. The preferred material may provide the ability to tailor bioabsorbance rates. Any suture-type material used medically may be used to form the bag 22 . The bag may be formed of plastic or even metal. In at least one embodiment, bag 22 is formed using a combination of resorbable and/or nonresorbable thread. Bag 22 may include a fill opening 27 which may be a bushing that could be a bioabsorbable and/or nonbioabsorbable plastic, ceramic or metal. The opening 27 may also be hydroxyapatite, or it could be plastic or metal. The opening 27 may also be characterized as a pore 25 , wherein a pore 25 of the fabric 23 has been expanded to allow a catheter 20 or other fill device to pass into the interior 21 of the bag 22 . The bag 22 could be formed from a solid material to which perforations are added. The bag 22 may be partially or totally absorbable, metal, plastic, woven, solid, film or an extruded balloon.
[0054] In embodiments of the present invention a damaged tissue of a body, such as a vertebra 10 may be treated in accordance with the following procedures such as are depicted in FIGS. 1-9 .
[0055] Initially, the vertebra 10 needing repair is surgically exposed by forming at least one cavity 16 . The cavity or cavities 16 may be formed by several different means such as by reaming. Reaming may be accomplished by several means such as including the use of a reamer 14 such as, for example, the Kuslich Expandable Reamer, U.S. Pat. No. 5,015,255, the entire content of which is incorporated herein by reference. Next, the unexpanded mesh bag or Expandable Fabric Bag Device (EFBD) 22 is inserted into the cavity or cavities via catheter 20 or other means. At some point, the fill material 19 is prepared for insertion or injection into the EFBD 22 . Following preparation of the fill material 19 , the material is injected or otherwise inserted into the bag 22 using sufficient pressure to fill the bag 22 to its expanded state, thus producing rigidity and tension within the cavity or cavities 16 to reach the degree of correction required by virtue of the compression fractures. Finally, the fill opening 27 is closed to prevent egress of inflation material 19 .
[0056] FIGS. 10-15 show a form of the invention in which a balloon 30 and catheter tube 32 is employed. The balloon 30 is surrounded by an expandable fabric bag 22 to protect the balloon 30 from being punctured during the inflation steps and to remain in place to prevent undesired egress of material injected into the cavity formed in the bone. Balloon 30 may be any medical-grade elastomeric balloon. The balloon 30 may be constructed from latex, urethanes, thermoplasic elastomers or other substances suitable for use as an expandable member. Examples of suitable balloons include, but are not limited to: balloons utilized with the FOGARTY.RTM. occlusion catheter manufactured by Baxter Healthcare Corporation of Santa Ana, Calif.; balloons of the type described in U.S. Pat. No. 5,972,015 to Scribner et al., and others. The methods involve placement of the expandable fabric bag 22 of the invention about the balloon 30 of the Scribner et al. device. The expandable bag 22 is left in place before the cavity 16 is filled with bone substitute or bone cement. The expandable fabric bag 22 prevents breakage of the balloon 30 and greatly limits the ability of fill material from leaking out of the cavity through bone fissures where it could cause damage.
[0057] As may best be seen in FIGS. 11, 13 and 15 , the bag 22 may include a neck 29 which extends outwardly from the bag 22 to completely overlap the shape of balloon 30 . The bag 22 and/or balloon 30 may each have a variety of shapes and sizes.
[0058] If desired, the expandable fabric bag 22 may be used as the sole inflation device, eliminating the Scribner et al. balloon 30 if the fabric porosity is tight and the inflation media is reasonably viscous.
[0059] While many of the previous embodiments have described the use of the bag 22 for repair of tissue such as a spinal body, in FIGS. 16-18 show how the bag 22 may be used in treating avascular necrosis of the femoral head. In FIG. 16 , a femoral head 40 is shown which is in need of repair. FIG. 17 shows the femoral head being reamed out with a reamer 14 , such as previously described. The reamer 14 forms a cavity 16 . In FIG. 18 , a bag 22 is shown within the cavity 16 formed within the femoral head 40 . The opening 27 of the bag 22 is closed off after being filled and expanded with bone substitute material.
[0060] In an alternative embodiment, the Scribner et al. balloon, as previously described, may also be used with the bag 22 for repair of the femoral head 40 .
[0061] Turning to an embodiment of the invention shown in FIGS. 19-21 , a tibial plateau 48 is shown having a fracture 50 . The fracture 50 is repaired by forming a cavity 16 with a reamer 14 , such as is shown in FIG. 20 . As is shown in FIG. 21 , once cavity 16 is properly reamed, bag 22 may be inserted therein and filled with bone repair media 19 .
[0062] Other tissue and bone abnormalities may also be treated with the inventive methods and bag 22 described herein. The present invention is not limited to only treatment of spinal bodies, femoral heads, and tibial plateaus. The bag 22 and the methods of treatment described herein, may be utilized throughout a mammalian body to treat many types of bone and tissue abnormalities including those described herein as well as others.
[0063] In addition to being directed to the specific combinations of features claimed below, the invention is also directed to embodiments having other combinations of the dependent features claimed below and other combinations of the features described above.
[0064] The above disclosure is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the claims where the term “comprising” means “including, but not limited to.” Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims.
[0065] Further, the particular features presented in the dependent claims can be combined with each other in other manners within the scope of the invention such that the invention should be recognized as also specifically directed to other embodiments having any other possible combination of the features of the dependent claims. For instance, for purposes of claim publication, any dependent claim which follows should be taken as alternatively written in a multiple dependent form from all prior claims which possess all antecedents referenced in such dependent claim if such multiple dependent format is an accepted format within the jurisdiction (e.g., each claim depending directly from claim 1 should be alternatively taken as depending from all previous claims). In jurisdictions where multiple dependent claim formats are restricted, the following dependent claims should each be also taken as alternatively written in each singly dependent claim format which creates a dependency from a prior antecedent-possessing claim other than the specific claim listed in such dependent claim below (e.g., claim 3 may be taken as alternatively dependent from claim 2 ; claim 5 may be taken as alternatively dependent on claim 3 , claim 6 may be taken as alternatively dependent from claim 3 ; claim 7 may be taken as alternatively dependent from claims 3 , 5 or 6 ; etc.).
BACKGROUND OF THE INVENTION
[0066] 1. Field of the Invention
[0067] This invention relates to an apparatus and method for removing, debriding and/or resecting tissue fragments from a body cavity. In particular, the present invention is directed for use in medical procedures where it may be necessary to remove tissue from a body region. The apparatus and method of the present invention may be especially useful in medical procedures such as orthopedic surgery.
[0068] 2. Description of the Related Art
[0069] Medical procedures involving the removal of tissue from a bone or other region of a body are well known in the art. Of particular interest to the present invention are procedures relating to removal of diseased or damaged tissue of a spinal disk, such as a discectomy.
[0070] The spinal disc consists of two types of tissues: the nucleus, and the annulus. The annulus is further divided into the inner and outer annulus. Disc hernias usually consist of a bulge of the nucleus and inner annulus through a rent in a small area of the outer annulus. Partial discectomies are frequently performed when a disc herniation causes pressure on a spinal nerve. The operation consists of removal of the herniated nucleus and portions of the inner annulus. In the past surgeons have used a variety of tools to remove spinal disc tissue during a discectomy. The simplest tools for disc removal are the scalpel and tweezer-type “pick-ups,” which are well known in the art. These tools are very inefficient, as the stringy annular tissues tend to simply move aside and remain attached when these tools are used. Scalpels and pick-ups tend to leave behind fragments of tissue. These fragments can lead to re-herniation—a painful condition that might require a second or even a third operation.
[0071] So-called “pituitary rongeurs” and “curettes” are the most frequently utilized instruments. Some examples of these instruments may be seen in the following U.S. Patent references:
[0000] U.S. Pat. No. Inventor(s): 6,200,320 B1 Michelson
[0072] 6,142,997 Michelson 5,961,531 Weber et al. 5,766,177 Lucas-Dean et al. 5,653,713 Michelson 5,484,441 Koros et al. 5,451,227 Michaelson 5,312,407 Carter 5,026,375 Linovitz et al. 5,061,269 Muller 4,990,148 Worrick, III et al. 4,777,948 Wright 4,733,663 Farely 4,722,338 Wright et al. 3,902,498 Niederer 3,628,524 Jamshidi 2,984,241 Carlson.
[0073] Tools, such as those described in the above cited references, while useful, were not specifically designed to remove disc tissue, and tend to require multiple passes to completely clean out the inner annulus tissue. The use of rongeurs and curettes also tends to leave behind fragments of tissue that may also lead to re-herniation. Furthermore, because these rongeurs and curettes require multiple passes, the operation may be prolonged, possibly leading to increased bleeding and higher infection rates.
[0074] Many pituitary rongeurs utilize a single cutting blade at the end of a single, unopposed beam. Actuation of the beam, by means of a drive rod, tends to force the distal shaft to move away from the tissue being cut. An open section in the middle of the beam helps reduce this movement, but does not effectively eliminate the unwanted movement.
[0075] Other methods and devices which have been developed in order to improve the effectiveness of a disc removal operation include electrical and laser based cautery. While electrical cautery does effectively destroy disc tissue, it produces heat and smoke in the process. Heat can injure surrounding tissue, including delicate spinal nerves, potentially causing further harm to the patient. In addition, the production of smoke may obscure vision and interfere with the surgeons ability to properly perform the operation. Laser cautery like electrical cautery methods also produce heat and smoke. Low energy lasers tend to be less effective and therefore the disc removal procedure can be prolonged and less than complete. Higher energy lasers produce more heat and smoke and therefore can lead to tissue damage beyond the area of intended removal.
[0076] Other devices such as low and high-speed pneumatic or electrical powered rotary burrs are also used. But while they are very useful for removing hard tissues, such as bone, they do not efficiently and effectively remove soft tissues, such as disc material. An example of such a rotary burr is shown in U.S. Pat. No. 5,490,860 to Middle et al., the entire contents of which being incorporated herein by reference. Another type of rotary burr is commercially available and is sold under the name Disc Whisk™ available from Surgical Dynamics Inc. of Norwalk, Conn. Rotary burrs attempt to automate and improve the efficiency of disc removal, but these motorized devices are potentially dangerous when used around the spinal cord and spinal nerves as they develop heat, may grab soft tissue and may penetrate too far.
[0077] In light of the above it is clear that there remains a need for an improved, hand-powered tool specifically designed for the removal of diseased soft tissue, such as disc tissue. The current invention improves on the current state of the art by providing a apparatus and method which may be used to efficiently, effectively and safely remove soft tissue from a spinal member such as a disk.
BRIEF SUMMARY OF THE INVENTION
[0078] The present invention is directed to a unique reamer tool that may be used to circumferentially resect tissue from a diseased area of a body. The reamer tool of the present invention consists of a sturdy, yet small diameter, hand powered, multi-bladed cutting tool and its method of use.
[0079] In at least one embodiment of the invention the reamer tool has a cutting beam which is pivotally engaged to the tool assembly, a push rod and handle in a rack and pinion relationship to allow the cutter beam to be pivoted relative to the distal end of the tool assembly. The cutter beam may have a plurality of cutting blades or surfaces. As the cutter beam is pivoted as a result of compression of the handle, the cutting blades cut into and resect the surrounding tissue.
[0080] In at least one embodiment of the invention the reamer tool may be equipped with a variety of devices designed to make the surgical procedure more efficient. For example the reamer tool may have an attached or integrated suction tube which may be used to remove the tissue which has been resected by the cutting action of the cutter beam. Other devices may also be employed.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0081] A detailed description of the invention is hereafter described with specific reference being made to the drawings in which:
[0082] FIG. 22 is a perspective view of an embodiment of the invention;
[0083] FIG. 23 is a cut-away side view of an embodiment of the invention in the non-actuated position;
[0084] FIG. 24 is a cut-away side view of the embodiment of the invention shown in FIG. 2 in the actuated position;
[0085] FIG. 25 is a side view of the distal end of an embodiment of the invention wherein the pivoting action of the cutter beam is illustrated;
[0086] FIG. 26 is a perspective view of the linkage assembly of the distal end of the reamer tool shown in FIG. 4 ;
[0087] FIG. 27 is a top-down view of an embodiment of the cutter beam;
[0088] FIG. 28 is a cut-away side view of a two handed embodiment of the invention in a non-actuated position;
[0089] FIG. 29 is cut-away side view of a two handed embodiment of the invention in an actuated, cutting position; F
[0090] FIG. 30 is a side view of a serrated cutting beam;
[0091] FIG. 31 is an end view of the serrated cutting beam of FIG. 9 ;
[0092] FIG. 32 is an enlarged side view of the end of the tool showing the cutting beam attachment; FIG. 33 is an anterior view of a spine showing a way in which the present invention may be used, without a guide tube over the tool;
[0093] FIG. 34 is a top view of a vertebral body showing one location where the tool can enter and provide reaming; and
[0094] FIG. 35 is a side view of a spine section showing an alternative manner in which the present invention may be used.
DETAILED DESCRIPTION OF THE INVENTION
[0095] As may be seen in FIG. 220 the reamer tool, indicated generally at 100 may be thought of as being comprised of three main portions: a proximal portion 120 , a middle portion 140 , and a distal portion 160 .
[0096] As may be seen in FIGS. 23 and 24 , the proximal or handle portion 120 consists of a handle body 200 , a handle body lever 220 , a rack 240 and pinion 260 , a pinion handle lever 280 , a shoulder bolt 300 , and a biasing member or return spring 320 . The middle portion 140 consists of a shaft tube 400 through which a drive rod 420 is longitudinally actuated. The drive rod 420 is engaged to the distal end 500 (as may be seen in FIG. 25 ) of the rack 240 . When a gripping action supplied by a user (not shown) pivotally actuates the pinion handle lever 280 about the pivot member 340 , the teeth 360 of the pinion 260 engage the teeth 380 of the rack 240 resulting in the back and forth movement of the drive rod 420 within the shaft tube 400 . As indicated by arrows 440 and 460 the actuation of the pinion handle lever 280 resulting from a compressive force supplied by a user will move the drive rod 420 distally such as shown in FIG. 24 , or proximally when the force is removed, as is shown in FIG. 23 . The position of the pinion handle lever 280 relative to the handle lever 220 , and thus the position of the drive rod 420 , will depend on the extent of the compressive force supplied by a user to the pinion handle lever 280 and handle body lever 220 .
[0097] In FIG. 23 the reamer 100 is shown in the at rest or non-actuated position. The shoulder bolt 300 is engaged to the proximal end 520 of the rack 240 . The biasing member or return spring 320 is disposed about a bolt shaft 540 which extends proximally from the rack 240 passing through a return member 580 . The bolt shaft 540 ends in an enlarged spring retaining portion 560 of the shoulder bolt 300 . The return spring 320 is biasedly engaged between the spring retaining portion 560 of the shoulder bolt 300 and the return member 580 . This return spring exerts a force sufficient to keep the drive rod 420 extended distally. The force exerted by the return spring 320 is overcome when the pinion handle lever 280 is engaged by the gripping action of the user previously described and shown in FIG. 24 . When the user's grip is relaxed the force exerted by the return spring 320 against the spring retaining portion 560 and the return member 580 will place the reamer back in the at rest position shown in FIG. 23 . The tool is returned to the rest position so that its profile is small enough to be removed from a guide tube or a hole in bone.
[0098] The lever may be actuated by an air cylinder, an electric solenoid or any other actuator means. Hand operated levers are shown which are less expensive and easier to clean. In the embodiment shown in FIGS. 22-24 , the proximal end 120 contains only one handle body lever 220 and one pinion lever 280 . This embodiment is designed for single-handed operation. However, in at least one alternative embodiment, shown in FIGS. 28 and 29 the reamer tool may be designed for two-handed actuation. As may be seen, a two handed reamer tool 100 has a the proximal end 120 having a handle body lever 220 which is equipped with opposing grip portions 900 and 920 , as well as a pinion lever 280 having opposed section 940 and 960 as well. The present embodiment of the reamer tool 100 may be designed in such a manner that in order to rotate the cutter 600 an two handed grip of alternating action is required to actuate the opposing grips and lever sections 900 , 940 and 920 , 960 respectively.
[0099] Turning to FIG. 25 , the distal portion or end 160 of the reamer 100 contains the reamer head or cutting beam 600 . The beam has a plurality of cutting surfaces 610 . In the embodiment shown, the cutting blades are located at the both ends 860 and 880 of the beam. The beam 600 is pivotally connected to a handle body extension 620 by a lower pivot member 640 .
[0100] The beam 600 is also engaged to the a distal end 660 of the drive rod 420 via linkage assembly 680 . The linkage assembly 680 comprises a pair of beam engagement projections 700 , as best shown in FIG. 26 , which are disposed about the linkage tab 720 of the beam 600 , as best shown in FIG. 27 . As may be seen in FIG. 25 , a proximal pivot member 740 passes through the linkage tab 720 and the beam engagement projections 700 . As may be seen in FIG. 26 , the linkage assembly 680 also includes a pair of rod engagement projections 780 . As shown in FIG. 25 , a distal pivot member 760 passes through the pair of rod engagement projections 780 as well as the distal end 660 of the drive rod 420 . As indicated by arrows 800 , the unique arrangement of the beam 600 to the drive rod 420 and extension 620 via the linkage assembly 680 provides the reamer 100 with the ability to rotate the beam 600 about the lower pivot member 640 when the drive rod 420 is distally extended in the manner previously described. When the beam 600 is rotated, the cutting edges 610 will cut into and abrade any tissue which is encountered by the moving cutting edges 610 .
[0101] As may be seen in FIG. 27 , the cutting edges 610 are positioned on both ends 860 and 880 of the beam 600 and may be on opposing sides of the beam 600 , such as may be seen in FIG. 25 . In the present embodiment shown in FIG. 27 , the cutting blades 610 may be curved about the shape of a semi-circle, however, the blades 610 may also be provided with other shapes as desired. In addition, the entire perimeter 820 of the beam 600 , or a portion thereof, may include bladed portions 610 which extend beyond the semi-circle shape to form a “U” shape, such that cutting may occur along the lateral edges 630 of the perimeter 820 as well as the semi-circular ends 860 and 880 . As a result, the reamer 100 may be configured to provide a variety of cutting options which will provide a smooth uniform resecting action as the beam 600 rotates back an forth as indicated by arrows 800 in FIG. 25 .
[0102] In another embodiment of the invention the beam 600 may include one or more backward cutting blades 650 , as is shown in FIG. 25 , allowing cutting in both the forward and reverse directions.
[0103] The reamer 100 of the present invention may be used in a number of different manners as may be recognized by those of skill in the art. When employed to debride an intervertebral disc, it may be understood that the reamer 100 may be used in the following manner.
[0104] After adequate exposure of a small portion of the disc is accomplished by the surgeon using well known standard techniques, any appropriately sized standard drill may be used to perforate the disc. The drill is guided in a direction that crosses the central portion of the disc, to a depth that comes close to, but does not penetrate the far side of the disc.
[0105] The distal end 160 of the reamer 100 is then placed into the disc to the full depth of the drilled hole. The reamer 100 is oriented such that its beam 600 , with attached cutting blades 610 , is parallel to the transverse plane of the disc.
[0106] The application of a manual compression force, such as by gripping the pinion lever 280 toward the handle body lever 220 forces the drive rod 420 in the distal direction. This causes the beam 600 to rotate in an elliptical manner around the lower pivot member 640 . As is shown in FIG. 25 , the beam 600 may be pivotally displaced at least 90 degrees when the pinion lever 280 is actuated such as may be seen in FIG. 24 . The cutter will typically provide more than 100 degrees of cutting. This motion causes the cutting blades 610 (and 630 ) to move against any intervening tissue, cleanly cutting that tissue. The return spring 320 forces the drive rod 420 and the beam 600 back to their original and respective non-actuated positions when the pinion lever 280 is relaxed, such as may be seen in FIG. 23 . This procedure may be used to remove the outer nucleus as well as the inner annulus of a spinal disk, leaving the outer annulus intact. Such a procedure is the goal of a partial disectomy. The reamer 100 may then be reoriented 180 degrees, so that the opposite side of the disc can be debrided.
[0107] In addition, to providing the cutting motion described above, the present invention may also utilize a variety of blade types to provide for different cutting and resecting characteristics. For example, in FIGS. 4 and 6 the cutter beam 600 may be seen to employ one or more straight edge blades on the cutting edges 61 . Alternatively, one or more of the cutting edges 610 may also have serrated teeth 900 such as may be seen in FIGS. 30 and 31 .
[0108] As may best be seen in FIG. 32 , when the reamer tool 100 is in the at rest or non-actuated position, the cutter beam 600 is maintained in a position such that the distal end 160 retains a profile substantially less than the distal end would have when in the actuated position such as is shown illustrated in phantom in FIG. 25 . The reduced profile of the non-actuated distal end is sufficiently small to allow insertion of the distal end 160 into a small space or cavity 100 such as is shown in FIG. 33 .
[0109] In FIGS. 33-34 , the reamer tool 100 is seen in use in merely one of a myriad of potential uses. As presently shown, the distal end 160 of the reamer tool 100 may be inserted into an opening or cavity 1000 of a spinal body 1020 . As the cutter beam 600 is actuated, such as previously described, the cutting surfaces 610 abrade the surrounding tissue 1040 to form a transverse cavity 1060 . Alternatively, the reamer tool 100 may be used to resect tissue from a spinal body 1020 in the middle of a vertebral compression fracture, such as may best be seen in FIG. 35 .
[0110] After the cavity has been formed, the tool 100 along with any resected tissue is removed. The newly formed cavity may then be filled with filler material such as bone cement and/or graft material. The cavity created by the tool would tend to place the filler in a position where it could accumulate and develop pressure that would tend to elevate or re-expand (or reduce—in orthopedic terms—) the fracture, thereby forcing bone fragments into their pre-injury positions as illustrated in FIG. 35 .
[0111] In addition to the uses described above, the various embodiments of the reamer tool 100 as described herein may also be used in a wide variety of other procedures. For example, the present reamer tool may be used for removing bone cement from the intramedullary canal of long bones during reconstructive procedures such as joint replacement. The tool may also be useful for debriding cartilage from joints during arthoscopic procedures. Another use may involve using the present reamer tool for certain types of joint arthrodesis, e.g. ankle, inter-tarsal, metatarsal-phalangeal, etc., wherein the tool is used in debriding and preparation of surfaces.
[0112] Other uses for the present invention may include: using the reamer tool for producing or sculpting channels for tendon insertion and/or reattachment, such as anterior curciate or rotator cuff repairs. The reamer tool may be used in nasal or sinus surgery for sub-mucosal resections. The reamer tool may also find use in certain gynecological procedures such as a dilation and curettage procedure (D&C). Yet another potential use for the present invention would be for fat immobilization during lipo-suction operations. In such a use the tool could be useful in freeing up fatty tissue to improve removal.
[0113] In addition to being directed to the embodiments described above and claimed below, the present invention is further directed to embodiments having different combinations of the features described above and claimed below. As such, the invention is also directed to other embodiments having any other possible combination of the dependent features claimed below.
[0114] The above examples and disclosure are intended to be illustrative and not exhaustive. These examples and description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the attached claims. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims attached hereto. | A method of treating a compression fracture in a bone comprising the steps of forming a transverse cavity within said bone defined by at least one substantially flat surface lying substantially in a transverse plane formed by and communicating with said transverse cavity, the transverse cavity having a substantially uniform transverse extent and a maximum height, the maximum height being less than said transverse extent and applying a force within said transverse cavity generally normal to said surface to displace said surface and restore said bone to its substantially normal anatomic position. | 0 |
FIELD OF THE INVENTION
This invention relates to flextensional microphones which are made up of a piezoelectric substrate having opposing surfaces, typically parallel surfaces when the substrate is crystalline or ceramic, and at least one sound receiving surface physically tied to the piezoelectric substrate. The microphones are at least partially isolated via a biocompatible material, e.g., by a covering or a coating. The inventive microphones may be subcutaneously implanted. The inventive microphones may be used as components of surgically implanted hearing aid systems or as components of hearing devices known as cochlear implants. Preferably the microphones are used in arrays and when used as a component of a hearing assistance or replacement device, are preferably used in conjunction with a source of feedback information, preferably another microphone. The feedback information usually relates to sound re-emitted from physical portions of the ear, e.g., the eardrum, where those portions have been directly or indirectly driven by the actuator of the implanted hearing aid.
BACKGROUND OF THE INVENTION
For an implantable hearing device to transmit acousto-mechanical signals to the middle-ear or the inner ear, or electrical signals to an inner ear electrode, a microphone is needed to sense environmental sounds. To make the hearing device fully implantable, the microphone and associated wiring must be placed under the skin. Subcutaneous placement of the microphone allows the entire hearing device, i.e., that microphone, the output transducer, the battery, and associated sound processor to be implanted entirely inside the body. Fully implanted hearing devices have the important cosmetic advantage of being entirely invisible.
The inventive microphones may also be used as a component of a partially implantable hearing aid system. In a typical partially implantable hearing aid, the microphone and output transducer are implanted in the body but the power supply and sound-processing electronics are outside the body. Communication from the microphone sound processor is achieved with implanted coils using RF techniques.
Others have proposed implanting microphones into the body as a part of a hearing aid. Several microphone implantation methods have been proposed. These devices fall into two generic classes. In the first such class, the microphone is implanted subcutaneously. In the other group, the microphone is placed outside the skin and the signal is sent trans-cutaneously by a pair of coils. Our inventive microphones are generally used as subcutaneous microphones, although obviously, they have other uses.
In the first noted class of hearing aids, those using subcutaneous microphones, the transducers fall into at least four basic categories. In the first, a commercially available electret microphone is used. The electret microphone is encased and sealed in an acoustic chamber thereby making it compatible for implantation in tissue. This approach was originally described in: Kodera, K., Suzuki, K., and Ohno, T. (1988). “Evaluation of the implantable microphone in the cat,” in Suzuki, J.-I., editor, Middle Ear Implant: Implantable Hearing Aids , pages 117-123. Karger, Basel. More recently, such a method is found in U.S. Pat. No. 5,814,095, to Willer et al. and in U.S. Pat. No. 5,859,916, to Ball et al.
In another method, the vibrations of the malleus are sensed by a piezo transducer. This approach is suggested in U.S. Pat. No. 5,531,787, to Lesinski et al.; U.S. Pat. No. 5,788,711, to Lehner et al.; U.S. Pat. No. 5,842,967, to Kroll; and U.S. Pat. No. 5,836,863, to Bushek et al.
In yet a third method, sound vibrations in the ear canal are sensed by a PVDF (Kynar) based piezo transducer placed in the concha. This approach is shown in U.S. Pat. No. 5,772,575, to Lesinski et al.
Finally, U.S. Pat. No. 5,782,744, to Money, describes a sensor placed in the middle ear cavity to transduce the sound produced by the eardrum, or in the cochlea to transduce the fluid pressure produced by stapes motion.
In each of these techniques, the sensing microphone has been placed in various locations within the auditory periphery.
None of these documents show the use of our inventive microphone and particularly not within the array or hearing device described herein.
SUMMARY OF THE INVENTION
The inventive microphone is an acousto-active device made up of an acousto-active substrate having a pair of opposed planar surfaces. The substrate, typically made from piezoelectric single crystals (SCP) or ceramics such as PZT, PLZT, PMN, PMN-PT, have a 3 direction orthogonal to the planar surface defined by the 1 and 2 directions parallel to the planar surfaces. These materials generate a voltage measurable between the two planar surfaces when the material is strained or stressed in at least one of said three directions. The coefficients of d 33 , d 31 and d 32 commonly relate the induced voltage induced to the induced strain. In regards to the coefficient d ij , the ij subscripts denote the orthogonal coordinate system. The substrate itself may be a single crystal, a single layer, or may be a multi-layer composite. Most preferred, the substrate is a single crystal. The substrate typically is generally circular although it need not be. In certain circumstances, the substrate may have at least one linear edge, e.g., it may be rectangular.
The acoustic stress is applied to the substrate by at least one stress-inducing member attached to the substrate. One of the stress-inducing members induces stress across at least one of the directions in the 1-2 planar surface having piezo coefficients d 31 or d 32 when a flat portion of the member is exposed to an acoustic pressure. Another stress-inducing member is also attached to the other side of the substrate, but it need not be a sound receiving member.
The microphone preferably is isolatable from the surrounding body using a biocompatible material, perhaps a covering, casing, or bag over at least a portion of the stress-inducing members. It is highly preferable that the substrate be capable of producing a detectable voltage across its planar surfaces when the first stress-inducing member is subjected to a sound in the audible frequency range (100 Hz-100 kHz), and levels of 40-120 dB corresponding to a microphone sensitivity of 0.2 mV/Pa to 50 mV/Pa and a noise figure of less than 40 dB SPL (Sound Pressure Level).
The system including the inventive transducer may further include a voltage receiver, e.g., a detector, an A/D converter, an amplifier, or the like, for receiving the voltage generated across the substrate surfaces when the stress-inducing members are exposed to sound or to vibrations due to sound. The voltage produced as a result of the stress applied to the substrate is measured across electrodes placed on the substrate surfaces. The electrodes may be independent, may be an adhesive affixing the stress-inducing members to the substrate, or may be the stress-inducing members themselves. The electrodes may be metallic or a conductive polymer.
The first or primary stress-inducing member generally includes a sound receiving diaphragm generally parallel to the adjacent substrate planar surface. The sound forces impinging on the sound receiving diaphragm are transmitted to the substrate via any of a number of structures. The preferred structure is a frusto-conical shell section (a “cymbal”) further having an outer lip fixedly attached to the substrate. Other structures include frusto-hemispherical shell sections (a “moonie”), bridge shaped components having at least two linear spacing members attached both to the sound receiving diaphragm and to the substrate, and prismatoid shell sections. Other structures are also suitable.
The inventive device may be included in an array of microphones or used as a singlet. The preferred array is linear, i.e., the microphones are in a line and the sound receiving diaphragms all point in the same direction.
Furthermore, the inventive method for detecting audible sound typically comprises the steps of placing in the path of an audible sound, at least one inventive flextensional microphone that is at least partially isolated with a biocompatible coating. It is desirable that the microphone be subcutaneously implanted. It should produce a first electric signal related to the audible sound which is amplified and introduced to an output actuator coupled to a human ear component.
The flextensional microphones are preferably situated in an array to allow detection of the direction of a path of said audible sound.
It is also desirable to use an independent microphone situated so that it can hear sound re-radiated by an human ear component, e.g., the eardrum, and produce a feedback signal related to that re-radiated sound. The feedback signal is then compared to the signal sent from the microphone array and then is used to modify the amplified signal to produce a feedback-free signal for the output actuator.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a piezoelectric crystal and the conventions for naming the specific piezoelectric strain coefficients as related to an orthogonal coordinate system.
FIGS. 2A, 2 B, and 2 C show respectively cross-section side view, perspective view, and top view of one variation of the inventive device.
FIGS. 3A and 3B show respectively cross-section side views of hemispherical variations of the inventive device.
FIGS. 4A and 4B show perspective views of two variations of the inventive device having bridge-like endcaps.
FIGS. 5A, 5 B, 5 C, and 5 D show respectively perspective view, side view, end view, and top view of the prismatoid variation of the inventive device.
FIGS. 6A and 6B show respectively cross-section side views of variations of the inventive device having polymeric substrates.
FIGS. 7A, 7 B, and 7 C show partial side-view cross-sections of representative methods of attaching the endcaps to the substrate.
FIG. 8 shows a generalized schematic of a circuit which may be used with the inventive microphone devices.
FIGS. 9-12 show placement of the inventive device within the ear structure.
FIG. 13 shows exterior placement of an array of the inventive device.
DESCRIPTION OF THE INVENTION
The inventive microphone is based on the principles of flextensional design. Preferred are the “cymbal” or “moonie” transducers discussed in more detail below. Also preferred is the use of these inventive microphones as a subcutaneous component in a surgically implantable hearing aid system, cochlear implant system, or other related devices.
The preferred inventive microphones include a piezo element in a flextensional mode to sense the acoustic pressure of environmental sounds. The piezo substrate for the inventive microphone may be a single crystal piezo (SCP), or a ceramic, polymer or other type of piezo element. The substrate may be a composite as is discussed below.
In each variation of the invention, acoustic energy causes contractions and expansion of a piezoelectric transducer. For instance, the length, width, and height of a rectangular transducer, or the thickness and diameter of a disk-shaped transducer will vary in response to physical manipulation of that substrate via imposition of sonic energy to that substrate. The expansions and contractions in turn produce an electrical signal that is proportional to the applied force. That is to say: the diaphragm vibrates; the piezoelectric substrate vibrates; the piezoelectric substrate generates a voltage. This is based on the classical mechanical-to-electrical piezo property that was mathematically deduced from fundamental thermodynamic principles by Lipton in 1881.
Derivable from constitutive laws that govern operation of piezo transducers, are the set of piezo constants g mn relating the electric field produced by a mechanical stress (g=open circuit electric field/applied mechanical stress) to that mechanical stress. The units are typically expressed as volts/meter per Newtons/square-meter. The output voltage is obtained by multiplying the calculated electric field g by the piezo thickness t (V 0 =g·t). These coefficients are a measure of the voltage generated across a surface (m) due to a given force in a specified direction (n). As is shown in FIG. 1, subscript “33” indicates that both the electric field and the mechanical stress are along the same polarization axis. A “31” subscript signifies that the pressure is applied at right angles to the polarization axis, with the voltage across the same electrodes as for the “33” case.
One way of increasing the sensitivity of piezo-metal or piezo-plastic or composite microphones is the use of a transducer based on flextensional designs. Flextensionals have existed since the 1920s and are made up of a piezoelectric sensor element sandwiched between two specially designed endcaps. The endcaps serve to mechanically amplify the forces and, consequently, the generative voltages of the piezos. A force in the axial direction of the endcaps allows both the g 31 , and g 33 coefficients of the piezo element (again, see FIG. 1) to cooperate in producing a much larger electric field [g h =(g 33 +g 31 )] than is possible with just the piezo element. See, Xu, Q., Yoshikawa, S., Belsick, J., and Newnham, R. (1991). “Piezoelectric composites with high sensitivity and high capacitance for use at high pressures,” IEEE Transactions of Ultrasonics, Ferroelectrics, and Frequency Control 38(6):634-639.
The shape of the endcaps or shells, to a large extent, determines this mechanical amplification. Two basic types, described in more detail below, are called the “cymbal” and the “moonie”. The general design of these transducers may be found, e.g., in Dogan, A. (1994). Flextensional ‘moonie and cymbal’ actuators. Ph.D. thesis, The Pennsylvania State University; Tressler, J. F. (1997). Capped ceramic underwater sound projector: The ‘Cymbal’ Ph.D. thesis, The Pennsylvania State University; and in U.S. Pat. No. 5,729,077, to Newnham et al.
Clearly, one important advantage of these transducers is the potential for increase in the effective piezo constants (such as the figure of merit g h ) by an order of magnitude or more. In flextensional microphones, the force imparted by the acoustic signal on the endcaps or shells of the transducer is increased by the lever action or moment arm of the shell at the piezo sensor element. This mechanical advantage, combined with the use of certain SCP's results in effective overall values of g 31 and g 33 , that are typically 3-4 times greater than ceramic piezo substrates (see U.S. Pat. No. 5,804,907 to Park et al.) and consequent generated voltages that are 30-40 times (about 30 dB) greater than other existing methods. This is an important advantage because the combined effect will be an increase in signal level for the same background noise (i.e., due to the electronics) and the resulting signal-to-noise ratio of the overall hearing device is greatly improved.
When implanting these inventive microphones below the skin, it is desirable to match the impedance of the microphone to the impedance of the surrounding tissue. Otherwise, the overall sensitivity of the device is compromised. Ceramic piezo transducers are more difficult to match due to their high impedance in comparison to the impedance of air. PVDF (Kynar) based microphones, on the other hand, are generally easier to match because the impedance of this material is very close to the impedance of fluid and body tissues. In general, the inventive microphones are tailored to have the impedance approximating that of tissue so that energy transfer through the skin is optimized. As will be noted below, the physical parameters of the endcaps or stress-inducing members of the inventive microphones are varied to provide such a match.
In one variation of the invention, the inventive microphone is implanted in the external ear canal, either between the malleus and the eardrum or between the skin and the temporal bone. In an implantable hearing aid application, sound is generated by the output actuator to drive the inner ear, or alternative the middle ear. It is well known that the middle ear provides a pressure gain from the ear-canal to the vestibule in forward direction. See, Puria, S., Peake, W., and Rosowski, J. (1997). “Sound-pressure measurements in the cochlear vestibule of human-cadaver ears,” J. Acoust. Soc. Am. 101(5):2754-2770. It is also known that in the reverse direction the middle ear can transmit sounds that originate from the inner ear. See, Puria, S. and Rosowski, J. J. (1996). “Measurement of reverse transmission in the human middle ear: Preliminary results,” in Lewis et al., T., editor, Diversity in Auditory Mechanics. World Scientific, as well as Hudde, H. and Engel, A. (1998). “Measuring and modeling basic properties of the human middle ear and ear canal. part III: Eardrum impedances, transfer functions and model calculations,” Acustica—acta acustica 84:1091-11109. Otoacoustic emissions are evidence of this reverse sound transmission path. See, Kemp, D. T. (1978). “Stimulated acoustic emissions from within the human auditory system,” J. Acoust. Soc. Am. 64:1386-1391. Under these circumstances, the eardrum acts as loudspeaker. Consequently, a microphone placed in the ear canal may result in acoustic feedback due to the presence of the output transducer of an implantable hearing aid. To further attenuate the feedback path from the eardrum to the microphone, it may be desirable that the microphones be placed as far away from the eardrum as possible. Thus, an advantage of microphones located outside the ear canal is a substantial reduction of feedback due to sound generated by the eardrum in the reverse direction.
Directional microphone technology may be used to improve the signal-to-noise ratio (SNR) for sounds emanating from a desired direction. Suitable directional microphone technology includes the use of microphones such as dual-port single-diaphragm microphone or two omnidirectional microphones with electronic delay or an array of omnidirectional microphones electronically arranged to provide beam forming. See, e.g., Soeda, W. (1990). Improvement of Speech Intelligibility in Noise. Ph.D. thesis, Delft University. ISBN 90-9003763-2 and Schuchman, G., Valente, M., Beck, L., and Potts, L. (1999). “User satisfaction with an ITE directional hearing instrument,” The Hearing Review 6(7):12-23. For practical and cosmetic reasons, we prefer to place the microphone array outside the external ear canal and between the skin and the temporal bone.
FIGS. 2A, 2 B, and 2 C show respectively side cross section, perspective, and top views of a first variation ( 100 ) of the inventive microphone. This is the shape we generally will refer to as the “cymbal” microphone. The substrate ( 102 ) is shown to be a multi layer composite of a ceramic piezoelectric material. As is noted elsewhere, the substrate ( 102 ) preferably comprises a SCP of a solid solution of lead-zinc-niobate/lead titanate or lead-magnesium-niobate/lead titanate, described by the formulae: Pb(Zn 1/3 Nb 2/3 ) 1−x Ti x O 3 or Pb(Mg 1/3 Nb 2/3 ) 1−y Ti y O 3 ; where 0≦x<0.10 and 0≦y<0.40. Other especially suitable materials include ceramics such as PZT, PLZT, PMN, PMN-PT and piezoelectric polymers such as PVDF, sold as Kynar. The substrate ( 102 ) in this variation has a pair of opposing planar surfaces. It is across these opposing surfaces where the resulting voltage may be found. The planar surfaces of the substrate ( 102 ) is adherent to at least a pair of stress-inducing members ( 104 , 106 ). Typically, one of the stress-inducing members (e.g., 104 ) will be exposed to the sound to be detected by the hearing aid assembly. A stress-inducing members ( 104 , 106 ) will typically be made up of a sound receiving diaphragm ( 108 ) separated from the substrate ( 102 ) by a frusto-conical section ( 110 ).
The stress-inducing members ( 104 , 106 ) also typically have a lip ( 112 ) which transmits force from the sound receiving diaphragm ( 108 ) through the frusto-conical section ( 110 ) to the substrate ( 102 ). The stress-inducing members ( 104 , 106 ) may be made of a variety of materials, e.g., metals and alloys such as brass, titanium, Ni/Ti alloys such as nitinol, etc. and polymers. Although a variety of polymers are suitable, engineering polymers are desired.
Further, at least a portion of the microphone, e.g., the stress-inducing members ( 104 , 106 ) and the edges of the substrate, should be isolated from the surrounding body with a biocompatible material. Suitable materials include coatings or coverings of, e.g., titanium, titanium oxide, gold, platinum, vitreous carbon, and a number of other appropriate and known polymers. A polymeric, metallic, or composite bag of appropriate size and composition is also appropriate. Care is taken not to short-circuit the two planar surfaces of the substrate with the isolating material.
The stress-inducing members ( 104 , 106 ) may be glued to the substrate ( 102 ) by an adhesive ( 114 ). The adhesive, preferably those sold as CRYSTAL BOND and MASTER BOND (sold by Emerson and Cuming), may be used as the electrodes for picking up the resulting electrical signal by including, e.g., powdered metals, in the adhesive layer ( 114 ). The stress-inducing members ( 104 , 106 ) may similarly be used as those electrodes.
It should be noted that stress-inducing member ( 104 ) need not be the same physical shape as stress-inducing member ( 106 ). Stress-inducing member ( 104 ) “sees” the impinging sound (depicted by the direction arrows in FIG. 2A) and, when the device is implanted, the backside stress-inducing member ( 106 ) is not necessarily in the path of the sound. The stress-inducing member ( 106 ) need not, for instance, have the same size diaphragm ( 109 ). Indeed, in some variations, it need not have a planar diaphragm ( 109 ) at all.
The components of stress-inducing member ( 104 ) are optimized to maximize the resulting pressure imposed upon the substrate ( 102 ). For instance, the planar diaphragm ( 108 ) may be maximized in size or in diameter in keeping with the goal of maximizing radial displacement in the plane of the substrate ( 102 ).
Typically, the size of the inventive microphone is less than 5 mm but is not limited to this dimension.
FIGS. 2B and 2C show that the overall shape of this variation of the device is circular.
FIG. 3A shows a cross section side view of an additional variation ( 200 ) of the inventive microphone. The main components of the device are substantially the same as was the case with the variation shown in FIGS. 2A, 2 B, and 2 C, with the exception of the spacer lever arm ( 202 ) between planar diaphragm ( 204 ) and peripheral lip ( 206 ). The adhesive ( 208 ) is also shown between lip ( 206 ) and piezoelectric substrate ( 210 ). It should be noted that the substrate ( 210 ) is depicted as a single crystal. A single crystal of a solid solution of lead-zinc-niobate/lead titanate or lead-magnesium-niobate/lead titanate, described by the formulae: Pb(Zn 1/3 Nb 2/3 ) 1−x Ti x O 3 or Pb(Mg 1/3 Nb 2/3 ) 1−y Ti y O 3 is the most preferred piezoelectric substrate ( 210 ). Other especially suitable materials include ceramics such as PZT, PLZT, PMN, PMN-PT and piezoelectric polymers such as polyvinylidenefluoride (PVDF), sold as KYNAR.
FIG. 3B shows a cross section, side view of an additional variation ( 230 ) of the inventive microphone. Again, the main components of the device are substantially the same as was the case with the variation shown in FIGS. 2A, 2 B, and 2 C. However, the caps or stress-inducing members ( 232 , 234 ) are of a different design. Stress-inducing member ( 232 ) is a relatively solid section with a dome-shaped cavern inside adjacent the substrate ( 236 ) surface. This variation has a very large planar diaphragm ( 236 ). Another variation of the stress-inducing member ( 234 ) is similar to stress-inducing members ( 232 ) but has a groove ( 238 ) included for the purpose of rendering the stress-inducing members ( 234 ) somewhat more flexible than its cousin stress-inducing member ( 232 ). In a single device, either of the stress-inducing members ( 232 , 234 ) may have either design or both may be the same.
FIG. 4A shows a perspective view of still an additional variation ( 250 ) of the inventive microphone. In this variation, the transducer is rectangular, perhaps square. The stress-inducing members ( 252 , 254 ) are bridge-like, and open on the sides. The respective planar diaphragms ( 256 , 258 ) similarly have one or more linear sides and are separated from the adherent lips ( 260 , 262 ) by spacer/lever arms ( 264 , 266 ).
FIG. 4B shows a perspective view of an additional variation ( 270 ), referred to as the X-spring actuator, of the inventive microphone. In this variation, the transducer ( 270 ) has a plurality of stacked substrates ( 274 ) separated by complementary substrates ( 276 ). The substrates ( 274 ) and complementary substrates ( 276 ) are aligned to form a composite substrate ( 278 ). The planar regions ( 272 ) for intercepting audible sound are supported by arms ( 280 ) that are attached to the composite substrate ( 278 ).
FIG. 5A shows another variation of the inventive flextensional microphone ( 300 ) having a pair of trapezoidal closed endcaps ( 302 , 304 ). In this variation, endcap ( 302 ) has a planar surface of ( 306 ) and extending lips ( 308 , 310 ) which adhere to the substrate ( 312 ). The endcaps ( 302 , 304 ) are closed and contain a volume inside. The angle of the side panels ( 314 ) and ( 316 ) may be altered to, e.g., variously maximize the size of the planar diaphragm ( 306 ) or enhance the mechanical advantage of the planar diaphragm ( 306 ) with respect to substrate ( 312 ).
FIG. 6A shows, in cross-section, side view, still another variation ( 340 ) of the inventive device. In this variation, the respective endcaps ( 342 , 344 ) are depicted to be of the “cymbal” form as discussed above. However, they may be any of the endcap variations discussed above and elsewhere herein. The major variation from the others previously discussed is the use of a piezoelectric polymeric substrate ( 346 ). Piezoelectric substrate ( 346 ) may be made from a number of different known piezoelectric materials but preferably is polyvinylidenefluoride (PVDF), sold as Kynar. The polymer is typically shaped into a generally domed, perhaps hemispherical, central portion ( 348 ) which oscillates upon imposition of energy from the receiving plane region ( 350 ) to accentuate the amount of electrical energy created by the movement of the endcaps ( 342 , 344 ). The central portion ( 348 ) of substrate ( 346 ) need not be dome-like; it may be flat as was the case with those ceramic and SCP substrates mentioned above, or it may have a shape approximating but not reaching that of hemisphericity. Substrate ( 346 ) is attached to the endcaps ( 342 , 344 ) using adhesive or the like. The choice of material for joining substrate ( 348 ) to endcaps ( 342 , 344 ) is broader in this variation than is the choice for those variations discussed earlier. A typical adhesive is depicted at ( 352 ) in FIG. 6 A.
FIG. 6B shows another variation ( 360 ) of the inventive microphone. It is similar to the device discussed with regard to FIG. 6A, excepting that it has dual transducers ( 362 ) and ( 364 ) which are spaced apart from each other. Again, these transducer substrates ( 362 , 364 ) are preferably provided with a generally permanent pre-form as shown in FIG. 6B, although the shape may vary as it is mechanically excited by the respective endcaps.
It should also be understood that the substrates shown in FIGS. 6A and 6B may alternatively be constructed of the non-polymeric materials mentioned above.
FIGS. 7A, 7 B, and 7 C all show close up, side view, partial cutaways of methods of attaching endcaps to the substrate. The collection of drawings is not all-inclusive; others will be similarly appropriate.
FIG. 7A shows a variation in which substrate ( 700 ) is covered by a conductive covering ( 702 ). Conductive covering ( 702 ) may be, e.g., sputtered metal, metals, or alloy, such as a member of the Platinum Group of the Periodic Table (Ru, Rh, Pd, Re, Os, Ir, and Pt) or gold. Titanium (Ti) is also especially suitable. Because of the nature of the substrates, it is often desirable to place these metals on the surface of the substrate by, e.g., sputtering, evaporation, plating or other deposition methods.
The combination of substrate ( 700 ) and sputtered coating ( 702 ) is then made to adhere to endcap ( 704 ) via, e.g., an adhesive ( 706 ). The adhesive ( 706 ) may be conductive, or not, as desired. Similarly, the endcap ( 704 ) may be used as a site for an electrical lead for that plane of the substrate ( 700 ), if such is desired. If the adhesive ( 706 ) is not conductive, the electrical signal would be taken from sputtered coating ( 702 ) and coating ( 708 ).
It should be noted that although conductive coating ( 702 ) is shown to extend across the complete surface of substrate ( 700 ), it is within the scope of this invention that the applied conductive metallic layer may be limited in size, such as is depicted by layer ( 708 ). In most instances, it is not critical that the conductive layers reach completely across substrate ( 700 ).
FIG. 7B shows a similar variation having substrate ( 700 ) and conductive adhesive ( 710 ) attaching the endcap ( 704 ) to the substrate ( 700 ). Conductive adhesive ( 710 ) may be conducted via the use of, e.g., powdered metals or the like in the adhesive mixture, or by use of inherently conductive materials. Again, this allows the use either of the adhesive itself ( 710 ) or the conductive endcaps ( 704 ) as sites for picking the signal generated by the piezoelectric substrate ( 700 ).
FIG. 7C shows a variation in which the substrate ( 720 ) has a partial outer lip ( 722 ) which can help to minimize radial movement of the endcaps ( 726 ) with relation to the substrate ( 720 ). It is very important that the lip configuration not be allowed to bind the overall movement of the substrate, however. In proper circumstances, i.e., that of a very tightly fitting endcap, the endcap may be used without adhesive.
FIG. 8 shows a generalized schematic of a circuit diagram for use of the inventive arrays in a preferred aided hearing device. The schematic corresponds to an array used either with a patient's right or left ears. At the top of the diagram is shown the presence of a generally linear array of at least two microphones (i and i+n, where n is at least 1). These microphones can also be arranged superior to inferior, or combinations of anterior-posterior, medial-lateral, and/or superior-inferior to gain the desired effect. These microphones intercept sound and because of the spatial relationship among them, are able to differentiate the direction from which sound is coming. For the sound shown in the top of FIG. 8, the lateral microphone hears the sound initially, the mid microphone hears it next, and the medial microphone hears it last. These differences are useful to the patient user. Ideally, the information from the microphones is passed through a filter. A filter may be chosen to correct or to minimize a number of ambient sounds not needed by the user. For instance, sharp sounds such as a hand scratching the microphone as that hand combs the user's hair may be filtered from the signal by a “pop” filter. In any event, the input from the microphones is fed into an amplifier. Similarly, output from a feedback microphone may be introduced into the amplifier. The feedback microphone generally is placed in the region of the human ear which re-emanates sound produced by the output transducer. In general, the output transducer may drive a bone in the human ear, as discussed below, which may in turn provide a physical drive to the eardrum. The eardrum would then act as a speaker cone on a high fidelity entertainment speaker, at such a level that it could be heard by one of the three lateral, mid, or medial microphones. In such an instance, “feedback” occurs and a large and undesirable squeal would be the result in the output transducer. The feedback microphone is placed in the human body in such a way that it “hears” the sound emanating from the body part (e.g., eardrum) and feeds it via a comparator into the amplifier to cancel the effect of the feedback.
These feedback elimination procedures are well known in the art and do not form a critical portion of this invention.
The so-adjusted output from the amplifier is then fed to the output transducer for introduction of amplified sound input into the ear.
FIGS. 9-12 show various desirable placements of the inventive microphones in the body, either alone or as a component of a system in the body.
In FIG. 9, the inventive microphone ( 600 ) (shown here in the so-called “cymbal” configuration) is placed in the external auditory meatus (ear canal) just medial to the concha. This portion of the ear canal has soft tissue and thus the cymbal preferably is anchored to the bony portion of the ear canal to prevent migration of the cymbal.
FIG. 10 shows the inventive microphone ( 600 ) at a more medial location in the ear canal. Here the inventive microphone ( 600 ) is placed within the bony portion of the ear canal. One endcap is buried in bone while the second endcap lies just under the skin. Alternatively, the cymbal could be made of a single endcap that lies under the ear-canal skin.
FIG. 11 shows the placement of the inventive microphone ( 600 ) beneath an elevated portion of the tympanic membrane. The fibrous layer that joins the eardrum and the malleus handle (superior to the umbo region), commonly referred to as the tympano-malleolar fold, has been separated to allow the introduction of the inventive microphone ( 600 ). The inventive microphone ( 600 ), in this instance, has been shaped to accommodate the malleus handle and is slipped between the eardrum and the malleus handle. Placement in this location is advantageous because in the forward direction (normal sound transmission) the cymbal is pressed against the high impedance bony handle. In the reverse direction, due to the sound emanating from the inner ear, the inventive microphone ( 600 ) will typically have the lower impedance tympanic membrane to push against. Thus, this placement of the cymbal microphone lowers the potential for acoustic feedback.
Clearly, when a microphone is implanted in the ear canal, there will be concern of feedback. Feedback could be reduced acoustically by creating a greater distance between the eardrum and the microphone. Such an arrangement is shown in FIG. 12 . Here, the inventive microphone ( 600 ) is placed under the skin just above the helix of the pinna. A small indentation may be made in the bone (mastoid and/or squamous portion) to facilitate placement of the inventive microphone ( 600 ). The skin is then placed on the cymbal endcap and the wires arranged so that they are accessible by the electronics.
An extension of the configuration shown in FIG. 12 is to place a plurality of the inventive microphones arranged in a linear array. Such a concept is illustrated in FIG. 13. A linear array of such microphones gives the designer an opportunity for providing directivity, or beam forming. Such an arrangement is important for increasing the signal-to-noise ratio. FIG. 13 shows five microphones placed approximately 1 cm apart. However, the number of microphones may be reduced for sound processing simplicity. With just two microphones and associated delay and electronics, it is possible to increase the SNR by approximately 4-5 dB while a SNR of 8-10 dB is achievable with an array of five microphones, See, e.g., Soede, above and Killion, M. C. (1997). “SNR Loss: ‘I can hear what people say but I can't understand them’,” The Hearing Review 4(12):8-14.
Although others have suggested the use of microphone arrays to increase SNR in hearing aids, it has not been practical due to the large size of the array (5-10 cm) needed to obtain significant improvement.
The most popular notion has been to put a microphone array on the side, or in front, of eye glasses. This microphone is then attached to a behind the ear (BTE), or an in the ear (ITE), hearing aid. But, for cosmetic reasons, such a configuration has never been popular. Placement of a subcutaneous array microphone circumvents cosmetic issues because the array is substantially invisible.
A shortcoming of microphones that are somewhat exposed, such as those shown in FIGS. 12 and 13, is that they are susceptible to spurious noises. For example, if the wearer brushes their hand against the skin overlying the microphone then a loud sound could be produced by the output actuator of the hearing aid, or equivalent electrical signals of a cochlear implant. However, by using multiple microphones (as shown in FIG. 13) it is possible to differentially detect and filter such spurious signals.
These placements of the inventive microphones may be used for detecting audible sounds by the steps of placing an inventive flextensional microphone that is at least partially covered with a biocompatible coating and subcutaneously implanted as shown just above in the path of an audible sound. This flextensional microphone then produces an electric signal which is related to the audible sound. The electrical signal coming from the microphones is amplified, as discussed above, to produce an amplified signal which is then sent to an output transducer which is desirably coupled to some component of the human ear. Further, the process may include the step of planting at least one of the flextensional microphones subcutaneously in the human body. Desirably, they are placed in an array, perhaps linear, at the side of the human head, perhaps below a layer of skin. A further step in the process may be the detection of sound re-radiated by some component of the human ear and producing a signal which is both related to the re-radiated sound and is in such a form that it may be used in an amplifier to minimize the feedback potentially present in the inventive system.
This invention has been described and specific examples of the invention have been portrayed. Use of those specific examples is not intended to limit the invention in any way. Additionally, to the extent that there are variations in the invention which are within the spirit of the disclosure and yet are equivalent to the inventions found in the claims, it is our intent that those claims cover those variations as well. | This relates to flextensional microphones which are made up of a piezoelectric substrate having opposing surfaces, typically parallel surfaces when the substrate is crystalline or ceramic, and at least one sound receiving surface physically tied to the piezoelectric substrate. The microphones are at least partially isolated via a biocompatible material, e.g., by a covering or a coating. The inventive microphones may be subcutaneously implanted. The microphones may be used as components of surgically implanted hearing aid systems or as components of hearing devices known as cochlear implants. Preferably the microphones are used in arrays and when used as a component of a hearing assistance or replacement device, are used in conjunction with a source of feedback information, usually another microphone. The feedback information usually relates to sound re-emitted from physical portions of the ear, e.g., the eardrum, where those portions have been directly or indirectly driven by the actuator of the implanted hearing aid. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 61/772,798 to David Randolph Smith filed Mar. 5, 2013, and entitled “Through Tubing Perpendicular Boring Method and Apparatus,” which is hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present disclosure is directed to methods and apparatus to extract fluids from subterranean reservoirs, particularly hydrocarbons and water reservoirs. More specifically, this disclosure provides methods and apparatuses to increase the recovery to surface of subterranean fluids, such as oil, water, and gas, from subterranean reservoirs using novel drilling methods, fluids and apparatus taught by my invention disclosure herein.
BACKGROUND
[0003] Conventionally, the oil and gas industry deploys massive hydraulic fracture of subterranean reservoirs, commonly known as “fracking,” to enhance fluid production from wells when a subterranean reservoir may not have sufficient conductivity to flow fluid through the natural reservoir permeability and into a wellbore connected to the surface of the earth at flow rates that are timely and or commercial. This “fracking” method hydraulically cracks the subterranean reservoir using water pumped down wells from surface at high pressure with triplex pumps, injecting chemicals such as polyacrylamides, and other chemicals into the subterranean earth reservoir. The cracks that this “fracking” method creates are uncontrolled and propagate in a direction dictated by the in-situ stress of the reservoir and require vast amounts of water and chemicals to be injected into said reservoirs. Hence the current art of “fracking” cannot create or increase reservoir conductivity in all directions from a wellbore placed in a subterranean reservoir, but can only produce and propagate cracks from the wellbore in directions perpendicular to the least principal in-situ stress of the reservoir. This hydraulic fracture treatment often allows reservoir fluids to be recovered at commercial rates, but has significant environmental impact due to large water injection volumes, induced micro-seismic events and large surface location foot prints to accommodate hydraulic fracturing equipment and sand injection with hydraulic fracture fluids.
[0004] Another conventional method used in the oil and gas industry to enhance a reservoir's fluid conductivity is to drill a horizontal bore through the reservoir. This method of drilling a wellbore horizontal in a fluid productive subterranean reservoir is combined with the hydraulic fracture of said horizontal wellbore to further enhance a reservoir's flow of fluid into wellbores. However, once again using fracture or “fracking methods,” the direction of the crack and hence the direction of the enhanced reservoir permeability due to said hydraulic fracturing is limited to the predetermined direction driven by the in-situ rock stresses and earth's overburden and tectonic stresses. What is needed are methods and apparatuses to more homogenously stimulate and enhance the reservoir's fluid flow that are not limited to directions controlled by in-situ stress nor require large amounts of fracture waters and chemicals to be pumped underground in both vertical or horizontal wellbores.
BRIEF SUMMARY
[0005] When it is desirous to produce a subterranean fluid to surface without the use of hydraulic fracturing, so called “fracking” technology, an alternative method for stimulating subterranean reservoir fluid flow to the surface of the earth is disclosed below. In one embodiment, enhanced subterranean fluid extraction methods and apparatuses are disclosed that allow for the directionally controlled drilling of a plurality of boreholes from a principal or common wellbore. These methods and apparatuses may enhance the injection of fluids into subterranean reservoirs for the purposes of enhanced oil, water, brine, mineral, and gas recovery, both in primary fluid recovery phases of a well's life as well as the secondary recovery phase of a well's life, commonly known as Enhanced Oil Recovery (EOR). Further, the disclosed methods and apparatuses may enhance the disposal and sequestering of fluids in subterranean rocks.
[0006] In some embodiments, methods and apparatuses for drilling said horizontal bores off perpendicular to the common wellbore are disclosed, such as using novel directional apparatus, using novel drilling fluids like cryogenic fluids and supercritical fluids, and using hydraulic assist methods to propel a small drilling string into the reservoir through a tubing or drill pipe string disposed in the wellbore.
[0007] In one embodiment, a method provides for the placement of a plurality of bores substantially perpendicular to the common wellbore at a given depth or position in the said common wellbore.
[0008] In one embodiment, multiple common boreholes may be placed in a subterranean reservoir wherein at least one of the common boreholes has a plurality of additional boreholes substantially horizontal to this common borehole.
[0009] Prior art practitioners attempting to drill boreholes from a substantially perpendicular direction to the common wellbore taught away from using metal alloy tubes and shafts and instead taught the use of rubber hoses and other flexible non-metal substances. In some embodiments, the use of super elastic and pseudoelastic alloys for drilling strings is possible, as opposed to other alloys or elastomeric tubes. In some embodiments, cryogenic fluids are pumped through said drilling strings. Moreover in some embodiments, a method may include the translation of a drilling tube through down hole tubulars, and down hole directional guidance devices using hydraulic drag forces, reverse thrusting hydraulic jets, and use of a system of fluids being pumped to propel the drilling string away from the common wellbore out into the reservoir using hydraulic drag forces.
[0010] In some embodiments, a method of assisting the moving of a drilling string may include applying a dragging hydraulic force whereby the drilling tools and drilling string can be passed through curved hydraulic conduits of a through tubing guidance apparatus to direct the tight radius change of the new borehole constructed to be substantially perpendicular to the common borehole.
[0011] In some embodiments, a method of drilling the substantially perpendicular bores to the common borehole may include using a method of underbalanced drilling wherein the drilling fluid used has a fluid hydrostatic pressure less than the reservoir pressure thereby allowing the production of the drilling fluid and the produced reservoir fluid simultaneously to the surface during the construction of the substantially perpendicular bores.
[0012] In some embodiments, stimulating the substantially perpendicular borehole to the common wellbore may be performed by means of pumping stimulation fluids, such as acids, bases, explosives, cryogenic fluids, and/or by deploying shaped charges down the constructed substantially perpendicular boreholes and thereafter detonating the shaped charges, further enhancing the reservoir conductivity along the substantially perpendicular bores constructed off the common wellbore without using massive hydraulic fracture techniques. This greatly reduces the environmental concerns of pumping billions of gallons per year of water, tons of chemicals, and sand into reservoir using hydraulic fracture methods and then flowing back these waters and chemicals to surface of the wells where they have to be disposed.
[0013] To meet the needs of enhancing reservoir fluid conductivity and increasing the recovery of fluids from subterranean strata as discussed above and herein, and to address the disadvantages of conventional drilled bore completions that use hydraulic fracture methods, the present application discloses a simple low cost method, small surface foot print system, and down hole apparatus to construct from a common wellbore a plurality of directional boreholes substantially perpendicular to said common wellbore.
[0014] In one embodiment, the method includes drilling a common wellbore and thereafter deploying on or near the distal end of a drill pipe string or tubing string a directional guidance tool. The drill or tubing string is then oriented in the required direction at the required depth by deploying, for example, a wire line gyro-directional tool, and by rotating the drill or tubing string at the surface. The exit direction of the distal end guidance tool is selected and fixed per the wire line deployed gyro or other such directional sensing tool deployed on wire line or communicated to the surface via pressure pulses or other radio or electromagnetic means. Once this guidance tool is oriented in the selected direction, the wire line is pulled out of the drill or tubing string and a guidance tubing string is disposed down the drill or tubing string where said guidance string is landed on its distal end inside the distal guidance tool. A drilling string or continuous conduit is then deployed and lowered from the surface through the guidance string and assisted through the guidance tool with the pumping of fluid through the guidance string, thereby hydraulically dragging the drill string through the guidance string and guidance tool and out into the reservoir. The drilling string has a drilling fluid pumped from the surface that is used to carry drilling cuttings to surface. Further, the drilling fluids may have a hydrostatic fluid weight less than the reservoir pressure, thereby allowing the reservoir fluids and drilling cuttings and drilling fluid to flow to the surface. The drilling string can be equipped with any of the commonly known drilling assemblies having a suite of devices such as drill bits, drilling motors, stabilizers, hydraulic and electric pulsed data communication tools (such as Logging While Drilling (LWD) tools), fluid jets, jars and other well-known drilling devices. The drilling string comprises a super elastic alloy that further assists the drilling string in bending through the curved path of the down hole guidance tool and guidance string.
[0015] In yet another embodiment, the drilling string can be equipped with a core device on the distal end that cores out, through a guidance device, a plug of well casing and cement prior to drilling the substantially perpendicular borehole into the subterranean reservoir. This core is extracted to the surface and then the drilling string and assembly are deployed back out into the position where the core was extracted by means of keeping the distal guidance tool fixed during coring and construction of the substantially perpendicular borehole from the common borehole. This procedure can be repeated multiple times at the same well position or depth by simply rotating the distal guidance tool and cutting another core followed by another substantially perpendicular bore to the common bore. Once the desired number of substantially perpendicular bores are created off the common wellbore at a given depth or position along a horizontal common bore, the drill or tubing string having the distal directional guidance tool can be moved to a new position and the above procedure is repeated, thereby constructing a plurality of substantially perpendicular bores to the common borehole at many positions along the length of the common borehole. A further embodiment uses an explosive device deployed into the well and through the guidance device to create a passage through the previously-drilled common wellbore, casing, and cement.
[0016] In another embodiment, a plurality of common wellbores are constructed in a reservoir strata, for example a large shale strata such as the Eagle Ford Shale of South Texas, having hundreds of feet of thickness wherein a horizontal wellbore is placed along the top 20 feet of the strata and boreholes are drilled from the common horizontal borehole radially like spokes from a wagon wheel hub, and said spoke positions are radially drilled all along the length of the horizontal common bore so that the horizontal common bore has many hundreds or more boreholes drilled radially around it at many hundreds of points along the horizontal length, and this is repeated in further horizontal wellbores placed deeper and under the previously mentioned horizontal borehole.
[0017] According to one embodiment of the disclosure, a method of increasing the recovery of fluid from a subterranean strata by constructing boreholes from a previously drilled common borehole comprises attaching to a well tubular conduit a directional guidance device having at least one internal conduit passage; deploying said well tubular conduit and said directional guidance device from a surface into said previously-drilled common borehole, wherein said well tubular conduit has a proximal end at the surface of the earth, and wherein said attached directional guidance device is attached near a distal end of said well tubular conduit; constructing a drilling string comprising a pseudoelastic alloy; attaching a drilling device to a distal end of said drilling string; translating said drilling string and said drilling device from said surface into said well tubular conduit through said directional guidance device; pumping a drilling fluid through said drilling string and said drilling device; drilling new boreholes from inside said previously-drilled common borehole into subterranean substances with said drilling device and said drilling string; flowing subterranean fluids into said common well borehole from said new boreholes; and producing fluids to said surface.
[0018] In certain embodiments, said subterranean substance being drilled is a subterranean strata; said pseudoelastic alloy is NITINOL; said drilling string comprises at least one tube having a distal end attached to said drilling device and a proximal end attached on said surface to a fluid pumping system; drilling fluid being pumped is at least at surface a cryogenic fluid; said drilling fluid comprises a fluid that has a hydrostatic weight less than a reservoir pressure of said subterranean strata that is in said common wellbore; said drilling string is attached on a proximal end to a surface drilling or workover rig; said drilling string is attached on a proximal end to a coiled tubing injection device; said drilling string is passed through a blowout preventer device; said drilling string comprises a string of threaded and jointed pipe joints; said drilling string comprises a string of continuous tubing; said drilling string comprises a mixed string of jointed and continuous tubing; said drilling device comprises at least one jet nozzle; said translating comprises translation that is at least assisted by a reactionary force of fluid jets on said drilling device pulling said drilling string away from said common wellbore; said translation is at least assisted in moving said drilling string through said well tubular conduit and said directional guidance device by hydraulic fluid drag forces imposed on an outer diameter of said drilling string by pumping a fluid from said surface down a well tubular conduit while said drilling string and said drilling device are deployed inside said well tubular conduit; said produced fluid is a reservoir fluid; said drilling device comprises a drilling motor; said drilling device comprises a pulsed data transmission device; said directional guidance device is rotated at a given well depth or length by rotating said well tubular conduit from said surface and a new borehole is drilled in another direction from said common wellbore; said common wellbore has had casing previously disposed in it and the method further comprises drilling through said casing and out beyond said casing into said subterranean strata; said directional guidance device is translated to a new depth position after drilling said borehole in said common wellbore and the method further comprises repeating the step of constructing said boreholes from said common bore hole at said a new depth position in said common wellbore; said drilling string is pulled from a new well bores directional placed from said common wellbore; a core drilling device is first translated through said well tubular conduit and said directional guidance device, a core is cut of a subterranean substance of said common wellbore, said core and coring device are pulled from the common wellbore, and a drilling string with a drilling device is thereafter deployed through said well tubular conduit and directional guidance device and out through the void created by said core device where drilling of substances is commenced off said common wellbore; an explosive charge is first translated through said well tubular conduit and directional guidance device, said charge is detonated at or near said common wellbore to form a passage or cavity out into said common wellbore, the detonated explosive charge is pulled from said well tubular conduit and said directional guidance device, said drilling string with drilling device is thereafter deployed through said well tubular conduit and said directional guidance device and out through a void in said common wellbore created by the explosive charge detonation where drilling said subterranean substances is commenced off said common wellbore through said void created by said explosive charge; said common wellbore is a substantially horizontal wellbore; said common wellbore is substantially vertical; said new boreholes from said common wellbore are substantially perpendicular to said common wellbore; said drilling string comprises a solid member comprising a super elastic alloy; said drilling string comprises a pseudoelastic alloy; and/or the step of drilling boreholes comprises drilling a plurality of common horizontal or vertical wellbores from said surface into said subterranean strata.
[0019] In another embodiment, a directional guidance apparatus comprises a body comprising at least one proximal entry fluid passage starting at a proximal end, said fluid passage extending through the said body and forming a curvature radius that terminates at an exit port located on a longitudinal side of said body.
[0020] In certain embodiments, the apparatus further comprises pipe threads on said proximal end; at least one additional fluid port hydraulically connected to the fluid passage starting at the said proximal end of said entry fluid passage, said at least one additional fluid port terminating in a position different than said longitudinal exit port; and/or at least one drag tube to be disposed inside said directional guidance apparatus fluid passage.
[0021] In one embodiment, a method of enhancing the injection of fluid from a surface into at least one subterranean strata by constructing boreholes from a previously drilled common borehole intersecting said subterranean strata, comprises attaching to a well tubular conduit a directional guidance device having at least one internal conduit passage; deploying said well tubular conduit and said directional guidance device from said surface into said previously drilled common borehole, wherein said tubular conduit has a proximal end at said surface of the earth and said attached directional guidance device is attached near a distal end of said tubular conduit; constructing a drilling string comprising a pseudoelastic alloy; attaching a drilling device to a distal end of said drilling string; translating said drilling string from said surface into said well tubular conduit through said directional guidance device; drilling new boreholes into subterranean substances with said drilling device and drilling string; injecting surface fluids into said common wellbore and out into said constructed boreholes; and injecting said surface fluids into said subterranean strata.
[0022] In certain embodiments, fluids from said at least one subterranean strata are produced to said surface from at least one additional wellbore not drilled from said common wellbore; said injected fluids comprise at least one gas; said injected fluids comprise supercritical fluids; said injected fluids comprise a liquid; said injected fluids comprise at least one cryogenic fluid; said injected fluids are injected into said common wellbore and into said reservoir through said new boreholes off of said common wellbore for a period of time and then fluids are returned from said new boreholes and said common wellbore to said surface; at least one hydraulic jarring device is attached to said drilling string; and/or at least a portion of said drilling string comprises a super elastic form of NITINOL.
[0023] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 illustrates three phases of well construction using the deployment of the down hole direction guidance apparatus according to one embodiment of the disclosure.
[0025] FIG. 2 shows a drawing of a directional guidance device attached to a well tubular member that extends to the surface of the earth according to one embodiment of the disclosure.
DETAILED DESCRIPTION
[0026] As used herein, “a” or “an” means one or more. Unless otherwise indicated, the singular contains the plural and the plural contains the singular. Where the disclosure refers to “perforations” it should be understood to mean “one or more perforations”.
[0027] As used herein, “surface” may refer to locations at or above the surface of the earth.
[0028] As used herein, “super elastic alloy” may refer to alloys that have an elastic (reversible) response to an applied stress, caused by a phase transformation between the austenitic and martensitic phases of a crystal. It is exhibited in shape-memory alloys. Super elasticity sometimes referred to as pseudoelasticity is from the reversible motion of domain boundaries during the phase transformation of an alloy, rather than just bond stretching or the introduction of defects in the crystal lattice (thus it is not true superelasticity but rather pseudoelasticity). Even if the domain boundaries do become pinned, they may be reversed through heating. Thus, a pseudoelastic material may return to its previous shape (hence, shape memory) after the removal of even relatively high applied strains. These alloys include but are not limited to a family of alloys known as Nitinol (an alloy comprising nickel and titanium and/or other elements).
[0029] Pseudoelasticity, sometimes referred to as superelasticity, is an elastic (reversible) response to an applied stress, caused by a phase transformation between the austenitic and martensitic phases of a crystal. It is exhibited in shape-memory alloys. Pseudoelasticity is from the reversible motion of domain boundaries during the phase transformation, rather than just bond stretching or the introduction of defects in the crystal lattice (thus it is not true superelasticity but rather pseudoelasticity).
[0030] Superelastic alloys belong to the larger family of shape-memory alloys. When mechanically loaded, a superelastic alloy deforms reversibly to very high strains—up to 10%—by the creation of a stress-induced phase. When the load is removed, the new phase becomes unstable and the material regains its original shape. Unlike shape-memory alloys, no change in temperature is needed for the alloy to recover its initial shape.
[0031] The term drilling herein is intended to encompass the art of cutting holes in substances, and includes but is not limited to the use of high pressure fluid jets, abrasive cutting jets, cutting bits, milling bits, which can include rotational methods, as well as hammering methods.
[0032] A brief description of the method used to drill boreholes through a previously constructed common borehole largely perpendicular to said previously constructed common wellbore is disclosed herein. It should be noted that this method may be applied to all manners of recovery of subterranean substances, such as, but not limited to, oil, gas, bitumen, kerogen, tar, water, CO 2 , helium, methane, bromine, iodine, gold, silver, platinum, lithium, rare earths, etc.
[0033] Once the common borehole is constructed to the subterranean depth required, the well casing may or may not be grouted into the common wellbore. For casing is grouted into place, an additional step of this method includes first cutting or coring the casing. Once the common wellbore is drilled to the required depth, the drilling rig can be substituted with a work over rig, which may be a smaller, more economical surface rig. The work over rig can be used to deploy into the well a tubing or drill pipe string.
[0034] At a high level, the embodiment in FIG. 1 shows first phase 110 . In this embodiment, direction guidance device 1 forms a passage for the deployment of stick pipe 10 , or other devices such as cable, tubes, and solid rods 11 through said guidance device 1 as shown in second phase 120 . Third phase 130 depicts a guidance tube 3 disposed through the guidance apparatus device 1 body from the surface down a well tubing 2 shown on the first phase 110 . FIG. 1 further shows a drilling string 4 inserted through guidance tube 3 in the third phase 130 . As shown in phase 130 of this embodiment, the drilling string 4 is depicted as a tube having a drilling fluid pumped from the surface down inside the drilling string 4 and out a drilling device 5 at the distal end of drilling string 4 shown in the third phase 130 , where the depicted device 5 is a jetting device having reverse jets imposing a reactionary force on the drilling string 4 that pulls the drilling string 4 away from the directional guidance apparatus 1 and away from common wellbore 12 . The third phase 130 further shows a fluid 6 being pumped down the annular space between the drilling string 4 outer diameter and the guidance tube 3 internal diameter, where said fluid pumping action imposes a drag force on the drilling string 4 which assists in the translation of the drilling string through the guidance tube 3 and the curved passage of the directional guidance apparatus and out into the reservoir 7 . Other types of drilling devices 5 are also contemplated. Drilling strings presented herein may be of types commonly known in the art, such as, for example, threaded and jointed pipe joints, electric wire line, or continuous tubing.
[0035] According to one embodiment of the present disclosure, the directional guidance device comprises a body with at least one proximal entry passage starting at a proximal end, said passage extending through the directional guidance device body said passage forms a curvature radius that terminates said passage through the directional guidance device body at an exit port located on a longitudinal side of said body representing an exit port substantially perpendicular to the proximal entry passage. In one embodiment, the directional guidance device has at least one additional port hydraulically connected to the main passage through the body wherein said additional port terminates in a position different than the longitudinal exit port. For example, said additional port in said passage through the directional guidance device terminates on the distal end of the directional guidance device.
[0036] Turning to FIG. 1 and FIG. 2 , a sequential depiction of one embodiment is depicted wherein string 2 is shown in a tubular string of casing 14 deployed from the surface of the earth by way of, for example, a work over rig and through a blowout preventer on the top of the common wellbore at the surface. In this embodiment, said string 2 is lowered into the common wellbore 12 with a tubular guidance device 1 on or near the distal end of string 2 . String 2 is lowered to the required position depth in said common well bore 12 where a subterranean reservoir 7 is located. At this point the well tubular member, tubing string 2 , is held stationary at the surface of the earth with slips set on the floor of the work over rig. This stationary holding of string 2 at surface holds tubular guidance device 11 at the distal end of string 2 stationary at the required position depth near the reservoir 7 in said common well bore 12 . In one embodiment, the common wellbore 12 is an open hole completion wherein no casing is deployed, and as such the tubular guidance device would be built to have an external diameter close to or indeed the same as the diameter of the borehole 12 . In another embodiment, as shown in first phase 110 , said common wellbore 12 is completed with a casing string 14 . Common wellbore 12 , in one embodiment, is grouted into place with cement 15 across the reservoir 7 .
[0037] According to one embodiment, a second phase 120 of FIG. 1 depicts, by way of the surface workover rig draw works, the lowering of drill string 10 having a drill rod 11 attached to the distal end of said string 10 and a drilling device 20 on the distal end of said drill rod 11 . The drilling rod 11 in one embodiment comprises an alloy known as Nitinol. Drill string 10 can be of various sizes, such as 1.5″ OD and is lowered through tubing string 2 previously disposed in common wellbore 12 , through directional guidance device 1 , where drilling device 20 encounters common wellbore 12 and casing 14 . Drill string 10 is then rotated from the surface using a workover rig rotary device, common to all oil and gas rotary drilling rigs well known in the industry. Fluid 30 from the surface is pumped down well tubular 2 where said fluid 30 flows out of the directional guidance device 1 and flows up the common wellbore 12 casing 14 to the surface. The pumping of fluid 30 assists to drag the drilling rod 11 through the passage in the directional guidance device and out into the common wellbore. In an alternative embodiment, drilling rod 11 device can be replaced with a drilling tube 4 or electric wireline. In the embodiment shown in phase 120 of FIG. 1 , drag fluid 30 is pumped from surface down well tubing 2 and into the proximal end of the directional guidance device 1 connected to the distal end of well tubing 2 where fluid 30 passes out of the directional guidance device distal end ports. Drag fluid 30 is used to propel drilling device 20 and drilling rod 11 through the passage of directional guidance device 1 into the casing 14 where said drilling device bores through said casing and out into the reservoir 7 . Once the core or hole is cut in the casing 14 and cement grout 15 , drill pipe 10 and drilling device 20 are extracted back to the surface from well tubing 2 .
[0038] According to one embodiment, during third phase 130 , a drag tube 3 is lowered through well tubing 2 into the directional guidance device 1 from the surface using the workover rig draw works. This drag tube 3 can be attached to a drill string 10 as shown in phase 120 or other well tubular member well known to those familiar with the art of well construction. Examples of other drill strings include coiled tubing and jointed stick pipe. Once this drag tube 3 is lowered into place through the passage in the directional guidance device 1 , it is held at the surface with slips, and a further jet drilling tube 4 having a drilling jetting bit assembly 5 on the distal end of said jet drilling tube 4 is lowered into said drag tube 3 from the surface, through the directional guidance device 1 , and out into the cavity or bore created in phase 120 process by the previously discussed drilling device 20 of the second phase 120 .
[0039] In one embodiment, the process of placing and passing the jet drilling tube 4 and jet drilling assembly 5 is assisted by pumping a drag fluid 6 from surface down drag tube 3 wherein said drag fluid assists in pulling said jet drilling tube 4 through said drag tube 3 which was previously disposed in the directional guidance device 1 . A surface pump then is attached to the jet drilling tube 4 and fluid 21 is pumped down the jet drilling tube 4 and out the drilling jet bit assembly 5 . Fluid 21 is returned to the common wellbore 12 and into casing 14 along with drilling substances and the combined fluid mix of fluid 6 and fluid 21 are flowed back to the surface. In one embodiment fluid 21 is cryogenic nitrogen. In another embodiment fluid 6 is a gas. In one embodiment, the jet drilling assembly 5 comprises reverse thrusting jet nozzles to assist in propelling the jet drilling tube 4 away from the common wellbore 12 and out into the subterranean strata 7 to form a new substantially perpendicular borehole 25 connected to the common borehole 12 . In this embodiment, the method of surface lowering devices for, pushing, and translating the jet drilling tube 4 away from the common wellbore 12 can be accomplished with a surface coiled tubing injector head well known to those in the field of coiled tubing deployment in the oil and gas industry or a drilling rigs draw works. In one embodiment, jet drilling fluid 21 is nitrogen, in whole or in part, such that the high pressure nitrogen coming out of the jet nozzle 5 assists in lifting fluids from common wellbore 12 , cuts the formation 7 , and propels the jet drilling tube 4 with the reactionary force exerted on said jet drilling string 4 from the reactionary force of the nitrogen exiting the jets of jet drilling assembly 5 .
[0040] Once the jet drilling bit of the third phase 130 extends a sufficient distance from common wellbore 12 , jet drilling tube is extracted from the well to the surface and the drilling rig rotates the tubular string 2 to a new radial position at the same depth in common wellbore 12 . The process of coring and creating a new borehole 25 at the new position in the common wellbore is repeated as depicted in phase 120 . The step of coring can be eliminated in some cases where the casing and cement grout are cut with high pressure jetting fluids coming out of the jet bit drilling assembly 5 . Or the core step can be replaced by an explosive perforating step wherein a wire line device having an explosive charge attached to a wireline truck is disposed down the drag tube 3 from the surface, and moved through the directional guidance device 1 and drag tube 3 by pumping a drag fluid 6 down the drag tube 3 whilst lowering the wireline. Once the explosive charge is fired, and the casing and cement grout is penetrated by the explosive charge, the wireline is retracted to the surface and a jet drilling string 4 is disposed down the drag tube, as discussed above in phase 130 , to start drilling the formation 7 and creating a borehole 25 . In embodiments involving open hole completions, the core or perforating step can be eliminated and the extraction of drag tube 3 is not required between the construction of each new radially drilled borehole 25 . According to the present disclosure, different jet drilling fluids 21 are contemplated, including, for example, acids, nitrogen, gases, cryogenic liquids, bentonite gel fluids, guar gel liquid systems, polyacrylamide gel liquid systems, oil lubricants, salt waters, attipulgite clay salt water systems, and the like.
[0041] In one embodiment, borehole 25 is enlarged by jetting with high pressure fluid 21 and further enhancing the reservoir 7 fluid conductivity to the substantially perpendicular borehole 25 to the common wellbore 12 . The enlargement by jetting of the borehole 25 can be done by pumping hydrochloric acid as fluid 6 down the jet drilling tube 4 while boring out away from the common wellbore 12 or jetting with acid while returning the jet drilling tube 4 to the common wellbore 12 . In one embodiment, cold fluids, such as cryogenic nitrogen, are pumped down the jetting tube 4 to assist in cracking and jetting the formation 7 and casing 14 . Furthermore, it is understood that the construction for at least a portion of the jet drilling tube 4 and drilling rod 11 may use alloys of pseudoelastic and or super elastic materials. These materials include the family of alloys known as NiTiNol.
[0042] FIG. 2 shows a drawing of a directional guidance device 1 attached to the distal end a well tubular member 2 that proceeds to the surface of the earth according to one embodiment of the disclosure. FIG. 2 further shows a guidance drag tube 3 disposed inside the well tubular member 2 from the surface and terminating on the distal longitudinal side end near the end of the curved path of the directional guidance apparatus 1 . Drilling string 4 is loosely disposed inside guidance drag tube 3 and has attached, at its distal end, jet drilling assembly 5 . Drilling fluid 21 is pumped down jet drilling string 4 through jet drilling assembly 5 and cuts a borehole 25 in reservoir 7 . FIG. 2 further depicts reservoir 7 producing reservoir fluid 8 from a previously bored hole while jet drilling assembly 5 is drilling another hole 25 . Drilling fluid 21 and drag fluid 6 are mixed outside directional guidance device 1 in common wellbore 12 and produced up the common borehole 12 with reservoir fluid 8 to the surface while the drag fluid 6 is being pumped down the guidance drag tube 3 such that the drag forces of drag fluid 6 react on drilling tube 4 , thereby assisting to translate the drilling tube 4 down through drag tube 3 and out into the reservoir 7 .
[0043] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, and composition of matter, means, methods and steps described in the specification. As one of ordinary skilled in the art will readily appreciate from the disclosure of the present invention, processes, devices, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, devices, manufacture, compositions of matter, means, methods, or steps. | Methods for extracting more fluids from oil and gas wells reservoirs than is currently possible using the current art of drilling and hydraulic fracturing wells may be accomplished with methods and apparatuses to directionally control the construction of a plurality of substantially perpendicular boreholes from a common wellbore at a plurality of positions along said common wellbore. One method may include drilling a plurality of the substantially perpendicular boreholes off a previously constructed common wellbore using underbalanced methods and producing the reservoir fluids while drilling the substantially perpendicular boreholes. In some methods, injection of fluids from surface into subterranean reservoirs may be used for the purpose of sequestering fluids or recovering fluids to the surface. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Entry of International Application No. PCT/FR2006/002584, filed Nov. 24, 2006, claiming priority to French Patent Application No. 05/11962, filed Nov. 25, 2005, both of which are incorporated herein by reference.
BACKGROUND AND SUMMARY
[0002] The invention relates to a secure method for collecting and analysing samples.
[0003] In many fields, and particularly in the legal field, it is necessary to be able to guarantee the origin of a sample, such as a clue taken from the scene of a crime, the conditions under which it was collected and its integrity during subsequent handling of this sample. This is because, in the legal field, a sample collected at the scene of a crime may serve as evidence, possibly leading to the conviction or acquittal of a person on trial. It is therefore of the utmost importance to be able to certify with certainty the collection conditions and the integrity of the sample used as evidence in order to avoid any judicial error. In other words, it is necessary to be able to certify with certainty that the sample that underwent analysis was indeed present at the scene of the crime and that it has not been modified, swapped or degraded during handling. At present, the guarantee concerning the collection conditions and the origin of the samples and also the conditions under which it was analysed rests on the word of the police and the scientists in charge of the analysis.
[0004] In other fields, particularly the medical field, the guarantee of the collection conditions and origin of the samples analysed may prove to be of the utmost importance. This is because, for reasons of viability of the sample and of relevance of the analysis, it is important to know the time that has elapsed between the collection and the actual analysis of the sample. This time must be as short as possible and must not exceed the period of viability of the sample. At present, this guarantee rests on the human word and on the indications given by the person in charge of collection. The date of collection may therefore be questioned. The human word can always be questioned regardless of whether the persons giving their word do so in good faith or not. During a trial, the guarantee concerning the collection and analysis conditions of a sample may be the subject of debates and questions which may lead to the conviction or acquittal of a person on trial without there being any certainty that justice has indeed been done in the case. It will therefore be understood that it is necessary to provide this guarantee in a certain and reliable manner and not simply via the human word.
[0005] The invention aims to provide a solution to this problem by proposing a secure method for collecting and analysing samples, in which all the information relating to the collection and analysis are recorded on a tamper-proof support in which the sample is collected.
DETAILED DESCRIPTION
[0006] The invention relates to a secure method for collecting and analysing samples using a device for storing the samples which comprises an information storage means and at least one collection receptacle which can be associated therewith, the device being equipped with means for verifying and guaranteeing the integrity of the receptacle before and after use thereof when said receptacle is associated with the device, the receptacle comprising information storage means which previously comprise identification information relating to said receptacle, said method being characterised in that it comprises the following steps:
a. identifying at least one person charged with the collection, and storing this identification in the information storage means of the device and in the storage means of the receptacle; b. writing the place, date and time of collection to the storage means of the device and to the storage means of the receptacle; c. identifying the collection receptacle and storing this identification in the storage means of the device; d. verifying the integrity of the collection receptacle before use thereof; e. opening the receptacle, if the verification indicates that the receptacle has not previously been used, and collecting the sample; f. closing the receptacle and applying means for guaranteeing the integrity of the receptacle after use thereof; g. transmitting the data stored in the storage means to remote storage means; h. subsequently analysing the sample.
Thus, the information relating to the collection conditions and to the preservation of the sample are written on a support which is irreversibly linked to the sample. In this way, a novel guarantee is provided concerning the origin and authenticity of the sample.
[0015] Furthermore, according to one embodiment, the step of identifying at least one person in charge of the collection and/or analysis is supplemented by an identification of at least one witness and by the storage of this identification in the storage means of the device and in the storage means of the receptacle. Thus, the steps necessarily carried out by physical persons take place under the surveillance of at least one clearly identified witness, which reduces the possibilities for fraudulent manipulation of the samples. In order to guarantee that the place, date and time of collection are exact, the information relating to the place of collection is supplied to the storage means by a positioning device, such as a GPS, the data of which cannot be falsified, and the information relating to the date and time of collection is supplied to the storage means by a clock, of the atomic clock type which also cannot be falsified. The device for storing the samples and the collection receptacle which can be associated therewith conform for example to the biological analysis system described in the document FR-2 787 042 and in the document FR-2 865 190 filed in the name of the applicant.
[0016] Such an analysis system makes it possible to avoid any sample identification error and to obtain an automatic traceability of the samples. Furthermore, the receptacle makes it possible to see whether or not integrity has been conferred thereon. In such a system, the information storage means of the receptacle are formed by an electronic label, the content of which can be read remotely. Furthermore, it is provided that the storage device is equipped with means for verifying and guaranteeing the integrity of the receptacle before and after use thereof when said receptacle is associated with the device. In order to obtain information about the integrity of the receptacle, the latter may conform to the tube described in the document FR-2 865 190 as indicated above.
[0017] According to one embodiment and in order to guarantee and certify the analysis conditions of the samples, the analysis step h. may comprise the following steps:
i. identifying at least one person charged with the analysis, and storing this identification in the storage means; j. verifying the conformity of the identity of the receptacle to be analysed based on information contained in the remote storage means with the identity of the receptacle handled by the person charged with the analysis based on information contained in the storage means of said receptacle; k. verifying the integrity of the collection receptacle after it has been closed during the collection process; l. actually analysing the sample.
Thus, the same guarantees are provided during the analysis as during the collection.
[0022] In order to preserve all the information in the storage means of the device and in the storage means of the receptacle, it is possible to furthermore provide one or more steps of recording comments relating to the collection in the storage means of the device and in the storage means of the receptacle during the collection and/or analysis of the sample. Thus, it is also possible to certify the location and the time at which the comments relating to the sample were made. In order to facilitate visual identification of the sample and thus to avoid electronic reading of the receptacle when it is desired to identify it, the method may furthermore comprise a step of printing a visual identification means which is associated with the receptacle after identification of the latter by the collection device.
[0023] In the case where the analysis is not carried out directly after collection, the method comprises a storage step between the collection steps and the analysis steps. A writing of storage data to the storage means of the device and to the storage means of the receptacle, such as the storage date, the storage location and the sample removal date, is carried out during the storage step. It is possible to provide steps of encrypting the information recorded in the storage means of the device and in the storage means of the receptacle in order to ensure that the recorded information can be read only by persons having sufficient authority to do so. The device is able to receive a plurality of collection receptacles, the identification steps being repeated for each receptacle. Thus, all the clues collected at the scene of a crime can be associated with the same device.
[0024] The use of the device and of the receptacle associated therewith takes place as follows: the collection receptacle is associated with the device before step a. then is removed from the device during step e. then is reassociated with the device during step f., the means for guaranteeing the integrity of the receptacle after use thereof being applied by the device. A data input and reading element for writing and reading the information on the storage means of the device and on the storage means of the receptacle, said element being handled by the person identified in said storage means. Such an element is for example a portable computer or a pocket electronic assistant, such as a PDA organiser (palm digital assistant), making it possible to input information and to transmit this information. Such input and reading elements are commercially available. The positioning device and the clock may be integrated in the input and reading element.
[0025] The certain identification of the user of such an input and reading element may be carried out by means of a biometric identification system. The user is then identified for example by means of his digital fingerprint. Such an identification system is also available commercially and can easily be associated with the input and reading element. The storage means of the device and of the receptacle may also store photographs, for example of the scene of the crime. It is then possible to use a digital apparatus which sends the photos taken to these storage means.
[0026] The method according to the invention therefore makes it possible to combine all the information relating to a collection of samples in a storage means which is irreversibly linked to the support containing these samples, which provides a guarantee concerning the authenticity of this information. Such a method can be used in all fields in which the verification of the authenticity of the conditions under which samples are collected, stored and analysed may prove to be of the utmost importance. | The invention concerns a secure method for collecting and analyzing samples using a device for storing samples comprising data storage means and at least one sampling receptacle capable of being associated therewith, the device being provided with means for verifying and ensuring the integrity of the receptacle before and after its use when said receptacle is associated with the device, the receptacle including data storage means already including data for identifying said receptacle, the method providing for recording of all data concerning sampling and analysis in the storage means. | 1 |
The present application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/643,093, filed Jan. 11, 2005, which application is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to implantable leads for providing electrical stimulation and, more particularly, relates to leads having multiple electrode contacts and methods of making such leads.
BACKGROUND
Many types of implantable leads are currently used to treat a variety of maladies. Two common treatment applications use leads having multiple electrode contacts. Cochlear stimulator systems use a multiple electrode contact lead inserted into one of the cochlear chambers to stimulate the cochlear nerve. Another application where a multiple electrode contact lead is used is the treatment of chronic pain through stimulation of the spinal cord.
Spinal cord stimulation systems generally have two implantable components: an implantable pulse generator (IPG) and at least one lead connected to one output of the IPG. Generally, however, the IPG is a multi-channel device capable of delivering electrical current through the electrode contacts of the lead. The term “lead” used herein will refer to an elongate device having any conductor or conductors, covered with an insulated sheath and having at least one electrode contact attached to the elongate device, usually at the distal portion of the elongate device. The lead can have an inner stylet lumen running through most of the length of the lead and which lumen has an opening at the proximal end of the lead. A stylet may be placed into this stylet lumen during steering and implantation of the lead. The inserted stylet in the lumen can help stiffen the lead so that the stylet/lead combination may be more easily inserted through tissue.
There are two types of leads that may be used with the IPG. The first type is a paddle lead, which has a multiplicity of electrode contacts spread out over a flat, paddle-like surface that is attached to one end of the lead. A paddle lead advantageously permits the electrode contacts to be spaced apart to provide wide coverage over a stimulation area. A disadvantage presented with a paddle lead is that it usually requires a laminectomy or laminotomy, which are highly invasive surgical procedures necessary to implant the large, non-isodiametric paddle.
A second type of lead that is commonly used is a percutaneous lead, which has multiple electrode contacts positioned along the distal portion of an elongate lead. U.S. Pat. No. 6,205,361 issued to Baudino et al. describes the making of a multi-contact electrode array for a lead. The distal end of the lead may be about the same thickness or diameter as the remainder of the lead. The percutaneous lead is dimensionally configured for tunneling to a target stimulation site. No invasive surgical procedure such as a laminotomy is required; the percutaneous lead may be placed through an epidural type needle reducing surgical trauma.
The method of making a multi-contact percutaneous lead can be involved. In general, it is desirable to make the lead efficiently, with the fewest number of process steps, maximize the manufacturing yield, and hence reduce the cost of goods of building the leads. There is thus a continual need to improve the design of a percutaneous lead in order to improve its performance and to improve the method of manufacturing the lead.
BRIEF SUMMARY
A method of making a lead is provided. In one embodiment of the invention the method comprises: providing a plurality of conductive contacts located at the distal end of the stimulation lead; connecting a conductor wire to each of the conductive contacts; placing spacers between pairs of adjacent conductive contacts; placing monofilament within void spaces not occupied by a conductor wire, wherein the monofilament is the same material as the spacers; placing a heat shrink tubing around the spacers, conductive contacts and monofilament; and heating the spacers and monofilament just below the melting temperature to cause thermal fusion between the monofilament and spacer.
The conductive contacts may be connector contacts located at the proximal portion of the lead, which contacts are used to connect to the IPG, or the conductive contacts may be electrode contacts located somewhere on the lead (e.g., usually at the distal end of the lead).
In another embodiment of the method of making the lead, the method comprises: providing a plurality of conductive contacts located at the proximal end of the stimulation lead; connecting a conductor wire to each of the conductive contacts; placing spacers between pairs of adjacent conductive contacts; placing monofilament within void spaces not occupied by a conductor wire, wherein the monofilament is a different material than the spacers; placing a heat shrink tubing around the spacers, conductive contacts, and monofilament; and heating the spacers and monofilament to a temperature to cause thermal flow or melting of at least one of the spacers or monofilament.
Hence, while the monofilament and spacers may be the same material with the same melting temperatures, that is an optional part of the invention. The monofilament and spacers may actually be different materials, e.g., a type of thermoplastic polyurethane monofilament and another type thermoplastic polyurethane spacer, with different hardness and melting points in order to yield a particular stiffness.
In an embodiment of the invention, a lead assembly is provided comprising: a plurality of electrically conductive contacts; spacers placed between each adjacent contacts; a conductor wire connected to each conductive contact; and monofilament placed into void spaces not occupied by conductor wire, wherein the monofilament is made from the same insulative material as the spacer; and wherein the spacer and monofilament are thermally fused from heat applied to the lead assembly, which heat is just below the melting temperature of the spacer and the monofilament material.
In yet another embodiment, a lead assembly is provided comprising: a plurality of electrically conductive contacts; spacers placed between each adjacent contacts; a conductor wire connected to each conductive contact; and monofilament placed into void spaces not occupied by conductor wire, wherein the monofilament is made from a different insulative material as the spacer; and wherein the spacer and monofilament are heated to a temperature to cause either the spacer or monofilament material to thermally reflow or melt.
The monofilament and spacer may be the same thermoplastic material to have the same melting point and to thereby allow thermal fusion upon heating at a temperature just below the melting temperature of the material or the monofilament and spacer may have different melting points.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other aspects of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
FIG. 1 shows a generalized spinal cord stimulation system with a percutaneous lead connected to an implantable pulse generator (“IPG”);
FIG. 2 shows an illustration of the percutaneous lead implanted into the epidural space of a human spinal cord;
FIG. 3A shows a side view of the distal end of a percutaneous lead.
FIG. 3B shows a side view of the proximal (connector) end of the percutaneous lead shown in FIG. 3A ;
FIG. 4 shows a view of the proximal end of the lead assembly showing the connector contacts and conductor wires that connect to each connector contact;
FIG. 5A shows a cross-sectional view of the percutaneous lead shown in FIG. 3A at line 5 A- 5 A;
FIG. 5B shows a cross-sectional view of the percutaneous lead shown in FIG. 5A along line 5 B- 5 B;
FIG. 5C shows a perspective view of the lead body, having a central stylet lumen and surrounding smaller lumens for containing conductor wires;
FIG. 6A shows a close-up, partial, longitudinal view of the lead assembly at the distal portion of the lead; and
FIG. 6B depicts how polyurethane monofilament or a thermoplastic material is used to fill the voids and is incorporated into the lead by applying heat.
Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention. The scope of the invention should be determined with reference to the claims.
FIG. 1 shows a generalized stimulation system that may be used in spinal cord stimulation (SCS), as well as other stimulation applications. Such a system typically comprises an implantable pulse generator (“IPG”) 12 , an optional lead extension 14 , a lead 16 and an electrode array 18 . The electrode array 18 includes a plurality of electrode contacts 17 . In a percutaneous lead, the electrode contacts 17 can be arranged in an in-line electrode array 18 at the distal end of the lead 16 . Other electrode array configurations can also be used. The IPG 12 generates stimulation current pulses that are applied to selected electrode contacts 17 within the electrode array 18 .
The proximal end of the lead extension 14 can be removably connected to the IPG 12 and a distal end of the lead extension 14 can be removably connected to a proximal end of the lead 16 . The electrode array 18 is formed on a distal end of the lead 16 . The in-series combination of the lead extension 14 and lead 16 conduct the stimulation current from the IPG 12 to electrode contacts 17 of the electrode array 18 . It is noted that the lead extension 14 need not always be used with the neural stimulation system 10 . Instead, the lead extension 14 may be used when the physical distance between the IPG 12 and the electrode array 18 requires its use, or for the purpose of a temporary trial procedure.
The IPG 12 contains electrical circuitry, powered by an internal primary (one-time-use-only) or a rechargeable battery, which through the use of electrical circuitry can output current pulses to each stimulation channel. Communication with the IPG can be accomplished using an external programmer (not shown), typically through a radio-frequency (RF) link.
FIG. 2 shows a transverse, mid-sagittal view of a spinal cord and a generalized, implantable, spinal cord stimulation system. The stimulation system shown is being used as a spinal cord stimulator (SCS) system. In such an application, the lead 16 and, more particularly, the electrode array 18 are implanted in the epidural space 20 of a patient in close proximity to the spinal cord 19 . Because of the lack of space near the lead exit point 15 where the electrode lead 16 exits the spinal column, the IPG 12 may be implanted in the abdomen or above the buttocks. Use of lead extension 14 facilitates locating the IPG 12 away from the lead exit point 15 .
FIG. 3A shows, in accordance with the invention, a distal portion of a percutaneous stimulating lead 16 . The stimulating lead 16 is used to stimulate neural tissue by delivering electrical stimulus pulses through at least one of the electrode contacts 17 . The electrode contacts 17 can be separated by electrode contact spacers (or an insulative material) 61 that insulate the electrode contacts 17 from each other. A radiopaque marker 30 located at the distal tip of the lead 16 may be optionally included. Alternatively, the tip of the lead may be the same material as the remainder of the lead insulation. The IPG 12 may be configured to permit connection to the two stimulating leads, each having eight electrode contacts 17 . A pair of stimulating leads 16 may be connected to an IPG 12 and an electrical circuit may be created between one electrode contact on the first lead and another electrode contact located on the second lead. The IPG 12 , for example, may have sixteen independently programmable outputs that allow programming of pulse amplitude, pulse width and frequency of the pulse width. The electrode contacts 17 are to be made of a bio-compatible, electrically conductive electrode material such as platinum/iridium alloy, platinum, titanium or the like.
As an example, the stimulating lead 16 may have a diameter of between about 0.03 to 0.07 inches for spinal cord stimulation applications. An insertion cannula (not shown), e.g., a 14 gauge insertion needle may be used, while a 0.05 inch diameter stimulating lead is inserted within the cannula to help implant the stimulating lead 16 . The stimulating lead 16 may come in a variety of lengths, e.g., 30, 50, 70 and 90 cm. A practitioner can extend the length of any of the available lead lengths by opting to use an extension lead 14 (shown in FIG. 1 ). The proximal male end of the extension lead 14 should be configured to be insertable into the lead connector of the IPG and the distal female end of the extension lead should be configured to accept the proximal connector end of the stimulating lead 16 .
FIG. 3B shows, in accordance with the invention, a depiction of the proximal end of the lead 16 . This proximal lead end, including the eight, electrically conductive, connector contacts 40 , and a contact tip element 41 , collectively will be called herein as the proximal lead connector end 42 of the stimulating lead 16 . Connector contact spacers 45 are placed between the connector contacts 40 . The spacers 45 may be made from an implantable grade polyurethane such as Pellethane® 55D thermoplastic material. The contacts 40 may be made from a non-corrosive, electrically conductive material, e.g., platinum/iridium alloy or platinum. Contact tip 41 , however, is not electrically connected to any conductor and contact tip 41 may merely serve as a hard surface for a mechanical contact securing device, such as a set screw, which may be used to secure the lead connector end 42 with the connector block of the IPG 12 . Contact tip 41 is optional and does not need to be included as part of the lead. Instead, the contact tip of the lead may be of similar or the same insulation material as the remainder of the lead 16 or lead body 110 ( FIG. 5C ).
Preferably the lead 16 is substantially isodiametric, meaning that the diameter along the lead's entire length is equal or nearly equal. However, the lead 16 does not need to be isodiametric. For example, the connector contacts 40 at the proximal end may be larger (oversized) or smaller in diameter compared to the remainder of the lead 16 or lead body 110 (shown in FIG. 5C ). Likewise, the electrode contacts 17 may be larger (oversized) or smaller in diameter compared to the remainder of the lead 16 or lead body 110 (shown in FIG. 5C ).
FIG. 4 shows a proximal lead assembly with each of the connector contacts 40 welded to a respective one of conductors 122 . Each of the eight connector contacts 40 , as shown, are connected to a conductor 122 which, in turn, are connected to a respective electrode contact 17 at the distal end of the stimulating lead 16 . The insulating material between the connector contacts 40 and around the conductors 122 is not shown in FIG. 4 for purposes of better illustrating the connection between each conductor and its respective connector contact. The connection may be a weld. Cylindrical element 46 is optional and is not connected to any conductor. Cylindrical element 46 may be used as a contact element for a mechanical securing device such as a set screw in order to secure the lead 16 to the IPG 12 . Alternatively, or in addition, the cylindrical element 46 may function as a radiopaque element, provided that the material used for element 46 is radiopaque.
FIG. 5A shows a cross-sectional view of the lead of FIG. 3A along line 5 A- 5 A.
FIG. 5B shows a partial, cross-sectional view of the lead along the line 5 B- 5 B.
FIG. 5C shows a perspective view of an exemplary lead body 110 of the lead 16 , excluding conductor wires. The lead body is that portion of the lead insulation 112 that is between the distal electrode contact array 18 and the array of connectors contacts 40 ( FIG. 4 ) at the proximal lead connector end 42 . The lead body 110 may be extruded as a one-piece component. Note the central stylet lumen 114 and the surrounding eight conductor lumens 116 .
FIGS. 5A and 5B show an exemplary embodiment of an insulation section 112 of the lead body 110 having eight lumens 116 containing the conductor (wires) 122 , having individual strands 120 . For example 15 or 16 individual conductor strands 120 may be braided or bundled into a single conductor 122 . Also shown is a central lumen 114 that may be used to accept an insertion stylet (not shown) within the lumen to facilitate lead implantation. The opening of the lumen occurs at the proximal end of the lead 16 . The lead body 110 may be a biocompatible, insulating lead material. Preferably the lead body 110 is made from a polyurethane. In particular the material may be Pellethane® thermoplastic material, e.g. 55D, 65D, or other durometer hardness. As previously indicated for FIG. 5C , the lead body 110 shown in FIG. 5B may be extruded as one piece.
FIG. 6A shows a partial view of a longitudinal, cross-section at the distal end of the lead, in accordance with an embodiment of the invention. FIG. 6A shows a ring-like electrode contact 17 (which may be platinum, for example), multi-stranded conductor 122 and electrode contact spacer 61 (or an insulative material). The spacer 61 , which is ring-like in configuration, may be made of polyurethane insulative material, e.g., Pellethane®. Monofilament 60 , also may be made of thermoplastic Pellethane® material or other insulation material, e.g., polyester. During manufacture, the monofilament 60 may be inserted into the void spaces that are not filled by the conductor 50 . A heat shrink tube 65 is also shown placed around the electrode contacts 17 and conductor 122 assembly. The heat shrink tube 65 may be PTFE (e.g., Teflon® material) or a polyester heat shrink material. The heat shrink tube can be used during manufacturing and is not part of the stimulation lead.
FIG. 6B shows a two-frame, time-elapsed illustration of a partial view of the distal end of the lead as in FIG. 6A showing the conductor 122 connected (e.g., welded) to the electrode contact 17 . The first frame (i) of FIG. 6B shows the sequence in which the monofilament 60 fills a large part of the void space 70 . The part of the lead assembly shown is then placed into a heat, for example, at 190 degrees Celsius for a period of 30 seconds. The heat that may be used, e.g., for polyurethane material (such as Pellethane®), may range from about 140 to 250 degrees Celsius for a period of about between 15 to 120 seconds. However, importantly, the heat applied to the spacer and monofilament material, should be just below the melting temperature of the material. At this just-below-melting temperature, the spacer and monofilament will reflow and thermally fuse together as shown in the second frame (ii). The spacer 61 and the monofilament 60 may be exactly the same material with the same melting temperature in order to facilitate thermal fusion. For example, the material may be the same implantable grade polyurethane such as Pellethane 55D or 75D.
Alternatively, however, the monofilament may be of a different material than the spacer to alter the mechanical characteristic of the final lead assembly. The monofilament and spacer may have different melting points or very close melting points. The monofilament and spacers may be the same type of material but with different formulations, e.g., to provide different hardness. For example, the monofilament may be a 55D (durometer hardness) material and the spacer may be a 75D material. The predetermined temperature chosen to heat both the monofilament and spacers should cause at least one of the materials used to thermally reflow or, alternatively to melt. In some cases, the temperature may be chosen that one material melts while the other material thermally reflows.
While FIGS. 6A and 6B show the distal end of the lead, the same process of using a monofilament to fill up void spaces may be used at the proximal end of the lead assembly. At the proximal end of the lead assembly, the conductive contacts are not electrode contacts but, are instead, electrically conductive connector contacts 40 that must be in electrical connection with complementary contacts in the IPG connector. The connector contact spacers 45 at the proximal end of the lead (shown in FIG. 3B ) are placed between adjacent connector contacts 40 . In one embodiment of the invention, the connector contact spacers 45 may be oversized—that is, the spacers may have an initial diameter that is larger than the final lead diameter. The proximal connector end of the lead assembly 42 may then be heated to a temperature (just below melting point of the spacer and monofilament) for a duration of time previously described in order to produce thermal fusion of the connector contact spacer 45 and monofilament 60 to create a continuous reflow of material between the spaces not occupied by the connector contacts 40 and conductor wires 122 .
Alternatively, the monofilament 60 and spacer 45 may be different materials with different melting points or about the same melting points.
Hence, the method of placing monofilament into void spaces not occupied by the conductor 122 , may be used solely at the distal end of a lead, solely at the proximal end of a lead, or may be employed concurrently at both ends of a lead. If only one end of a lead employs monofilament, the other end of the lead may employ another method to finish the build, e.g., overmolding using a mold or injecting material such as epoxy, e.g., Hysol® into the void spaces between the contacts and conductor wires.
Example
The following steps illustrates one example embodiment of a method for making the lead, in accordance with the invention. Embodiments of the method can include one or more of the following steps (although not necessarily in the order presented). (1) A braided or bundled, insulated, multi-filament conductor, e.g., having 2-200 filaments, can be ablated of insulation at one end to expose the conductor. (2) The exposed end of the conductor can be welded to an electrode contact (located on the distal end lead assembly). (3) Oversized, distal lead spacers may be placed between the electrode contacts. (4) The multi-lumen tube (lead body) may be pre-cut with ablated section located at the distal and proximal ends. (5) Each end of the conductor cable can be inserted through the corresponding conductor lumens in the lead body. (6) The oversized spacers can be placed between each ring-like electrode contact at the distal end of the lead assembly; the spacers 61 may be “oversized”, meaning that they may have a diameter greater than the lead body 110 and in addition, the diameter of the electrode contacts 17 may be oversized compared to the diameter of the lead body 110 . (7) The distal end of each conductor cable can be welded to the ring-shaped electrode contact. (8) Polyurethane monofilament may be placed inside the void space as shown in FIG. 6A , and inside any empty conductor lumens 116 . (9) A heat shrink tube or wrap, preferably, made from PTFE (Teflon) or polyester, can be placed over the distal end of the lead assembly and over the electrode array; this distal end can be placed into a high temperature block, e.g., between about 140-250 degrees Celsius for a period of about 30 to 120 seconds. (10) The distal assembly can be removed from the heat and the shrink tube or wrap can be removed. (10) Optionally, the distal tip of the lead can be formed using an RF welder.
Post processing of the lead is not always required. For example, grinding of the distal or proximal ends of the leads is not necessary with this method of manufacturing, although optionally, a centerless grinding process may be used, if desired.
The method of making the distal and proximal part of the lead, in accordance with the present invention, eliminates most, if not all tooling, including eliminating the use of molds.
The method of making a lead and the resulting multi-contact lead, in accordance with the invention, provides advantages over conventional leads and methods of making a lead. A prior method of making the distal portion of the lead uses epoxy to fill the voids between the spacer 61 and the contacts 17 . This has certain disadvantages. For instance, use of an epoxy requires a curing step, e.g., of up to eight hours, adding to the total time required to build a lead. With use of epoxy, there may also be some variation in stiffness of the final lead assembly post-cure because the epoxy is generally a different material than the insulative body or spacers and because curing may occur unevenly. The use of like materials, e.g., polyurethane lead body, polyurethane spacers and polyurethane monofilament can yield a better bond between these parts.
Although the lead and method of making the lead are described in the context of a spinal cord stimulation lead, it will be understood by those skilled in the art that the same lead, albeit with appropriate dimensions for a particular application, and the method of making the lead may be used to make a multi-contact lead suitable for use in other applications, such as deep brain stimulation, cardiac stimulation and peripheral nerve stimulation.
While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. | A lead assembly and a method of making a lead are provided. The method of making a multi-contact lead assembly comprises providing conductive contacts located at an end of a lead body, disposing conductive wires in conductor lumens formed in the lead body, and connecting the conductive wires to the conductive contacts. The method further includes placing spacers between pairs of conductive contacts and inserting monofilament in at least a portion of at least one of the conductor lumens not occupied by the conductor wires. The method also includes reflowing at least one of the spacers or monofilament into at least one portion of at least one of the conductor lumens by heating the spacers and monofilament to a temperature to cause thermal flow or melting of at least one of the spacers or monofilament. | 8 |
This invention is concerned with an anode assembly for use in apparatus employed for electroforming replicas on record matrixes.
BACKGROUND OF THE INVENTION
In the manufacture of molded records, such as audio records and the more recently developed video records, a plastic composition is molded between a pair of metal plates referred to as stampers which have the information desired to be molded into the record defined in the surface thereof. The stampers are the end product of a multi-step replication process. The initial step in the replication process is to record the information desired to be molded into the record on a magnetic tape. The recorded magnetic tape is then used to control a cutting tool which cuts an information track in a flat, disc-shaped member referred to as a recording substrate. The resulting recording substrate has the surface relief pattern desired to be molded into the final record and could conceivably be played back on suitable apparatus to reproduce the recorded information. However, it is not practical to use the recorded substrate for playback because of, among other things, the extremely high cost involved in cutting the recording into the recording substrate. The recording substrate is, however, used in the replication procedure which ultimately results in the production of the stampers.
The next step in the replication process is to electroform a metal replica on the recorded surface of the recording substrate. The recording substrate is mounted and rotated in the cathode position of an electroforming apparatus while a supply of the metal to be electroformed on the substrate, typically nickel, is provided at the anode of the electroplating apparatus. The electroforming of the replica on the recording substrate is conducted by electroforming methods well known in the art. After a sufficient amount of metal has been electrodeposited on the recording substrate, the resulting electroformed part is then separated from the recording substrate. The resulting electroformed part is referred to in the art as a master, and is a negative replica of the starting recording substrate.
The master is in turn duplicated a number of times until the resulting replicas start to show significant loss of fidelity to the master on which they are electroformed. The electroformed replicas formed on the master are referred to in the art as molds or mothers. The molds or mothers are positive copies of the original recorded substrate.
Each of the molds or mothers is then, in turn, also replicated several times in a similar electroforming process to produce a third series of electroformed metal parts referred to as stampers. The stampers are negative replicas of the original recording substrate. As noted above, it is the stampers which are ultimately used as the molding plates to press molded records. The record molded on the stampers should be an accurate replica of the original recorded substrate, and on playback should result in a high fidelity reproduction of the information initially recorded on the recording substrate.
Many problems are, however, encountered in the electroforming process. One of the major problems encountered is that often the metal is electrodeposited on the part to be duplicated such as the recording substrate, the master or the mold (hereinafter referred to collectively as matrixes), in a non-uniformly thick layer so that the electroformed part has varying thicknesses across its diameter. The non-uniform deposition causes problems in the further replication of the master and molds, and is especially troublesome with regard to the stampers. The nonuniformity in thickness can cause defects in the molded records and also substantially reduce the useful life of the stampers.
A further problem encountered in the electroforming process is that often foreign particles, or even excessively large particles of the metal desired to be plated onto the replicas, are attracted to the surface of the matrix being duplicated. If these particles are not removed from the surface before any substantial amount of plating occurs, the particles can cause surface and internal defects in the resulting replicated part.
What would be highly advantageous would be an apparatus which would improve the uniformity of the plating and also which would prevent or substantially reduce defects caused by the presence of foreign materials or large pieces of metal on the surface of the matrixes during electroforming.
BRIEF SUMMARY OF THE INVENTION
It has been found in accordance with the present invention that the uniformity and overall quality of electroformed replicas formed on record matrixes can be substantially improved using an anode assembly which is comprised in combination of a bifurcated holder for supplying metal for the electroforming, an electrolyte distribution manifold positioned between the bifurcated parts of the holder and a pair of anode shields positioned in front of each of the holders for focusing the electroforming forces toward the cathode of the electroforming apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic pictorial illustration shown in three dimensions of an electroforming apparatus having the anode means of this invention.
FIG. 2 is an alternate type of anode shield for use in the anode assembly of this invention.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 there is illustrated in somewhat schematic form an electroforming apparatus 10. The electroforming apparatus 10 includes a tank 11 for holding electrolyte 12 and a cathode 13 having a rotatable cathode head 14 mounted at one end of the tank and the anode means 15 of this invention mounted at the opposite end of the tank 11.
The anode assembly 15 has a bifurcated anode supply means comprised of a pair of anode baskets 16, 17. The anode baskets 16, 17 can be made of various materials, such as certain plastic materials which are resistant to the chemicals and electrical conditions encountered in the electroforming process. The baskets 16, 17 are, however, preferably made of titanium in that titanium is not adversely affected by the chemical and electrical conditions encountered in the electroforming process. The baskets 16, 17, as illustrated in FIG. 1, are made in an open mesh-like configuration, but it should be appreciated that other configurations can be used which allow electrolyte 12 to flow through the baskets 16, 17 during electroforming.
The baskets 16, 17 are used to hold a supply of the metal desired to be electrodeposited on the matrix. The metal generally is supplied in the form of small pieces or buttons 18. The metal pieces or buttons 18 are inserted into the baskets 16, 17 as required during the electroforming process. The baskets 16, 17 are hung from the anode electrical supply 19 of the electroforming apparatus 10. As illustrated in FIG. 1, the pair of anode baskets 16, 17 are suspended into the electrolyte 12 in the tank 11 and are slightly separated from each other by a predetermined distance.
Positioned between the anode baskets 16, 17 is an electrolyte discharge manifold 20. The manifold 20 consists of an upright conduit 21 which has an opening 22 at its lower end to admit filtered electrolyte 12 from a filter and circulating pump (not shown). The upper end 23 of the upright conduit 21 is sealed and capped. Located along the length of the upright conduit 21 there are a plurality of outlet nozzles 24. The nozzles 24 are in communication with the interior of the upright conduit 21 so that the electrolyte 12 will flow from the interior of the pipe through the nozzles 24 as indicated by the flow arrows 25. The nozzles 24 can be of fixed internal size, but preferably should be individually adjustable for modulating the rate of flow from each of the nozzles 24 as required in order to obtain optimum results with the electroforming apparatus 10.
Positioned in front of each of the anode baskets 16, 17 is an anode plating shield 26, 27. The plating shields 26, 27 are made of material which will not be adversely affected by the chemical or electrical conditions encountered during the electroforming process. The anode shields 26, 27 are placed in position adjacent to the surface of the anode baskets 16, 17 facing toward the cathode head 14. The anode masks 26, 27 have chordal open sections 28, 29, which expose a predetermined portion of the anode baskets 16, 17. The chordal sections 28, 29 are somewhat less than semicircular, but when taken together with the opening occupied by the manifold 20, the combined diameter of the openings is the same, slightly more, or slightly less than the diameter of the replica which is to be electroformed on the matrix (not shown) held by the cathode head 14. The anode shields 28, 29 are interchangeable with other similarly shaped anode shields which have either larger or smaller chordal sections as required in order to obtain uniform plating of the replica, as will be explained below.
The anode shields 28, 29 as illustrated in FIG. 1 have smooth edges 31 about the chordal sections 28, 29 as this is the optimum configuration when it is desired to have as uniform a plating as possible over the surface of the matrix. However, it is also possible to vary the edge configuration of the chordal sections to impart special effects to the deposited replicas. An especially advantageous alternate embodiment is illustrated in FIG. 2 wherein the anode shields 32, 33 have saw tooth edges 34 about the chordal sections 32, 33. The use of the saw tooth edge 34 results in a feathering of the plating at the edge of the replica which is highly advantageous for certain matrixing applications and also assists in the separation of the replicas from the matrixes.
In use, the initial step is to mount a matrix (not visible in FIG. 1) which has had the grooved surface thereof passivated. The cathode head 14 is immersed into the electrolyte 12, and rotated as indicated by the arrow 30. The electrolyte 12 is circulated through the tank 11. The electrolyte 12 is removed through an outlet (not shown) and then subjected to filtering and other treatments to remove impurities from the electrolyte, especially particulate materials. The treated electrolyte is then introduced into the tank 11 through the inlet manifold 20. The outlet nozzles 24 and the pressure of the electrolyte flowing through the nozzles 24 are controlled so the electrolyte will flow through the bath and flush the face of the cathode head 14 as it rotates in the electrolyte 12. The force of the flow of electrolyte from the manifold 20 over the surface of the matrix removes most of the foreign particles and the large bits of nickel particles from the surface of the matrix before thy are plated into the replica causing defects. The nozzles 24 of manifold 20, if adjustable, are balanced to correct any minor adverse unbalanced conditions encountered in the electroforming process, and thereby improve the quality and levels of the electroformed part formed on the matrix. The particles which are flushed from the surface of the matrix by the flow of electrolyte are eventually circulated to the drain and then removed from the system in the filtering sytems.
The anode baskets 16, 17 are recharged as required with a supply of the metal desired to be deposited on the matrix. The metal is generally supplied in the form of small buttons or particles 18.
The anode shields 26, 27 are installed on the surface of the anode baskets 16, 17. The exact diameter of the opening defined by the chordal sections can be varied by using different size anode masks 26, 27 having either larger or smaller chordal openings 28, 29 as noted above. The selection of the proper size anode shield is dependent on a number of interrelated factors, such as the total distance between cathode head 14 and the anode baskets 16, 17, the amount of current employed during the electroplating process, and the composition of the electrolyte used in the plating process. These and other interrelated factors determine the lines of electrical force created during the electroforming operation in the plating bath. It is desirable to have the lines of force focused onto the surface of the replica being electroformed. It is one of the primary functions of the anode shield to provide the focusing in the apparatus of the present invention. The anode shields 26, 27, in combination with control of the flow from the manifold 20, are used to control the rates of deposition and to help to deposit the metal in a uniformly thick layer of metal on the matrix.
It has been found that using the anode means of the present invention the uniformity of the deposition can be more easily and accurately controlled, and that defects caused by the presence of foreign particles and the like are substantially reduced. | An anode assembly is provided for use in the electroforming of record matrixes. The anode assembly is comprised of a pair of spaced apart anode baskets for holding a supply of the metal to be electrodeposited, an electrolyte distribution manifold positioned between the baskets and a pair of anode shields positioned in front of each of the anode baskets for focusing the electroforming forces from the anode. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to the following commonly owned copending applications, incorporated herein by reference:
D. A. Elko et al., Ser. No. 09/677,341 filed concurrently herewith, entitled “METHOD AND APPARATUS FOR IMPLEMENTING A SHARED MESSAGE QUEUE USING A LIST STRUCTURE”; P. Kettley et al., Ser. No. 09/605,589, filed Jun. 28, 2000, entitled “METHOD AND APPARATUS FOR OPERATING A COMPUTER SYSTEM TO ENABLE A RESTART”; P. Kettley et al., Ser. No. 60/220,685, filed Jul. 25, 2000, entitled “METHOD AND APPARATUS FOR IMPROVING MESSAGE AVAILABILITY IN A SUBSYSTEM WHICH SUPPORTS SHARED MESSAGE QUEUES”; D. J. Dahlen et al., Ser. No. 60/219,889, filed Jul. 21, 2000, entitled “IMPLEMENTING MQI INDEXED QUEUE SUPPORT USING COUPLING FACILITY LIST STRUCTURES”.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method and apparatus for managing a list structure and, more particularly, to extensions to the architecture of a list processor that render it especially suitable for processing shared message queues.
2. Description of the Related Art
IBM's MQSeries® is a set of middleware products that allow user applications to intercommunicate using messages, without having to know the complexities of the underlying hardware and software platform. Applications communicate using the MQSeries application programming interface (API), issuing such calls as MQPUT to put a message onto a queue and MQGET to get a message from a queue. MQSeries is described in such publications as MQSeries Planning Guide , IBM GC33-1349-07 (January 1999), incorporated herein by reference.
The IBM S/390® Parallel Sysplex® configuration is a cluster of interconnected processing nodes with attachments to shared storage devices, network controllers, and core cluster technology components, consisting of coupling facilities, coupling support facilities, and external time references (ETRs). A coupling facility (CF) enables high-performance read/write sharing of data by applications running on each node of the cluster through global locking and cache coherency management mechanisms. It also provides cluster-wide queuing mechanisms for workload distribution and message passing between nodes.
The coupling facility is described in the following patents and publications, incorporated herein by reference:
“In a Multiprocessing System Having a Coupling Facility, Communicating Messages Between the Processors and the Coupling Facility in Either a Synchronous Operation or an Asynchronous Operation”, by D. A. Elko et al., Ser. No. 08/420,893, Filed Apr. 11, 1995, now U.S. Pat. No. 5,561,809; “Sysplex Shared Data Coherency Method And Means”, by D. A. Elko et al., Ser. No. 07/860,805, Filed Mar. 30, 1992, now U.S. Pat. No. 5,537,574; “Method And Apparatus For Distributed Locking Of Shared Data, Employing A Central Coupling Facility”, by D. A. Elko et al., Ser. No. 07/860,808, Filed Mar. 30, 1992, now U.S. Pat. No. 5,339,427; “Command Quiesce Function”, by D. A. Elko et al., Ser. No. 07/860,330, Filed Mar. 30, 1992, now U.S. Pat. No. 5,339,405; “Software Cache Management Of A Shared Electronic Store In A Sysplex”, by D. A. Elko et al., Ser. No. 07/860,807, Filed Mar. 30, 1992, now U.S. Pat. No. 5,457,793; “Multiple Processor System Having Software For Selecting Shared Cache Entries Of An Associated Castout Class For Transfer To A DASD With One I/O Operation”, by D. A. Elko et al, Ser. No. 07/860,806, Filed Mar. 30, 1992, now U.S. Pat. No. 5,493,668; “Command Execution System For Using First And Second Commands To Reserve And Store Second Command Related Status Information In Memory Portion Respectively”, by D. A. Elko et al., Ser. No. 07/860,378, Filed Mar. 30, 1992, now U.S. Pat. No. 5,392,397; “Integrity Of Data Objects Used To Maintain State Information For Shared Data At A Local Complex”, by D. A. Elko et al, Ser. No. 07/860,800, Filed Mar. 30, 1992, now U.S. Pat. No. 5,331,673; “Management Of Data Objects Used To Maintain State Information For Shared Data At A Local Complex”, by J. A. Frey et al, Ser. No. 07/860,797, Filed Mar. 30, 1992, now U.S. Pat. No. 5,388,266; “Clearing Data Objects Used To Maintain State Information For Shared Data At A Local Complex When At Least One Message Path To The Local Complex Cannot Be Recovered”, by J. A. Frey et al., Ser. No. 07/860,647, Filed Mar. 30, 1992, now U.S. Pat. No. 5,394,542; “Coupling Facility For Receiving Commands From Plurality Of Hosts For Activating Selected Connection Paths To I/O Devices And Maintaining Status Thereof”, by D. A. Elko. et al., Ser. No. 08/324,447, Filed Oct. 18, 1994, now U.S. Pat. No. 5,463,736; “Data Processing System And Method For Providing Notification In A Central Processor Of State Changes For Shared Data Structure On External Storage”, by J. A. Frey et al., Ser. No. 07/860,809, Filed Mar. 30, 1992, now U.S. Pat. No. 5,390,328; “Method And Apparatus For Performing Conditional Operations On Externally Shared Data”, by J. A. Frey et al., Ser. No. 08/383,532, Filed Feb. 1, 1995, now U.S. Pat. No. 5,742,830; “Apparatus And Method For List Management In A Coupled Data Processing System”, by J. A. Frey et al., Ser. No. 07/860,633, Filed Mar. 30, 1992, now U.S. Pat. No. 5,410,695; “Interdicting I/O And Messaging Operations In A Multi-System Complex”, by D. A. Elko et al., Ser. No. 07/860,489, Filed Mar. 30, 1992, now U.S. Pat. No. 5,394,554; “Method And Apparatus For Coupling Data Processing Systems”, by D. A. Elko et al., Ser. No. 07/860,803, Filed Mar. 30, 1992, now U.S. Pat. No. 5,317,739; “Authorization Method For Conditional Command Execution”, by D. A. Elko et al., Ser. No. 08/408,446, Filed Mar. 22, 1995, now U.S. Pat. No. 5,450,590; “Dynamically As signing a Dump Space in a Shared Data Facility to Receive Dumping Information to be Captured”, by D. A. Elko et al., Ser. No. 08/471,895, Filed Jun. 7, 1995, now U.S. Pat. No. 5,664,155; “Method And System For Capturing and Controlling Access To Information In A Coupling Facility”, by D. E. Neuhard et al., Ser. No. 08/146,647, filed Nov. 1, 1993, now U.S. Pat. No. 5,630,050; “Method and System for Determining and Overriding Information Unavailability Time at a Coupling Facility”, by D. A. Neuhard et al., Serial. No. 08/779,196, filed Jan. 6, 1997, now U.S. Pat. No. 5,875,484; “Requesting a Dump of Information Stored within a Coupling Facility, in Which the Dump Includes Serviceability Information from an Operating System That Lost Communication with the Coupling Facility”, by D. A. Neuhard et al., Serial. No. 08/779,195, filed Jan. 6, 1997, now U.S. Pat. No. 5,860,115; “Method and Apparatus for Expansion, Contraction, and Reapportionment of Structured External Storage Structures”, by D. J. Dahlen et al., Ser. No. 08/304,458, filed Sep. 12, 1994, now U.S. Pat. No. 5,581,737; “Method of Managing Resources in One or More Coupling Facilities Coupled to One or More Operating Systems in One or More Central Programming Complexes Using a Policy”, by R. A. Allen et al., Ser. No. 08/607,053, filed Feb. 26, 1996, now U.S. Pat. No. 5,634,072; “Method and System for Managing Data and Users of Data in a Data Processing System”, by R. A. Allen, Ser. No. 08/146,727, filed Nov. 1, 1993, now U.S. Pat. No. 5,465,359; “Method and System for Reconfiguring a Storage Structure Within a Structure Processing Facility”, by R. A. Allen et al., Ser. No. 08/544,941, filed Oct. 18, 1995, now U.S. Pat. No. 5,515,499; “Method for Coordinating Executing Programs in a Data Processing System”, by R. A. Allen et al., Ser. No. 08/439,269, filed May 9, 1995, now U.S. Pat. No. 5,604,863; “Coherence Controls for Store-Multiple Shared Data Coordinated by Cache Directory Entries in a Shared Electronic Storage”, by K. S. Carpenter et al., Ser. No. 08/148,707, filed Nov. 8, 1993, now U.S. Pat. No. 5,544,345; “Method and System for Log Management in a Coupled Data Processing System”, by R. V. Geiner et al., Ser. No. 08/632,683, filed Apr. 15, 1996, now U.S. Pat. No. 5,737,600; and J. M. Nick et al., “S/390 cluster technology: Parallel Sysplex”, IBM Systems Journal , vol. 36, no. 2, 1997, pages 172-201.
It would be desirable to be able to use the list-processing capabilities of the coupling facility to implement a message queue that is shared by queue managers residing on different systems across a sysplex. To be suitable for this purpose, the CF list architecture should allow MQSeries to efficiently implement the following message-queuing semantics:
1. A message must be uniquely identified. 2. A message put cannot be visible to other units of work (UOWs) until it is committed.
When a message is written by a UOW, it must not be visible to other units of work anywhere in the queue-sharing group (QSG) until the message is committed. The uncommitted message however is available to the unit of work that wrote it.
3. Committed messages must be maintained in proper sequence.
Committed messages eligible to be read must be in priority sequence, from highest priority to lowest priority. If there are multiple messages with the same priority, then the set of messages must be maintained in order of arrival sequence within designated priority.
4. Messages read must be unavailable to others UOWs in the QSG.
When a committed message is read by a unit of work, then no other unit of work anywhere in the queue-sharing group can read the same message. If the message that is read is committed, it must be deleted from the CF list structure so that it is never visible again to another unit of work.
5. Messages read that are backed out must be reinserted into their proper committed positions with respect to both priority and time of arrival.
If the message that was read is backed out, it must again become visible to other units of work executing in the queue-sharing group. When the message is backed out, it must be reinserted into the committed portion of a list with respect to both its priority and its time of arrival (when the message was originally put).
6. Committing and aborting messages for a UOW must be efficient.
SUMMARY OF THE INVENTION
The present invention contemplates extensions to the CF list architecture that allow MQSeries to efficiently exploit the CF list model and provide for shared queues in a Parallel Sysplex emvironment. The present invention is not limited to use in a message queueing environment, however, but may be used in other applications as well.
One aspect of the present invention contemplates a program-specified unique list entry identifier (ID) in place of the list entry ID generated by the system. In a parallel implementation of MQSeries, the CF list architecture should allow user-generated list entry identifiers to be used as a direct entry-locating mechanism in order to insure that the identifier for each list entry is unique across CF list structures and consistent between MQSeries queue managers.
MQSeries could accomplish this in the existing architecture by using list entry names. However, entry names and entry keys are mutually exclusive means of specifying list entries, and MQSeries also requires the use of entry keys for identifying list entries. MQSeries requires a function that is equivalent to that provided today by entry IDs as a direct means of addressing a list entry in a list structure. Currently, however, entry IDs are generated internally by the coupling facility.
In accordance with one aspect of the invention, a new list structure control—a program list entry identifier indicator, or PLEIDI—is defined to allow the user to specify whether user-defined entry IDs are used when the list is allocated. This new option is provided as an attribute of list structure allocation.
Corresponding modifications may be made to the operating system components that exploit the CF list architecture. Thus, in the case of the OS/390 component known as Sysplex Services for Data Sharing (XES), an optional input may be added to the XES Connection Service that indicates whether the user wishes to provide unique list entry ID values or the system should generate entry ID values for each list entry created for the structure.
A connect request is rejected if the connector's requested attribute does not match the attribute in effect for the current allocated instance of the structure. In a preferred embodiment, list entry ID type is consistent for a whole list structure. Either all list entries in the structure are referenced by entry IDs generated by the system, or all list entries are referenced by entry IDs provided by the user.
Another aspect of the present invention contemplates a new delete list (DL) command. MQSeries requires an efficient means to delete entries from a given list without knowledge of the specific list entry IDs of the entries to be deleted. In accordance with this aspect of the invention, a new delete list command is added that sequentially processes list entries in the order in which they exist on the specified list. The starting point for the list entry selection is specified by the head or tail of the list, entry ID, entry name, entry key, secondary key or list cursor. The new delete list command allows specific criteria to be specified that provides a means to target only particular entries to be processed for deletion. This command scans entries on a particular list and does not involve a scan of the entire structure.
The present invention also contemplates a new move list entries (MLES) command. A new command of this type is required by MQSeries to optimize the performance of two of their critical processes: committing MQPUT list entries and backing out of MQGET list entries. This requires updating each affected list entry, either by changing the list entry key while keeping the list entry on the same physical list in the CF list structure or by moving the list entry from one list back to its original list while the list entry key for the list entry remains unchanged. In accordance with this aspect of the invention, a new move list entries command has been added that provides a performance-optimized means to process an input list of entries. Each list entry in the input list may be moved to a new position on a list in the CF list structure by updating the list entry key, or each list entry may be moved from one list to another list in the coupling facility list structure by specifying a new target list number. The new move list entries command allows both the list number and the list entry key for a list entry to be updated.
The new move list entries (MLES) command is a multiple-list entry command, which takes as input a list of specified entries to be processed. The move list entries command takes a list of entries identified by list entry ID or name. For each entry in the input list a target list number, a target list entry key and a target secondary key may be provided.
In a preferred embodiment, a new input parameter—granular version number comparison (GVNC)—is provided on the move list entries (MLES) command to allow the user to optionally perform granular version number comparison. The move list entries command also allows granular version number replacement given the granular version number comparison was successful. A specified set of compare and replace criteria may be specified for each entry in the input entry list.
In a preferred embodiment, the input operand granular version number comparison (GVNC) is also added to the delete list entries (DLES) command to allow the user to optionally perform granular version number comparisons with a specified compare value criterion specified for each entry in the input entry list. Currently, the DLES command supports nongranular comparison functions, that is, comparison is performed between a single specified compare value and each of the entries in the input entry list. By adding the granular version number comparison to both DLES and MLES, the commands are kept consistent. However, the DLES command is preferably not changed to support version number replacement because version number replacement on a delete request is not supported by the architecture; updating an entry that will be deleted does not make sense.
In a preferred embodiment, another new operand—halt on miscompare (HOM)—is added to the move list entries (MLES) and delete list entries (DLES) commands to allow the user to specify whether execution should halt when a miscompare is encountered or continue to the next entry as is done currently. Miscompares may occur on the list entry version number, list entry key, list entry secondary key or list number. Currently, these commands skip an entry if a miscompare is encountered and continue processing with the next entry in the input list. This leads to the unfortunate circumstance that when any comparisons are requested, it is not possible for the user to determine which entries in the input entry list were deleted and which were skipped due to a miscompare because, upon completion the request only tells you how many entries were deleted.
Another aspect of the present invention contemplates key comparison enhancements to the CF list architecture. MQSeries uses entry keys and entry version numbers to identify the list entries by MQSeries queue manager and priority. To accomplish this, key comparison enhancements have been added for both single- and multiple-entry commands. The key compare functions that have been added are as follows:
1. Location by keyed position has been enhanced to include operator types of range, less than or equal, and greater than or equal, for entry location of the first list entry to process on the read list (RL) and delete list (DL) commands. 2. For multiple-entry commands (i.e., commands for deleting, moving, reading and/or writing multiple list entries), the operands key request type (KRT), list entry key (LEK) and maximum list entry key (MLEK) (together with similar operands for the secondary keys described below) provide key comparison function operators of range, as well as key comparison function operators for less than or equal, and greater than or equal. 3. For single-list entry commands (i.e., commands for deleting, moving, reading and/or writing a single list entry), the operand key request type (KRT) (together with similar operands for the secondary keys described below) provides key comparison function operators of equal, less than or equal, and greater than or equal.
Yet another aspect of the present invention contemplates the following list monitoring enhancements:
1. List monitoring for a key range or a “subset of sublists”.
Currently, there are two levels of list notifications in the list model: (1) whole-list notification, to determine if the list is empty or not; and (2) sublist notification, to determine if the sublist defined by a list number and an entry key value is empty or not. This is not sufficient for MQSeries, which needs to be able to monitor lists with a granularity that lies between these two functions. As described in the related application referenced above, MQSeries uses key values to group entries on a list into two ranges: committed entries and uncommitted entries. It would be desirable to know whether the set of committed entries on a list is empty or not, without actually having to access the CF to do so. To accomplish this, in a preferred embodiment, new list controls called key range (minimum) list entry key (KRLEK) and key range maximum list entry key (KRMLEK) are defined for each list to allow list monitoring to be set up for a range of keys. These list controls may be updated using the write list controls (WLC) command or read using the read list controls (RLC) command. Suitable means allow a user to start or stop monitoring the key range.
2. List and key range threshold notification.
In a preferred embodiment, new list controls are added that allow the user to modify the list and key range empty-to-not-empty or not-empty-to-empty notification thresholds. These list controls, described below, may be updated using the write list controls (WLC) command. The list empty notification threshold (LENT) is the number of list entries that must remain in the list to suppress a not-empty to empty list notification. The key range empty notification threshold (KRENT) is the number of list entries that must remain in the key range to suppress a not-empty to empty list notification A list or key range is considered empty when there are no entries on the list or when the list contains fewer list entries than the list or key range empty threshold. The list or key range may be considered empty even though there are still entries on the list or in the key range if the number of entries have not exceeded the list or key range empty threshold. Similarly, the list not-empty notification threshold (LNENT) is the number of list entries that must be included in the list before an empty to not-empty list notification is generated, while the key range not-empty notification threshold (KRNENT) is the number of list entries that must be included in the key range before an empty to not-empty list notification is generated. A list or key range is considered not-empty when the number of list entries on the list is greater than the list or key range not-empty threshold. The list or key range may still be considered empty even there are entries on the list or in the key range, if the number of entries have not exceeded the list or key range not-empty count. The initial value of the list and key range empty and not-empty thresholds is zero.
3. Aggressive sublist notification.
In a preferred embodiment, a new event monitor control called an aggressive not-empty notification indicator (ANENI) is added to allow the user to specify whether, when monitoring a sublist, event monitor controls (EMCs) should be queued to the user's event queue for only the first entry added to the sublist or for each entry that is added to the sublist.
Yet another aspect of the present invention relates to keys. A new type of key, called a secondary key or, more particularly, a secondary list entry key (SLEK), is introduced that allows the user to specify a secondary key value as a means to identify a list entry. Secondary keys are associated with respective list entries and represent a second key ordering for each list in a CF list structure. A secondary key for an entry may be initialized, or set to null, when the entry is created. Secondary keys exist in parallel with primary keys and may be used and updated in a similar manner, as described below. In a preferred embodiment, a new list structure control called a secondary key indicator (SKI) is defined to allow for creation of secondary key control structures when the list is allocated. This allows the user to specify whether the keyed list structure should be allocated with only primary entry keys or with both primary and secondary entry keys.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a multiple-system complex (sysplex) incorporating the present invention.
FIG. 2 shows a put list associated with a particular shared queue, with committed and uncommitted portions.
FIG. 3 shows a get list associated with a particular shared queue manager.
FIG. 4 shows the format of a list entry key falling within the uncommitted key range.
FIG. 5 shows the format of a list entry key falling within the committed key range.
FIG. 6 shows the movement of list entries between the uncommitted and committed portions of a put list.
FIG. 7 shows the movement of list entries between a put list and a get list.
FIG. 8A shows the procedure for writing a message to a queue.
FIG. 8B shows the procedure for committing a write of a message to a queue.
FIG. 8C shows the procedure for aborting a write of a message to a queue.
FIG. 8D shows the procedure for reading (getting) a message from a queue.
FIG. 8E shows the procedure for committing a read (get) of a message from a queue.
FIG. 8F shows the procedure for aborting a read (get) of a message from a queue.
FIG. 9 shows the coupling facility and the list structures that it contains.
FIG. 10 shows a message command/response block.
FIG. 11 shows a list structure.
FIG. 12 shows a list.
FIG. 13A shows a key range monitor table.
FIG. 13B shows a list monitor table.
FIG. 13C shows an event queue.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the general configuration of a system complex (sysplex) 100 incorporating the present invention. Sysplex 100 comprises a plurality of systems 102 (an exemplary two of which, System A and System B, are shown), each of which is connected to a coupling facility (CF) 104 within which one or more shared message queues 106 are maintained. As is conventional, each system 102 comprises one or more processors and an operating system (not separately shown) and may constitute either a separate physical machine or a logical partition of a logically partitioned machine. Similarly, coupling facility 104 may constitute either a separate physical machine or a logical partition of a logically partitioned machine. Although the invention is not so limited, in a preferred embodiment the physical machines are IBM S/390 Parallel Enterprise Server® processors, while the operating system is the IBM OS/390® operating system.
Within each system 102 , user applications 110 perform sequences of operations, referred to herein as units of work (UOWs), on shared message queues 106 via a shared queue manager (SQM) 108 resident on that system. Shared queue managers 108 on different systems 102 that share the same message queue 106 are referred to herein as a queue-sharing group (QSG). In the preferred embodiment, each shared queue manager 108 in turn interacts with the coupling facility via a component 112 of the OS/390 operating system known as Sysplex Services for Data Sharing (XES). Sysplex Services for Data Sharing (XES) is described more fully in the IBM publication MVS/ESA Programming: Sysplex Services Guide , GC28-1495-02 (June 1995), incorporated herein by reference.
User applications 110 on a system 102 interact with the shared queue manager 108 on that system via a series of Message Queue Interface (MQI) calls, the most important of which are MQPUT (to put a message onto a message queue 106 ) and MQGET (to get a message from a message queue 106 ). In response to such a call, shared queue manager 108 issues a call to XES 112 to invoke a requested system service (e.g., IXLLIST, IXLLSTC, IXLLSTE and IXLLSTM, as described below) to communicate with the coupling facility 104 . In response to receiving a call from shared queue manager 108 , XES 112 sends an appropriate message command block (MCB) containing data and other operands to the coupling facility 104 to perform the requested operation. XES 112 receives back from the coupling facility 104 a message response block (MRB) containing data and/or a response code.
FIG. 10 shows the format of a message command/response block 1000 used for communications between the coupling facility 104 and a particular system 102 . Message command/response block 1000 comprises a message command block (MCB) 1002 , a message response block (MRB) 1004 , and an optional data block 1006 . Message command block 1002 contains a command block 1008 and request operands 1010 . Similarly, message response block 1004 contains a response descriptor 1012 and response operands 1014 . Command block 1008 contains a command code (CC) specifying the type of operation to be performed by coupling facility 104 , while request operands 1010 constitute input parameters, as described below.
As part of its list-processing capability, coupling facility 104 performs requested operations on lists composed of one or more entries. Referring now to FIGS. 2 and 3 , in accordance with one aspect of the present invention, each logical message queue 106 is implemented as a set of lists: a put list 202 , comprising a put list header (PLH) and optionally one or more list entries 204 , and one or more get lists 206 , each comprising a get list header (GLH) and optionally one or more list entries 204 . (The terms “list” and “list header” are used interchangeably herein in view of their one-to-one correspondence.) Each put list 202 is associated with a particular shared queue 106 and is shared by the shared queue managers 108 in the queue-sharing group. Each get list 206 , on the other hand, is associated with a particular shared queue manager 108 and may be used for multiple shared queues 106 . Each list entry 204 corresponds to a message. (The terms “list entry” and “message” are used interchangeably herein.) Associated with each list entry 204 , along with a message and other data, is a list entry key LEK that may be used to determine the order of the entry 204 in the list 202 or 206 . Keys LEK form the basis for partitioning the put list 202 into a committed portion 208 , in which the keys LEK fall within a committed key range, and an uncommitted portion 210 , in which the keys LEK fall within an uncommitted key range that does not overlap the committed key range.
Lists 202 and 206 and key ranges 208 and 210 supply the mechanism for writing, reading and committing messages 204 in accordance with the present invention. More particularly, the process of ‘hiding’ uncommitted messages 204 , hiding messages 204 that have been read and making committed puts globally visible is done simply by movement between list headers 202 and 206 and/or key assignment changes without the use of any explicit locking protocols.
The keys LEK that a list entry (message) 204 can be assigned are defined by the shared queue manager 108 , as described below. Referring to FIGS. 4 and 8A , when a message 204 is initially put (step 802 ), it is first assigned the following 16-byte key LEK in the uncommitted key range (step 804 ):
1 byte—value is X‘F6’ 1 byte—queue manager ID (QMID) of the shared queue manager 108 that wrote the message 204 1 byte—priority of the message 204 8 bytes—UOW ID: 1-byte queue manager ID (QMID) concatenated with a 7-byte store clock (STCK) value 2 bytes—put list header (PLH): the list header 202 to which the message 204 was put 3 bytes—binary zeroes.
The set of list entries 204 whose key LEK begins with X‘F6’ define the uncommitted portion 210 of the (put) list header 202 .
Referring to FIGS. 6 and 8B , when an uncommitted message 204 (first byte of key LEK is X‘F6’) is committed (step 806 ), it is moved from the uncommitted portion 210 of the list header 202 to the committed portion 208 of the same list header 202 . In this case, the list entry 204 moves from one position on the list header 202 to another position on the same list header 202 . The movement is accomplished by changing the list entry's key LEK so that it falls within the committed key range (step 808 ). Referring to FIG. 5 , the uncommitted put key LEK is changed to the following:
1 byte—priority in the inclusive range (0, 9) 8 byte—STCK value (from the uncommitted key, see above) 2 byte—put list header 202 (from the uncommitted key) 1 byte—queue manager ID (QMID) of the shared queue manager 108 that wrote the message 204 4 bytes—binary zeroes.
The set of list entries 204 whose keys begin with (00, 09) inclusive defines the committed portion 208 of the put list header 202 .
Referring to FIG. 8C , if a unit of work decides to abort a write of a message 204 (step 810 ), it deletes the message 204 from the uncommitted portion 210 of the put list 202 (step 812 ). This portion 210 of the put list is available only to the unit of work that originally wrote the message 204 and is invisible to other units of work.
Referring to FIGS. 7 and 8D , when a unit of work requests the highest committed message 204 on a get request (step 814 ), only the committed portion 208 of the list header 202 is eligible to be scanned, that is, list entries 202 whose keys begin with (00, 09) inclusive. Entries 204 that begin with X‘F6’ do not participate in the scan.
This is accomplished by using an IXLLSTE invocation (as described below) that examines the entry 204 at the head of the list 202 (step 816 ) and returns it only if the first byte of its key is in the inclusive range (00, 09). (This is referred to herein as key range checking on read.) If there are no messages 204 on the list header 202 or if the key of the message at the head of the list header begins with a value greater than or equal to X‘F6’ (step 818 ), then no message is returned (step 820 ).
If there are committed messages 204 , then the message 204 that is returned is the message at the head of the list header 202 , since the messages 202 are in priority order and within priority by time of arrival. Thus, if the message 204 at the head of the list 202 is a committed message (step 818 ), then two things happen in an atomic fashion:
1. The contents of the list entry 204 are copied from the list structure into virtual storage (step 822 ). 2. The selected list entry 204 is moved to the ‘reading’ shared queue manager 108 's uncommitted get queue 206 (step 824 ). This move operation makes the message 204 invisible to all other shared queue managers 108 in the queue-sharing group who issue a get request to the corresponding PLH 202 . As noted earlier, in a list structure, each shared queue manager 108 is assigned its own uncommitted get list header 206 .
Once the message 204 is moved to the shared queue manager 108 's uncommitted get queue 206 , it is no longer visible to other get requests because all get requests for the shared queue 106 reference the shared queue's put list header 202 .
The final disposition of the message read will be either commit or abort. Referring to FIG. 8E , if the disposition is commit (step 826 ), the message 204 is deleted from the shared queue manager 108 's uncommitted get queue 206 (step 828 ). Referring to FIG. 8F , if the disposition is abort (step 830 ), then the message 204 is moved back to the committed put list header 202 from whence it came into its proper priority/time sequence position (step 832 ).
The list architecture of coupling facility 104 , insofar as it is pertinent to the present application, will now be described.
Referring to FIG. 9 , coupling facility 104 contains microcode 904 , also referred to as coupling facility control code (CFCC), for managing one or more list structures 902 . Referring to FIG. 11 , each list structure 902 contains a set of list structure controls 1102 , a list set 1104 comprising one or more lists 1106 , user controls 1108 , a lock table 1110 comprising one or more lock table entries (LTEs) 1112 , and one or more event queue controls 1114 and corresponding event queues 1116 .
Referring to FIG. 12 , each list 1106 contains list controls 1202 (including a a key range monitor 110 table 1204 and a list monitor table 1206 ) and, optionally, one or more list entries 1208 . Each list entry 1208 in turn contains a set of list entry controls 1210 (including a list entry ID LEID and a list entry key LEK), a data list entry 1212 comprising one or more list elements (LEs) 1214 , and an adjunct list entry 1216 (including a secondary list entry key SLEK if defined).
List Structure Controls 1102
The fixed list structure controls 1102 are initialized when the list structure 902 is created and remain unchanged until it is deallocated.
The program-modifiable list structure controls 1102 are initialized when the list structure 902 is created. The program-modifiable control values may be changed by commands or CF processes.
The fixed list structure controls 1102 are summarized in the following table.
Fixed List Structure Controls
Acronym
List count
LC
List element characteristic
LELX
List structure type
LST
Maximum data list entry size
MDLES
Maximum structure size
MXSS
The program-modifiable list structure controls 1102 are summarized in the following table.
Program-Modifiable List Structure Controls
Acronym
Entry reapportionment-in-progress indicator
EREIPI
Event monitor controls count
EMCC
List set element count
LSELC
List set entry count
LSEC
Maximum event monitor controls count
MEMCC
Maximum list set element count
MLSELC
Maximum list set entry count
MLSEC
Marginal structure size
MRSS
Minimum apportionable structure size
MASS
Pending entry-to-element ratio
PETELR
Structure authority
SAU
Structure size
SS
Structure size change indicator
SSCI
Target maximum element count
TMELC
Target maximum entry count
TMEC
Target maximum event monitor count
TMEMC
Target structure size
TSS
User identifier vector
UIDV
User structure control
USC
Entry Reapportionment-in-Progress Indicator (EREIPI): Indicates whether an entry-to-element reapportionment process is currently active for the list structure 902 .
Event Monitor Controls Count (EMCC): Specifies the number of event monitor controls objects 1306 currently in a list set 1104 .
Extended User Structure Control (EUSC): An extension to the user structure control.
List Count (LC): Specifies the number of lists 1106 created.
List Element Characteristic (LELX): Specifies the number of bytes in each list element 1214 .
List Set Cursor (LSCUR): An integer that is either zero or contains the value of the current list number in the list set scan process.
List Set Element Count (LSELC): Specifies the number of list elements 1214 that have been assigned to list entries 1208 or retry-data blocks, or both, in the list set 1104 .
List Set Entry Count (LSEC): Specifies the number of existing list entries 1208 in the list set 1104 .
List Structure Type (LST): Indicates the list objects 1106 created on allocation. The first flag is a secondary key indicator (SKI), the second flag is a program list entry identifier indicator (PLEIDI), the third flag is a element count indicator (ECI), The fourth flag is a lock indicator (LI), the fifth flag is a data indicator (DI), the sixth flag is an adjunct indicator (AI), the seventh flag is a name indicator (NI), and the eighth flag is a key indicator (KI).
The secondary key indicator indicates whether secondary keys are supported.
The program list entry identifier indicator indicates whether the structure uses a coupling facility-assigned LEID value or a program-assigned LEID value.
The element count indicator indicates whether (1) list entry count and list entry count limit are defined or, alternatively, (2) list element count and list element count limit are defined.
The lock indicator indicates whether a lock table is created.
The data and adjunct indicators indicate respectively whether list entries have data entries and adjunct entries.
The name indicator indicates whether list entries are named.
The key indicator indicates whether list entries are keyed.
At least one of the lock, data or adjunct indicators is active (i.e., indicates that the condition is true). The name indicator and the key indicator are never both active. For the dequeue event monitor controls (DEMC), read event monitor controls (REMC), read event queue controls (REQC), and register event monitors (REMS) commands, the key indicator must be active; otherwise, the list structure type is invalid and a request exception is recognized.
Marginal Structure Size (MRSS): Specifies the minimum number of 4K-byte units of CF storage that are required for the creation of the requested lock table entries 1112 , lists 1106 , and associated controls for the list structure 902 , independent of either the storage increment size or the requested target entry-to-element ratio.
Maximum Data List Entry Size (MDLES): Specifies the maximum size of the data list entry 1212 as an integral multiple of the list element size.
Maximum Event Monitor Controls Count (MEMCC): Specifies the maximum number of possible event monitor controls objects 1306 in a list set 1104 .
Maximum List Set Element Count (MLSELC): Specifies the maximum number of list elements 1214 that are available for assignment to list entries 1208 or retry-data blocks, or both, in the list set 1104 .
Maximum List Set Entry Count (MLSEC): Specifies the maximum number of possible list entries 1208 in a list set 1104 .
Maximum Structure Size (MXSS): Specifies the maximum number of 4K-byte units of CF storage that can be allocated for the list 1106 .
Minimum Apportionable Structure Size (MASS): Specifies the minimum number of 4K-byte units of CF storage that can be allocated for the list 1106 , in integral multiples of the CF storage increment, that are sufficient for creating the requested lock table entries 1112 , lists 1106 , associated controls, enough event monitor controls 1306 and list entries 1208 with their associated controls to substantially satisfy the target monitor-to-entry storage ratio, and enough entries and elements to substantially satisfy the target entry-to-element ratio.
Monitor Reapportionment-in-Progress Indicator (MREIPI): Indicates whether a monitor-to-entry storage reapportionment process is currently active for the list structure 902 .
Pending Entry-to-Element Ratio (PETELR): Contains the last requested target entry-to-element ratio on an allocate list structure command. The PETELR object is updated when the list structure 902 is initially allocated and when a reapportionment process is initiated.
Pending Monitor-to-Entry Storage Ratio (PMTESR): Contains the last requested target monitor-to-entry storage ratio on an allocate list structure command. The PMTESR object is updated when the list structure 902 has been initially allocated and a monitor-to-entry storage reapportionment process is requested.
Reapportionment-in-Progress Indicator (REIPI): Indicates whether a reapportionment process is currently active for the list structure 902 .
Structure Authority (SAU): A value associated with each bit in the SID vector.
Structure Size (SS): Specifies the number of 4K-byte units allocated.
Structure Size Change Indicator (SSCI): Indicates whether an expansion or contraction process is currently active for the list structure 902 .
Target Maximum Element Count (TMELC): Specifies the target for the maximum number of list elements 1214 that are available for assignment to list entries 1208 or retry-data blocks, or both, in the list set 1104 .
Target Maximum Entry Count (TMEC): Specifies the target for the maximum number of possible list entries 1208 in a list set 1104 .
Target Maximum Event Monitor Count (TMEMC): Specifies the target for the maximum number of event monitor controls objects 1306 that are available for registration of interest in subsidiary lists within the list set 1104 .
Target Structure Size (TSS): Specifies the target number of 4K-byte units to be allocated.
User Identifier Vector (UIDV): A bit string with an initial value of zero. The bit positions start at zero and increase sequentially to the user identifier limit. The bit at position (i) in the string is set to one when a user is assigned with a UID value of (i). The bit at position (i) is reset to zero when a user is unassigned.
User Structure Control (USC): A field per structure defined by the user.
User Controls 1108
The user controls 1108 are created and initialized when a list structure user (such as a CF Manager component of shared queue manager 108 , as described below) is assigned and are deleted when the list structure user is unassigned.
The user controls 1108 are summarized in the following table.
User Controls
Acronym
List notification token
LNT
System identifier
SYID
User attachment control
UAC
User authority
UAU
User state
US
List Notification Token (LNT): Specifies a list notification vector to the system.
System Identifier (SYID): A value specified by the program when a message path is activated. The system identifier is maintained in the message path status vector and copied into the user controls 1108 when an attach list structure user command is communicated over the message path.
User Attachment Control (UAC): A field per attached user defined by the user.
User Authority (UAU): A value that is compared and conditionally updated.
User State (US): Specifies whether the user is attached.
Lock Table 1110
The lock table 1110 is a sequence of objects 1112 , called lock table entries. The number of lock table entries 1112 is determined when the table is created. The lock table entries 1112 are numbered from zero to the lock table entry count less one.
Each lock table entry 1112 has a global lock manager (GLM) object and an optional local lock managers (LLM) object. A lock table entry 1112 whose size is one byte has only a global lock manager object. When a lock table entry size is greater than one byte, the leftmost byte is the global lock manager object, and the remaining bytes form the local lock managers object. Lock tables 1110 with an entry size of one byte do not support local lock managers. Lock tables 1110 with an entry size of at least two bytes do support local lock managers.
The global lock manager object of a lock table entry 1112 contains an unsigned binary number called a user identifier.
The local lock managers object of a lock table entry 1112 contains a string of local lock bits, where each bit represents a user identifier. The bits in the object are numbered from left to right, starting at the value zero and proceeding upward to the bit for the highest valid user identifier.
The lock table objects have a value of zero when the table is allocated and may be modified by subsequent commands.
Event Queue Controls 1114
There is an event queue controls object 1114 for each event queue 1116 in a list structure 902 . All of the event queue controls of an event queue 1116 with the exception of the key type, are initialized to zero when the event queue 1116 is created or when the associated list structure user is detached. The key type is initialized to primary for the primary event queue controls and is initialized to secondary for the secondary event queue controls.
The event queue controls are summarized in the following table.
Event Queue Controls
Acronym
Event monitor controls queued count
EMCQC
Event notification entry number
ENEN
Event notification request type
ENRT
Event queue monitoring active bit
EQMAB
Event queue transition count
EQTC
Key type
KT
Event Monitor Controls Queued Count (EMCQC): Specifies the number of event monitor controls 1306 currently queued to the event queue 1116 .
Event Notification Entry Number (ENEN): Specifies a list notification vector entry associated with an event queue 1116 .
Event Notification Request Type (ENRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on an event queue 1116 . When active, this flag causes a user to be notified of empty-to-not empty transitions.
Event Queue Monitoring Active Bit (EQMAB): Specifies whether the user associated with the event queue 1116 is monitoring the event queue 1116 .
Event Queue Transition Count (EQTC): Specifies the number of empty to not-empty event queue transitions that have occurred.
Key Type (KT): Indicates the key type (primary or secondary) of the event monitor controls 1306 that are queued on the event queue 1116 . If the key type is primary, EMCs are queued for primary subsidiary lists; if the key type is secondary, EMCs are queued for secondary subsidiary lists.
Event Queue 1116
An event queue 1116 is a sequence of objects called event monitor controls 1306 (FIG. 13 C). There are zero, one, or two event queues 1116 created for each list structure user when the list structure 902 is allocated, depending on the list structure type. When the list structure 902 does not have keys, no event queues 1116 are created. When the list structure 902 has keys but not secondary keys, a single event queue 1116 is created for each user. This is referred to either as the event queue 1116 or the primary event queue 1116 When the list structure 902 has both keys and secondary keys, two event queues 1116 are created, a primary event queue 1116 that contains EMCs with list entry keys, and a secondary event queue 1116 that contains EMCs with secondary list entry keys. The event queues 1116 are deleted when the list structure 902 is deallocated.
An event monitor controls object 1306 is always queued to the rightmost position and dequeued from the leftmost position of the queue.
An event monitor controls object 1306 may be queued when (1) an empty to not-empty state transition occurs for a monitored subsidiary list, (2) notification of the initial subsidiary list state is requested on registration, or (3) a not-empty to not-empty state transition occurs for a monitored subsidiary list. An event monitor controls object 1306 may be withdrawn when a not-empty to empty state transition occurs for a monitored subsidiary list or when notification of the initial subsidiary list state is requested on registration, may be dequeued by means of the dequeue event monitor controls command, and may be deleted when a user deregisters interest in the subsidiary list or detaches from the list structure 902 .
List 1106
A list 1106 is a sequence of objects 1208 , called list entries. The number of possible entries 1208 , from one to 2 32 , is determined when the list structure 902 is created.
The relative position of a list entry 1208 in the sequence is determined when the entry is created and may be changed when any list entry 1208 is created, deleted, or moved.
A list entry 1208 is located by means of a list entry identifier, list entry name, or by position. List positions may be ordered by the time sequence of when list entries 1208 are created on or moved to a list 1106 or list positions may be in key order. There may be one or two key orderings for a list 1106 . If there is only one key ordering then list positions are ordered by increasing values of the list entry key. If two key orderings exist, then the primary key ordering is by increasing values of the list entry key and the secondary key ordering is by increasing values of the secondary list entry key.
The size of the largest list 1106 is limited by the free space and the size of all the controls required to support the list structure 902 .
A list entry 1208 has up to two objects: a data list entry 1212 and an adjunct list entry 1216 , depending on the list structure type.
A data list entry consists of from one to MDLES list elements 1214 . The data list entry size is determined when the data list entry is written. The list element size is a power of 2 that is at least 256 bytes. The adjunct list entry size is 64 bytes.
A list entry 1208 exists when it is created and ceases to exist when it is deleted.
Subsidiary List
A subsidiary list is a list within a list 1106 where all list entries 1208 have the same key. There are two types, depending on the type of key. Primary subsidiary lists consist of list entries 1208 on the same list 1106 with the same list entry key. Secondary subsidiary lists consist of all list entries 1208 on the same list 1106 with the same secondary list entry key.
A primary subsidiary list may only exist when a list set 1104 is created and the list entries 1208 are keyed. A secondary subsidiary list may only exist when a list set 1104 is created and secondary keys are supported in the structure.
Adjunct Data Entry
The adjunct data entry is a 64-byte storage object containing unformatted data. When the structure contains adjuncts and the adjunct format control bits in the list entry controls are inactive, the adjunct list entry is an adjunct data entry.
Adjunct Secondary Key Entry: The adjunct secondary key entry is a storage object containing the secondary list entry key and a secondary adjunct data area. When the structure contains secondary keys and the adjunct secondary key entry indicator in the adjunct format control is active, the adjunct list entry is an adjunct secondary key entry.
The adjunct secondary key entry objects are summarized in the following table.
Adjunct Secondary Key Entry
Acronym
Secondary list entry key
SLEK
Secondary adjunct data entry
SADE
Secondary List Entry Key (SLEK): Partially designates the position of the list entry 1208 in the list 1106 in secondary key order.
Secondary Adjunct Data Entry (SADE): A storage object containing unformatted data.
List Controls 1202
There is a list controls object 1202 for every list 1106 created in a list structure 902 . All the list controls 1202 except the list entry count limit and the list element count limit are initialized to zero when the list structure 902 is created.
The list controls 1202 are summarized in the following table.
List Controls
Acronym
Assignment key
AK
Assignment key threshold
AKT
Cursor direction
CDIR
Key range empty notification threshold
KRENT
Key range list entry key
KRLEK
Key range maximum list entry key
KRMLEK
Key range monitor table
KRMT
Key range not-empty notification threshold
KRNENT
List authority
LAU
List cursor
LCUR
List element/list entry count
LELC/LEC
List element count/list entry count limit
LELCL/LECL
List empty notification threshold
LENT
List monitor table
LMT
List not-empty notification threshold
LNENT
List state transition count
LSTC
Assignment Key (AK): Specifies the value assigned to a list entry key when a key assignment operation is executed for a list entry 1208 that is moved or created on the list 1106 .
Assignment Key Threshold (AKT): Specifies the maximum value of an assignment key.
Cursor Direction (CDIR): Indicates how the list cursor is updated (left to right or right to left) when the list cursor is maintained or initialized by a write list controls command.
Key Range Empty Notification Threshold (KRENT): Specifies a number which is one less than the number of list entries 1208 that must remain in the key range to suppress a not-empty-to-empty list notification.
Key Range List Entry Key (KRLEK): Specifies the lower value of the key range.
Key Range Maximum List Entry Key (KRMLEK): Specifies the upper value of the key range.
Key Range Not-empty Notification Threshold (KRNENT): Specifies one less than the number of list entries 1208 required in the key range in order to generate an empty-to-not-empty list notification.
List Authority (LAU): A value that is compared and conditionally updated.
List Cursor (LCUR): A list entry identifier that identifies a list cursor position.
List Element Count (LELC): Specifies the number of list elements 1214 currently in the list 1106 .
List Element Count Limit (LELCL): Specifies the maximum number of possible list elements 1214 in a list 1106 .
List Empty Notification Threshold (LENT): Specifies a number which is one less than the number of list entries 1208 that must remain in the list 1106 to suppress a not-empty-to-empty list notification.
List Not-empty Notification Threshold (LNENT): Specifies one less than the number of list entries 1208 required on the list 1106 in order to generate an empty-to-not-empty list notification.
List Entry Count (LEC): Specifies the number of list entries 1208 currently in the list 1106 .
List Entry Count Limit (LECL): Specifies the maximum number of possible list entries 1208 in a list 1106 .
Key Range Monitor Table 1204
The key range monitor table 1204 contains information used to process the list notification vector of each user who has registered interest in key range state transitions.
The key range monitor table 1204 is a sequence of objects 1302 (FIG. 13 A), called key range monitor table entries. The number of key range monitor table entries 1302 is determined when the table is created and is equal to the maximum number of list structure users plus one. The key range monitor table entries 1302 are numbered from zero to the user identifier limit.
Each key range monitor table entry 1302 has a key range monitoring active bit object, a key range notification request type object and key range notification entry number object.
Key Range Monitoring Active Bit (KRMAB): Specifies whether the user associated with the key range monitor table entry 1302 is monitoring the key range.
Key Range Notification Entry Number (KRNEN): Specifies a list notification vector entry associated with a monitored key range.
Key Range Notification Request Type (KRNRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on a monitored key range. When active, this flag causes the user to be notified of empty-to-not empty transitions.
Key range monitor table entry 1302
Key Range Monitor Table Entry Object Acronym Key range monitor active bit KRMAB Key range notification request type KRNRT Key range notification entry number KRNEN
List Monitor Table 1206
The list monitor table 1206 contains information used to process the list notification vector of each user who has registered interest in the state transitions of the list 1106 .
The list monitor table 1206 is a sequence of objects 1304 (FIG. 13 B), called list monitor table entries. The number of list monitor table entries 1304 is determined when the table is created and is equal to the maximum number of list structure users plus one.
The list monitor table entries 1304 are numbered from zero to the user identifier limit.
Each list monitor table entry 1304 has a list monitoring active bit object, a list notification request type object and a list notification entry number object.
List Monitoring Active Bit (LMAB): Specifies whether the user associated with the list monitor table entry 1304 is monitoring the list.
List Notification Entry Number (LNEN): Specifies a list notification vector entry associated with a monitored list 1106 .
List Notification Request Type (LNRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on a monitored list 1106 .
List Monitor Table Entry
List Monitor Table Entry Object Acronym List monitor active bit LMAB List notification request type LNRT List notification entry number LNEN
List Entry Controls 1210
There is a list entry controls object 1210 for every list entry 1208 within a structure. The list entry controls 1210 are initialized when a list entry 1208 is created and are deleted when a list entry 1208 is deleted. The list entry controls 1210 are summarized in the following table.
List Entry Controls
Acronym
Adjunct format control
AFC
Data-list-entry size
DLES
List entry identifier
LEID
List entry key
LEK
List number
LN
Version number
VN
Adjunct data entry
ADE
Adjunct Format Control (AFC): A bit string consisting of adjunct format bits. Each bit is associated with a particular adjunct format. The adjunct format control bits include an adjunct secondary key entry indicator and (2) an adjunct lock entry indicator. The bits are mutually exclusive; at most one bit is active. When all the bits are inactive, the adjunct list entry 1216 is unformatted and contains the adjunct data entry.
Data List Entry Size (DLES): Specifies the size of the data list entry 1212 as an integral multiple of the list element size.
List Entry Identifier (LEID): Designates the list entry 1208 .
List Entry Key (LEK): Partially designates the position of the list entry 1208 in the list 1106 .
List Number (LN): Designates the list 1106 that the list entry 1208 is in.
Event Monitor Controls 1306
There is an event monitor controls object 1306 for every user and subsidiary list combination for which a user has currently registered interest. The number of possible event monitor controls 1306 , from one to 2 32 −1, is determined when the list structure 902 is created and may be changed when structure storage is expanded or contracted or the monitor-to-entry storage ratio is reapportioned.
An event monitor controls object 1306 is created when a user initially registers interest and is deleted when a user deregisters interest in a subsidiary list or detaches from the list structure 902 .
All the event monitor controls 1306 except the event monitor queued indicator are initialized to the values provided as request operands 1010 during registration.
The event monitor controls 1306 are summarized in the following table.
Event Monitor Controls
Acronym
Aggressive not-empty notification indicator
ANENI
Event monitor queued indicator
EMQI
List entry key/Secondary list entry key
LEK/SLEK
List number
LN
Key type
KT
User identifier
UID
User notification control
UNC
Aggressive Not-empty Notification Indicator (ANENI): When inactive, indicates that the event monitor controls 1306 should be queued to the event queue 1116 for only the first list entry 1208 added to a subsidiary list. When active, indicates that the event monitor controls 1306 should be queued to the event queue for every list entry 1208 that is added.
Event Monitor Queued Indicator (EMQI): Indicates whether the event monitor controls object 1306 is queued to the event queue 1116 associated with the user ID contained within the object.
List Entry Key (LEK): Partially designates the primary subsidiary list.
List Number (LN): Partially designates the subsidiary list.
Key Type (KT): Indicates the key type (primary or secondary) in the event monitor controls 1306 . When the key type is primary, the key is a (primary) list entry key and the event monitor controls 1306 are associated with a primary subsidiary list. When the key type is secondary, the key is a secondary list entry key and the event monitor controls 1306 are associated with a secondary subsidiary list.
Secondary List Entry Key (SLEK): Partially designates the secondary subsidiary list.
User Identifier (UID): Identifies the user.
User Notification Control (UNC): A field per event monitor controls 1306 defined by the user.
List Structure Object States
List States
A list 1106 is either in the empty or the not-empty state.
Empty State: A list 1106 is in the empty state when the number of list entries 1208 on the list 1106 is less than or equal to the list empty notification threshold.
Not-empty State: A list 1106 is in the not-empty state when the number of entries on the list 1106 is greater than the list not-empty notification threshold.
When the empty and not-empty notification thresholds for the list 1106 are not equal and the number of entries on the list 1106 falls between the list empty notification threshold and the list not-empty notification threshold, inclusive of the latter, the state of the list 1106 is determined as follows:
1. If an empty-to-not-empty list notification has not been generated since the list 1106 was created, the list 1106 is in the empty state. 2. If an empty-to-not-empty list notification has been generated since the list 1106 was created, the state of the list 1106 depends on the last generated list notification; if the last generated list notification is an empty-to-not-empty transition, the state of the list 1106 is not empty, otherwise the list 1106 is empty.
List State Transitions
A user may register interest in the state transitions of a list 1106 by means of the register list monitor command. A list 1106 may change either from the not-empty to the empty state or from the empty to the not-empty state.
Empty to Not-empty List State Transition: A list 1106 that is in the empty state changes from the empty to the not-empty state when an entry is created on or moved to the list 1106 and the number of list entries 1208 on the list 1106 becomes one greater than the list not-empty notification threshold.
Not-empty to Empty List State Transition: A list 1106 that is in the not empty state changes from the not-empty to the empty state when an entry is deleted from the list 1106 or moved to another list 1106 and the number of list entries 1208 on the list 1106 becomes equal to the list empty notification threshold.
Key Range States
A key range is either in the empty or the not-empty state. A user may request a notification of the initial state of a key range by means of the initial notification request type on the register list monitor command.
Empty State: A key range is in the empty state when the number of list entries 1208 in the key range is less than or equal to the key range empty notification threshold.
Not-empty State: A key range is in the not-empty state when the number of entries in the key range is greater than the key range not-empty notification threshold.
When the empty and not-empty notification thresholds for the key range are not equal and the number of entries in the key range falls between the key range empty notification threshold and the key range not-empty notification threshold, inclusive of the latter, the state of the key range is determined as follows:
1. If an empty-to-not-empty list notification has not been generated since the key range was initialized, the key range is in the empty state. 2. If an empty-to-not-empty list notification has been generated since the key range was initialized, the state of the key range depends on the last generated list notification; if the last generated list notification is an empty-to-not-empty transition, the state of the key range is not empty, otherwise the key range is empty.
Key Range State Transitions
A user may register interest in the state transitions of a key range by means of the register list monitor command. A key range may change either from the not-empty to the empty state or from the empty to the not-empty state.
Empty to Not-empty Key Range State Transition: A key range that is in the empty state changes from the empty to the not-empty state when (1) an entry is created in the key range, (2) an entry is moved to the key range, or (3) key range initialization completes, and the number of list entries 1208 in the key range becomes greater than the key range not-empty notification threshold when the number had previously been less than or equal to the threshold.
Not-empty to Empty Key Range State Transition: A key range that is in the not empty state changes from the not-empty to the empty state when an entry is (1) deleted from the key range, (2) moved to another list 1106 , (3) moved to the same list 1106 with a new list entry key that is outside of the key range, or (4) key range initialization completes, and the number of list entries 1208 in the key range becomes less than or equal to the key range empty notification threshold when the number had previously been greater than the threshold.
Subsidiary List States
A subsidiary list is either in the empty or the not-empty state. A user may request to queue or withdraw the event monitor controls object 1306 to reflect the initial state of a subsidiary list by means of the initial notification request type on the register list monitor or register event monitors command.
Empty State: A subsidiary list is in the empty state when there are no entries in the subsidiary list.
Not-empty State: A subsidiary list is in the not-empty state when there are one or more entries in the subsidiary list.
Subsidiary List State Transitions
A user may register interest in the state transitions of a subsidiary list by means of the register list monitor or register event monitors command.
A subsidiary list may change either from the not-empty to the empty state, from the empty to the not empty state, or from the not-empty to the not-empty state.
Empty to Not-empty Subsidiary List State Transition: A subsidiary list changes from the empty to the not-empty state when the subsidiary list has no entries and an entry is created or moved to the subsidiary list.
Not-empty to Empty Subsidiary List State Transition: A subsidiary list changes from the not-empty to the empty state when the subsidiary list has one entry and the entry is deleted or moved to another subsidiary list.
Not-empty to Not-empty Subsidiary List State Transition: A subsidiary list changes from the not-empty to the not-empty state when (1) the subsidiary list is not empty, (2) an entry is created or moved to the subsidiary list, (3) the event monitor queued indicator is active and the aggressive not-empty notification indicator is active in the associated EMC.
Event Queue States
An event queue 1116 is either in the empty or the not-empty state. A user may request a notification of the initial state of an event queue 1116 by means of the initial notification request type on the register list monitor command.
Empty State: An event queue 1116 is in the empty state when there is no event monitor controls object 1306 queued to the event queue 1116 .
Not-empty State: An event queue 1116 is in the not-empty state when there are one or more event monitor controls objects 1306 queued to the event queue 1116 .
Event Queue State Transitions
A user may register interest in the state transitions of an event queue 1116 by means of the register list monitor command. An event queue 1116 may change either from the not-empty to the empty state or from the empty to the not-empty state.
Empty to Not-empty Event Queue State Transition: An event queue 1116 changes from the empty to the not-empty state when the event queue 1116 has no queued object and an event monitor controls object 1306 is queued to the event queue 1116 .
Not-empty to Empty Event Queue State Transition: An event queue 1116 changes from the not-empty to the empty state when the event queue 1116 has one event monitor controls object 1306 queued and the object is dequeued, withdrawn, or deleted.
Creating a List Structure
When a list structure 902 is created, the list structure type determines the attributes of the created structure. The list structure type has indicators for each of the following: program list entry identifier indicator, counters, locks, data, adjunct, name, key, and secondary key.
When the program list entry identifier indicator in the list structure type specified is inactive and allocation is successful, the list structure 902 uses list entry identifier values that are generated by the coupling facility.
When the program list entry identifier indicator in the list structure type specified is active and allocation is successful, the list structure 902 uses list entry identifier values that ate program assigned.
When the element count indicator in the list structure type specified is inactive and allocation is successful, the list controls 1202 for each list 1106 contain a list entry count and a list entry count limit. When the count indicator in the list structure type specified is active and allocation is successful, the list controls 1202 for each list 1106 contain a list element count and a list element count limit.
When the lock indicator in the list structure type specified is active and allocation is successful, a lock table 1110 is created with a width as specified by the lock table entry characteristic and a length as specified by the lock table entry count.
When the data indicator in the list structure type specified is active and allocation is successful, storage is allocated for the creation of list elements 1214 . The size of the list elements 1214 is specified by the list element characteristic.
When the adjunct indicator in the list structure type specified is active and allocation is successful, each list entry 1208 created in the structure has an adjunct list entry 1216 with a size of 64 bytes.
When the name indicator in the list structure type specified is active and allocation is successful, each list entry 1208 created in the structure has a list entry name associated with it.
When the key indicator in the list structure type specified is active and allocation is successful, every user identifier has primary event queue controls associated with it, each list entry 1208 created in the structure has a list entry key associated with it, and each list 1106 has a key range associated with it. The key range list entry key and maximum key range list entry key are both set to zero, and the key range is placed in the empty state.
When the secondary key indicator in the list structure type specified is active and allocation is successful, every user identifier has secondary event queue controls associated with it and each list entry 1208 created in the structure has a secondary list entry key associated with it stored in the adjunct list entry 1216 .
When a list structure 902 is created, (1) the free space and free control space global controls are updated, (2) the appropriate created bit in the structure identifier vector is set to one, and (3) the list structure and list controls 1202 are initialized, including the update of the target structure size and target count objects.
When a list structure 902 is created and the maximum structure size request operand 1010 is nonzero, the maximum structure size object is initialized to the largest storage size that the model can support given the structure size and is equal to or smaller than the maximum structure size request operand 1010 rounded up to the nearest integral multiple of the CF storage increment.
When a list structure 902 is created, target structure size request operand 1010 is zero, and the maximum structure size request operand 1010 is zero, the maximum structure size object is set equal to the computed target structure size.
Specifying a nonzero target structure size which is smaller than the marginal structure size or larger than the maximum structure size will cause the allocation to complete with an appropriate response code.
Comparing List Authorities
The list authorities are always compared when the write list controls command is executed. Otherwise, the comparison of list authorities is controlled by the list authority comparison type operand. When the value of the list authority comparison type is do not compare, the list authorities are not compared and list authority comparison is successful.
When the value of the list authority comparison type is compare for being equal or compare for being less than or equal or when a write list controls command is executed, the CLAU operand is compared with the value of the list authority control in the specified list 1106 .
The specified list 1106 is designated by the LN operand 1010 in the MCB 1002 . The only exception is that when the write and move list entry command results in the creation of a list entry 1208 , the specified list 1106 is designated by the TLN operand 1010 in the MCB 1002 .
When the value of the list authority comparison type is compare for being equal and they are equal, the list authority comparison succeeds, and the command continues.
When the value of the list authority comparison type is compare for being less than or equal and the list authority control is less than or equal to the CLAU operand, the list authority comparison succeeds and the command continues.
When the list authority comparison fails, command execution is completed with an appropriate response code.
Replacing List Authorities
The list authority control may be replaced when the write list controls command is executed. Otherwise, the replacement of list authorities is controlled by the list authority replacement type and list authority comparison type operands. When the value of the list authority replacement type is active, the value of the LAU operand is stored in the list authority control provided one of the following conditions exists:
The command is write list controls and list authority comparison is successful, and (1) The value of the LAUCT operand is do not compare, or (2) The value of the LAUCT operand is compare for being equal or compare for being less than or equal and list authority comparison is successful.
List authority comparison always occurs before any list objects are updated.
Comparing Keys
When the key comparison type is active, the list entry key object is compared with the list entry key request operand 1010 and optionally the maximum list entry key operand. The key request type operand specifies how the keys are compared.
When the secondary key comparison type is active, the secondary list entry key object is compared with the secondary list entry key request operand 1010 and optionally the maximum secondary list entry key operand. The secondary key request type operand specifies how the keys are compared.
When both the key comparison type and the secondary key comparison type are active, both key comparisons are performed and both must succeed in order for the key comparison to be successful.
For multiple list entry commands, the key comparison is on an entry basis, the key is compared for the entry and the delete, read, or move for the entry occurs if the key comparison is successful for the entry. When the comparison is successful, the list entry 1208 is selectable by a multiple list entry command. When the comparison is unsuccessful, the list entry 1208 is not selectable.
Initializing a Key Range
A key range is initialized when a write list controls command is executed and the key range list entry key and key range maximum list entry key are updated or when a list 1106 is created and the list 1106 is keyed. A key range is initialized by calculating the number of list entries 1208 in the key range, comparing the count to the key range threshold values, and setting the key range state to either the empty state or the not-empty state. Initialization of the key range can be continued or completed by either continued executions of the write list controls command with bit 7 of the LCT active or by continued execution of the register list monitor command with a monitor request type of key range monitor. If key range initialization is not complete, the WLC or RLM commands complete with appropriate response codes.
If key range initialization is not complete, and a WLC command is executed with bit 7 of the LCT inactive or a RLM command is executed and the monitor request type is not key range monitor, then the WLC and RLM commands are executed independently from key range initialization.
If the WLC command is executed with bit 7 of the LCT active, key range initialization is in progress, and the specified key range list entry key or key range maximum list entry key are different from the values associated with the key range, initialization of the prior key range is stopped and initialization of the new key range is started.
Comparing Global Lock Managers
Generally, a global lock manager comparison is performed before a lock table entry 1112 is written, and a global lock manager comparison may be performed before the next nonzero lock table entry 1112 is read, or before a list entry 1208 is created, replaced, read, moved, or deleted, or before an adjunct lock entry is updated by an adjunct locking operation.
The global lock manager object is compared with the comparative global lock manager specified. When they match, the global lock manager comparison succeeds. When they do not match, the global lock manager comparison fails.
Except for the reset lock managers command and the read next lock table entry command, when a lock table write is to be performed, when a list entry creation, replacement, read, movement, or deletion is to be performed, or when an adjunct lock entry is to be updated by an adjunct locking operation, if the global lock manager comparison is requested and succeeds, the command continues; if the global lock manager comparison is requested and fails, command execution is completed with an appropriate response code.
For the reset lock managers command with the unlock type operand set to either B‘10’ or B‘11’, if the global lock manager comparison succeeds, the command continues. If the global lock manager comparison fails and if the report mismatch type operand is B‘0’, then a lock manager mismatch response code is returned. If the global lock manager comparison fails and if the report mismatch type operand is B‘1’, then the current request block is skipped and the command continues to process the next request block.
For the reset lock managers command with the unlock type operand set to B‘01’, if the global lock manager comparison succeeds and the report mismatch type operand is B‘1’, or both global and local lock manager comparisons are successful, the command continues. If the global lock manager comparison or local lock manager comparison fails, and the report mismatch type operand is B‘0’, then a lock manager mismatch response code is returned. If the global lock manager comparison fails and if the report mismatch type operand is B‘1’, then the current request block is skipped and the command continues to process the next request block.
For the read next lock table entry command with the lock request type operand set to compare global lock managers, if the global lock manager comparison succeeds on a nonzero lock table entry 1112 , the entry is returned; if the global lock manager comparison fails, the entry is skipped and the scan of the lock table 1110 continues.
For the read next lock table entry command with the lock request type operand set to compare global lock or local lock managers, if either global lock manager or local lock manager comparison succeeds on a nonzero lock table entry 1112 , the entry is returned; if neither comparison succeeds, the entry is skipped and the scan of the lock table 1110 continues.
Comparing Local Lock Managers
Generally, local lock manager comparison may occur before a lock table entry 1112 is written, before an adjunct lock entry is updated by an adjunct locking operation, before the next nonzero lock table entry 1112 is read, or before a list entry 1208 is created, replaced, read, moved, or deleted.
Local lock manager comparison is also performed as part of the global lock manager replacement process, and may also be performed as part of the local lock manager replacement process.
When a local lock manager object exists and a global lock manager replacement is requested, the local lock manager object value is ANDed with a mask of all ones except for the local lock bit corresponding to the user identifier specified. This ANDed value is then compared with zero. When they match, the local lock manager comparison succeeds. When they do not match, the local lock manager comparison fails.
When a local lock manager object exists and a local lock manager comparison is requested, or when a local lock manager object exists and a local lock manager replacement that requires the local lock manager comparison to be performed, is requested, the local lock bit corresponding to the user identifier specified is compared with the local lock bit value specified. When (1) they match and local lock manager comparison is requested or (2) they do not match and local lock manager replacement is requested, the local lock manager comparison succeeds. When (1) they do not match and local lock manager comparison is requested or (2) they match and local lock manager replacement is requested, the local lock manager comparison fails.
Except for the reset lock managers command and the read next lock table entry command, when a lock table write is to be performed, when a list entry creation, replacement, read, movement, or deletion is to be performed, or when an adjunct lock entry is to be updated by an adjunct locking operation, if the local lock manager comparison is requested and succeeds, the command continues; if the local lock manager comparison is requested and fails, command execution is completed with an appropriate response code.
For the reset lock managers command, local lock manager comparison may be performed when the unlock type operand is B‘01’. In this case, if the global lock manager comparison succeeds and the report mismatch type operand is B‘1’, or both global and local lock manager comparisons are successful, the command continues. If the global lock manager comparison or local lock manager comparison fails, and the report mismatch type operand is B‘0’, then a lock manager mismatch response code is returned.
For the read next lock table entry command with the lock request type operand set to compare local lock managers, if the local lock manager comparison succeeds on a nonzero lock table entry 1112 , the entry is returned; if the local lock manager comparison fails, the entry is skipped and the scan of the lock table 1110 continues.
For the read next lock table entry command with the lock request type operand set to compare global lock or local lock managers, if either global lock manager or local lock manager comparison succeeds on a nonzero lock table entry 1112 , the entry is returned; if neither comparison succeeds, the entry is skipped and the scan of the lock table 1110 continues.
Locating a List Entry or List Entry Position
A list entry 1208 is located by unkeyed position. when an entry locator type of locate by unkeyed position is specified or an unkeyed list entry 1208 is created or moved; that is, the designated position or designated target position is specified by means of a list number and a direction.
A list entry 1208 is located by keyed position when the list entries 1208 are keyed and an entry locator type of locate by keyed position is specified or a keyed list entry 1208 is created or moved; that is, the designated position or designated target position is specified by means of a list number, direction, and a list entry key.
A list entry 1208 is located by list entry identifier when an entry locator type of locate by list entry identifier is specified; that is, the designated position is the position of the identified list entry 1208 .
A list entry 1208 is located by list entry name when the list entries 1208 are named and an entry locator type of locate by list entry name is specified; that is, the designated position is the position of the named list entry 1208 .
A list entry 1208 is located by list cursor position when an entry locator type of locate by list cursor position is specified; that is the designated position is the position of the identified list entry 1208 as specified by the list cursor.
A list entry 1208 has a position relative to the designated position or the designated target position. When a list entry 1208 is created, moved, or deleted, the relative positions of the successive list entries 1208 are changed. In these cases, the first entry is the designated list entry 1208 and successive entries are determined by the direction specified.
Regardless of how a list entry 1208 is located, when a left-to-right direction is specified, the last entry is the rightmost entry in the list 1106 , and when a right-to-left direction is specified, the last entry is the leftmost entry in the list 1106 .
Designated List Entry
The designated list entry 1208 is (1) the first entry relative to the designated position before an entry is deleted, moved, read, replaced, replaced and moved, moved and read, or read and deleted, or is (2) the first entry relative to the designated target position after an entry is created.
When a list entry 1208 is located by list entry identifier, the designated list entry 1208 is the identified list entry 1208 .
When a list entry 1208 is located by list entry name, the designated list entry 1208 is the named list entry 1208 .
When a list entry 1208 is located by list cursor position, the designated list entry 1208 is the identified list entry 1208 as specified by the list cursor.
When a list entry 1208 is located by unkeyed position and a left-to-right direction is specified, the designated list entry 1208 is the leftmost entry in the list 1106 . When a list entry 1208 is located by unkeyed position and a right-to-left direction is specified, the designated list entry 1208 is the rightmost entry in the list 1106 .
When (1) a list entry 1208 is located by keyed position the entry locator key type is primary, and the KRT does not indicate key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with an equal key, a less than or equal key, or a greater than or equal key, exists on the list 1106 , depending on the key request type, and (4) a left-to-right direction is specified, then the designated list entry 1208 is the leftmost entry with a key equal, with the largest key less than or equal, or with the smallest key greater than or equal to the specified list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is primary, and the KRT does not indicate key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with an equal key, a less than or equal key, or a greater than or equal key, exists on the list 1106 , depending on the key request type, and (4) a right-to-left direction is specified, then the designated list entry 1208 is the rightmost entry with a key equal, with the largest key less than or equal, or with the smallest key greater than or equal to the specified list entry key request operand 1010 . When (1) a list entry 1208 is located by keyed position, the entry locator key type is secondary, and the SKRT does not indicate key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with an equal secondary key, a less than or equal secondary key, or a greater than or equal secondary key, exists on the list 1106 , depending on the secondary key request type, and (4) a left-to-right direction is specified, then the designated list entry 1208 is the leftmost entry with a secondary key equal, with the largest secondary key less than or equal, or with the smallest secondary key greater than or equal to the specified secondary list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is secondary, and the SKRT does not indicate key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with an equal secondary key, a less than or equal secondary key, or a greater than or equal secondary key, exists on the list 1106 , depending on the secondary key request type, and (4) a right-to-left direction is specified, then the designated list entry 1208 is the rightmost entry with a secondary key equal, with the largest secondary key less than or equal, or with the smallest secondary key greater than or equal to the specified secondary list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is primary, and the KRT indicates key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with a key within range exists on the list 1106 , and (4) a left-to-right direction is specified, then the designated list entry 1208 is the leftmost entry with a key value greater than or equal to the specified list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is primary, and the KRT indicates key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with a key within range exists on the list 1106 , and (4) a right-to-left direction is specified, then the designated list entry 1208 is the rightmost entry with a key value less than or equal to the specified maximum list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is secondary, and the SKRT indicates key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with a secondary key within range exists on the list 1106 , and (4) a left-to-right direction is specified, then the designated list entry 1208 is the leftmost entry with a secondary key value greater than or equal to the specified secondary list entry key request operand 1010 .
When (1) a list entry 1208 is located by keyed position, the entry locator key type is secondary, and the SKRT indicates key range, (2) entry deletion, read, replacement, or movement is requested, (3) a list entry 1208 with a secondary key within range exists on the list 1106 , and (4) a right-to-left direction is specified, then the designated list entry 1208 is the rightmost entry with a key value less than or equal to the specified maximum secondary list entry key request operand 1010 .
Designated Position
The designated position is the position of the designated list entry 1208 before an entry is moved, deleted, read, replaced, replaced and moved, moved and read, or read and deleted.
The designated position is specified (1) by an unkeyed position, (2) by a keyed position, (3) by a list entry identifier, (4) by a list entry name, or (5) by a list cursor, depending on the entry locator type and the entry locator key type specified and the type of structure allocated.
When a list entry 1208 is located by list entry identifier or by list entry name, the designated position exists when the list entry 1208 exists.
When a list entry 1208 is located by list cursor, the designated position exists when the identified list entry 1208 exists as specified by the list cursor.
When a list entry 1208 is located by unkeyed position, the designated position exists when the list 1106 exists and there is at least one entry on the list 1106 .
When a list entry 1208 is located by keyed position and entry creation is not requested, the designated position exists when a list entry 1208 in the list 1106 has a key that is equal, greater than or equal, or less than or equal to the specified list entry key in the list 1106 , depending on the key request type.
When a list entry 1208 is located by keyed position, the entry locator key type is primary, and entry creation is not requested, the designated position exists when a list entry 1208 in the list 1106 has a key that is equal to, greater than or equal to, less than or equal to, or within the range specified by the list entry key and the maximum list entry operands, depending on the key request type.
When a list entry 1208 is located by keyed position, the entry locator key type is secondary, and entry creation is not requested, the designated position exists when a list entry 1208 in the list 1106 has a secondary key that is equal to, greater than or equal to, less than or equal to, or within the range specified by the secondary list entry key and the maximum secondary list entry operands, depending on the secondary key request type.
When the designated position does not exist, an appropriate response code is returned.
Designated Target Position
The designated target position is the position of the designated list entry 1208 after an entry is created or moved.
The designated target position is specified (1) by an unkeyed position or (2) by a keyed position, depending on the type of structure allocated.
When a list entry 1208 is located by unkeyed position and a left-to-right direction is specified, then the designated target position is the leftmost position in the list 1106 . When a list entry 1208 is located by unkeyed position and a right-to-left direction is specified, then the designated target position is the rightmost position in the list 1106 .
When (1) a list entry 1208 is located by keyed position, (2) entry creation or movement is requested, (3) a list entry 1208 with an equal key of the specified entry locator key type exists on the list 1106 , (4) a left-to-right direction is specified, then the designated target position is the position of the leftmost entry with the same key.
When (1) a list entry 1208 is located by keyed position, (2) entry creation or movement is requested, (3) a list entry 1208 with an equal key of the specified entry locator key type exists on the list 1106 , (4) a right-to-left direction is specified, then the designated target position is the position of the rightmost entry with the same key.
When (1) a list entry 1208 is located by keyed position, (2) entry creation or movement is requested, and (3) all entries on the list 1106 have a key of the specified entry locator key type greater than the specified key, the designated target position is the leftmost position in the list 1106 .
When (1) a list entry 1208 is located by keyed position, (2) entry creation or movement is requested, (3) at least one list entry 1208 on the list 1106 has a key of the specified entry locator key type less than the specified key, and (4) there is no list entry 1208 in the list 1106 that matches the specified key, then the designated target position is the first position after the rightmost entry with a key less than the specified list entry key in the list 1106 .
When a list entry 1208 is located by keyed position and entry creation or movement is requested, the designated target position exists when the list 1106 exists.
Comparing List Numbers
When the list number comparison type is active and a list entry 1208 is not created, a list number comparison is requested.
When list number comparison is requested, the list number object is compared with the list number specified. If they do not match, the list number comparison fails, command execution is completed with an appropriate response code or command execution continues by skipping the current list entry 1208 , depending on the command.
Comparing Counts
There are four sets of counts that are compared, depending on the process requested: the list set entry counts, the list set element counts, the event monitor controls counts, and the list entry counts or list element counts, depending on the element count indicator.
Comparing Event Monitor Controls Counts
The maximum event monitor controls count object is compared with the event monitor controls count object whenever an event monitor is registered and event monitor controls creation is requested. The event monitor controls object space is full when the maximum event monitor controls object equals the event monitor controls object.
Comparing List Element Counts
The list element count limit object is compared with the list element count object whenever a list entry 1208 is written or moved, the suppress list limit comparison control is inactive, and the element count indicator in the list structure type is active. If the sum of the list element count and the number of additional list elements 1214 required exceeds the list element count limit, the list 1106 is full. When the list 1106 is full and a write or move operation is requested, an appropriate response code is returned.
The list element count limit or list entry count limit is updated on a write list controls command, depending on the list control type.
Comparing List Entry Counts
The list entry count limit object is compared with the list entry count object whenever a list entry 1208 is created or moved, the suppress list limit comparison control is inactive, and the element count indicator in the list structure type is inactive. A list 1106 is full when the number of list entries 1208 created matches or exceeds the list entry count limit. When the list 1106 is full and a create or move operation is requested, an appropriate response code, depending on the command, is returned.
The record global lock manager command is an exception to list entry count limit comparison.
Comparing List Set Element Counts
The maximum list set element count object is compared with the list set element count object whenever a data list entry 1212 is written. If the sum of the list set element count and the number of additional list elements 1214 required exceeds the maximum list set element count, the list set 1104 is full. When the list set 1104 is full, and list entry creation or replacement, or retry data block creation is requested, an appropriate response code is returned.
Comparing List Set Entry Counts
The maximum list set entry count object is compared with the list set entry count object whenever a list entry 1208 is created. A list set 1104 is full when the number of list entries 1208 created and not deleted matches the maximum list set entry count. When a list set 1104 is full and list entry creation is requested, an appropriate response code, depending on the command, is returned.
Updating Counts
There are three types of counts that are updated, depending on the process requested: the list set entry count, the list set element count, and the list entry count or list element count, depending on the count indicator.
Updating the List Element Counts
The list element counts are updated when the element count indicator in the list structure type is active and a list entry 1208 is created, deleted, moved to another list 1106 , or replaced and the number of list elements 1214 associated with the list entry 1208 is changed or a retry data block is created or deleted. When the list entry 1208 is also the retry data block, the count is at most incremented or decremented by the number of list elements 1214 associated with the list entry 1208 .
Updating the List Entry Counts
The list entry counts are updated when the element count indicator in the list structure type is inactive and a list entry 1208 is created, deleted, or moved to another list 1106 .
Updating the List Set Element Count
The list set element count is updated whenever a list entry 1208 is created, deleted, or replaced and the number of list elements 1214 associated with the list entry 1208 is changed.
Updating the List Set Entry Count
The list set entry count is updated whenever a list entry 1208 created or deleted.
Comparing Version Numbers
Version numbers may be compared when an entry is replaced, read, moved, or deleted, or when an adjunct lock entry is updated by an adjunct locking operation, depending on the version request type and the version comparison request type specified. When the first bit of the version request type is B‘1’, the version number object is compared with the CVN request operand 1010 . When the VCRT is B‘0’ and they are equal or when the VCRT is B‘1’ and the version number object is less than or equal to the CVN operand, the comparison is successful and the command continues. If the comparison fails, command execution is completed with an appropriate response code or command execution continues by skipping the current list entry 1208 , depending on the command.
Updating a Version Number
When an entry is created, replaced, read, or moved, or when an adjunct lock entry is updated by an adjunct locking operation, a version number may be updated depending on the version request type specified.
When a version request type of B‘ 001 ’ is specified, or a version request type of B‘101’ is specified and version number comparison is successful, the version number is decremented by one.
When a version request type of B‘010’ is specified, or a version request type of B‘110’ is specified and version number comparison is successful, the version number is incremented by one.
When a version request type of B‘011’ is specified, or a version request type of B‘111’ is specified and version number comparison is successful, the version number object is set to the version number request operand 1010 .
Updating the List Assignment Key
The assignment key for the target list 1106 may be updated on a move list entry, a move list entries, a move and read list entry, a write and move list entry, or a write list entry command.
When the assignment key request type indicates that the key is assigned, the conditions for key assignment for the designated list entry 1208 are satisfied as specified by the AKRT operand, and the assignment key update type is increment the value of the assignment key increment is added to the assignment key and the resultant is compared with the assignment key threshold. If the resultant is less than or equal to the assignment key threshold, the resultant is stored in the assignment key. If the resultant is greater than the assignment key threshold, the assignment key is not updated and an appropriate response code is returned.
Writing a List Entry
A list entry 1208 may be written on a write list entry or a write and move list entry command. A list entry 1208 is written when an entry is created or replaced.
When a list entry 1208 is created, the data and adjunct indicators within the list structure type object are used to determine whether or not to write the data or adjunct list entry, or both. When a list entry 1208 is replaced, the data and adjunct indicators within the list entry type operand are used to determine whether or not to write the data or adjunct list entry, or both.
When the data indicator is active, the data list entry 1212 is written from the data block 1006 . When the adjunct indicator is active, the adjunct list entry 1216 is written from the adjunct list entry value request operand 1010 .
When the data list entry 1212 is replaced and the data list entry size operand is smaller than the data list entry size object, the data list entry is contracted to the new size, the data block 1006 is stored in the data list entry, and the data list entry size object in the list entry controls 1210 is updated with the value of the data list entry size operand. When the data list entry 1212 is replaced and the data list entry size operand is larger than the data list entry size object, the data list entry is expanded to the new size, the data block 1006 is stored in the data list entry, and the data list entry size object in the list entry controls 1210 is updated with the value of the data list entry size operand.
When an adjunct list entry 1216 is replaced and secondary keys are supported in the structure, bytes 0 to 31 in the adjunct list entry value request operand 1010 are not stored and bytes 32 to 63 in the adjunct list entry value request operand 1010 are stored in the secondary adjunct data entry. The secondary list entry key is not changed when the adjunct list entry 1216 is replaced.
Creating a List Entry
List entry creation is requested on a write list entry or write and move list entry command, depending on the write request type specified. List entry creation is also requested on a record global lock manager command or may be also requested by an adjunct lock request process.
When a write request type of create list entry is specified, list entry creation is unconditionally requested. When a write request type of replace or create list entry is specified, list entry creation is conditionally requested; that is, the list entry creation is requested when the designated list entry 1208 does not exist.
When the list set 1104 and the target list 1106 is not full and list entry creation is requested, a list entry 1208 may be created. When a list entry 1208 is created on the target list 1106 , (1) the list set entry count and when it exists, the associated list entry count are each incremented by one, (2) the list set element count and when it exists, the associated list element count are each increased by the value of the data list entry size, and (3) the write result response operand (WRES) 1014 is set to “a new list entry was created”.
A list entry 1208 is created at the first entry position relative to the designated target position, and the relative position of all succeeding entries is increased by one.
When a keyed entry is created by executing the write list entry command, if the AKRT operand is either assigned on create or assigned on create or move, and if the assignment key object in the target list 1106 is less than or equal to the assignment key threshold object, then the target key is set to the value of the assignment key object in the target list 1106 prior to updating the list assignment key. If the AKRT operand is either assigned on create or assigned on create or move, and if the assignment key object in the target list 1106 is greater than the assignment key threshold object, the command is completed without creating the list entry 1208 , and an appropriate response code is returned.
When a keyed entry is created by executing the write and move list entry command and if the AKRT operand is either not assigned or assigned on move, the MELT operand specifies which key value the target key is set to: zero means the LEK in MCB and one means the TLEK in MCB. If the AKRT operand is either assigned on create or assigned on create or move, and if the assignment key object in the target list 1106 is less than or equal to the assignment key threshold object, then the target key is set to the value of the assignment key object in the target list 1106 prior to updating the list assignment key. If the AKRT operand is either assigned on create or assigned on create or move, and if the assignment key object in the target list 1106 is greater than the assignment key threshold object, the command is completed without creating the list entry 1208 , and an appropriate response code is returned.
When a write request type of create list entry is specified and the list entry name already exists, an appropriate response code is returned.
When a list entry 1208 is created with a program list entry identifier indicator value of inactive, the coupling facility generates the list entry identifier value.
When a list entry 1208 is created with a program list entry identifier indicator value of active, the list entry identifier value for the entry is the value provided by the program in the list entry identifier operand in the MCB for the command. The LEID value stored in the list entry 1208 is the LEID operand. The LEID value is checked to ensure that it is unique in the structure. There is no requirement for the LEID value to be unique for any specific length of time and may be reused once the entry which has that LEID assigned to it is deleted.
Replacing a List Entry
A list entry 1208 may be replaced on a write list entry or write and move list entry command.
When a write request type of replace list entry or replace or create list entry is specified and the designated list entry 1208 exists, the list entry 1208 may be replaced.
When a list entry 1208 is replaced, the list set element count and when it exists, the associated list element count are each increased or decreased by the change in the data list entry size, and the write result response operand (WRES) 1014 is set to existing list entry replaced.
When a write request type of replace list entry is specified and the designated list entry 1208 does not exist, an appropriate response code is returned.
The position of an entry is not affected when it is replaced.
Reading a List Entry
A list entry 1208 may be read on a read list entry, move and read list entry, or read and delete list entry command, and one or more list entries 1208 may be read on a read list or read list set command.
When the data indicator in the list entry type specified is active, one or more data list entries 1212 may be read into the data area, depending on the command executed. When the adjunct indicator in the list entry type specified is active, one adjunct list entry 1216 may be read into the adjunct list entry value response operand 1014 , or one or more adjunct list entries are read into the data area, depending on the command executed.
When a read list or read list set command is executed, the adjunct or data list entries are always read into the data area. Otherwise, when any other command that does a read operation is executed, the adjunct list entry 1216 is read into the response operand 1014 .
The position of an entry is not affected by a read operation.
Moving a List Entry
A list entry 1208 may be moved on a move list entry, move list entries, write and move list entry, or a move and read list entry command. List entries 1208 may be moved between lists 1106 or to the same list 1106 within a list set 1104 .
The source list 1106 is the list 1106 associated with the designated list entry 1208 . The target list 1106 is the list 1106 associated with the designated target position.
When a list entry 1208 is moved from one list 1106 to another and the list entry count exists, the list entry count of the source list 1106 is decremented by one and the list entry count of the target list 1106 is incremented by one.
When a list entry 1208 is moved from one list 1106 to another and the list element count exists, the list element count of the source list 1106 is decreased by the value of the data list entry size and the list element count of the target list 1106 is increased by the same amount.
A list entry 1208 is moved from the first entry position relative to the designated position, and the relative position of all succeeding entries is decreased by one.
A list entry 1208 is moved to the first entry position relative to the designated target position, and the relative position of all succeeding entries is increased by one.
When a keyed entry is moved and if the AKRT operand is either not assigned or assigned on create, the MELT operand specifies which key value the target key is set to zero means the LEK in the list entry 1208 and one means the TLEK in MCB.
If the AKRT operand is either assigned on move or assigned on create or move, and if the assignment key object in the target list 1106 is less than or equal to the assignment key threshold object, then the target key is set to the value of the assignment key object in the target list 1106 prior to updating the list assignment key.
If the AKRT operand is either assigned on move or assigned on create or move, and if the assignment key object in the target list 1106 is greater than the assignment key threshold object, the command is completed without creating the list entry 1208 , and an appropriate response code 10 is returned.
A list entry key is updated by the move process if the target key is set to either the TLEK request operand 1014 or the assignment key object. The value of the list entry key may or may not be changed when it is updated. A list entry key is not updated by the move process if the target key is set equal to the list entry key object.
Similarly, a secondary list entry key is updated by the move process if the target secondary key is set to the value of the TSLEK request operand 1010 , and is not updated by the move process if the target secondary key is set equal to the SLEK object. The value of the secondary list entry key may or may not be changed when it is updated.
When a keyed entry is moved to the same list 1106 , the LEK object is not updated by the move process, and the MPKP operand is active, the TDIR operand is ignored and the designated primary key position is not changed.
When a keyed entry with secondary keys is moved to the same list 1106 , the SLEK object is not updated by the move process, and the MSKP operand is active, the STDIR operand is ignored and the designated secondary key position is not changed.
When a keyed entry with secondary keys is moved to the same list 1106 , neither the LEK nor the SLEK object are updated, and both the MPKP and MSKP operands are active, the TDIR and STDIR operands are ignored and no move operation occurs.
When a keyed entry with secondary keys is moved by a move list entries command, the SMELT operand specifies which key value the target secondary key is set to; inactive means the SLEK in the list entry 1208 and active means the TSLEK in the move block. When a list entry 1208 is moved by any other command, the SLEK is not changed. Assignment keys are not supported for secondary keys.
Deleting a List Entry
A list entry 1208 may be deleted on a delete list entry or read and delete list entry command and one or more list entries 1208 may be deleted on a delete list, delete list set or delete list entries command.
When a list entry 1208 is deleted, the list set entry count and when it exists, the list entry count are each decreased by one.
When a list entry 1208 is deleted, the list set element count and when it exists, the list element count are each decreased by the value of the data list entry size.
An entry is deleted at the first entry position relative to the designated position, and the relative position of all succeeding entries is decreased by one.
Notifying a Key Range Monitor
When a key range state transition occurs, one or more list notification commands are initiated for the key range.
When registration of a key range monitor is performed and the initial notification request type operand is active, one or more list notification commands are performed as primary processes for the user. When the specified key range is empty, a list notification command indicating a not-empty-to-empty key range state transition is performed; when the specified key range is not empty, a list notification command indicating an empty-to-not-empty key range state transition is performed.
Registration of a key range monitor may receive a list notification even if the initial notification request type operand is inactive and no key range state transition occurs. This is because the list notification command had been pending since before the last deregistration.
All commands capable of creating, deleting, or moving a list entry 1208 initiate list notification commands as secondary processes for the designated key range that changes state.
Updating the List Cursor
When the list cursor request type (LCURT) operand is active, the list cursor of the list 1106 in which the designated list entry 1208 resides is updated. When the list 1106 is keyed, the list order used in identifying the next and previous list entries 1208 is the primary key order.
When LCURT is inactive or not provided along with the command, no list cursor is updated with two exceptions. The two exceptions are: (1) when a list entry 1208 associated with a list cursor position is moved to another list 1106 , and (2) when a list entry 1208 associated with a list cursor position is deleted. In these two cases, the list cursor of the list 1106 in which the designated list entry 1208 resides is reset to zero.
When the LCURT operand is active, the list cursor is updated. The updated value of the list cursor depends on the designated position or target position, the specified direction, and the specified list cursor update type (LCUT) operand.
List cursor updated to next entry: When a list cursor update type of update cursor to next entry is specified, the list cursor is updated to the list entry identifier of the next list entry 1208 as specified by the designated list entry 1208 and the direction subject to the following boundary conditions:
1. When the designated list entry 1208 is the leftmost entry on the list 11106 and a right-to-left direction is specified, the list cursor is reset to zero. 2. When the designated list entry 1208 is the rightmost entry on the list 1106 and a left-to-right direction is specified, the list cursor is reset to zero.
When a list entry 1208 is created by executing the write and move list entry command, the direction is specified by the TDIR operand; otherwise, the direction is specified by the DIR operand.
List cursor updated to current entry: When a list cursor update type of update cursor to current entry is specified, the list cursor is updated to the list entry identifier of the designated list entry 1208 , provided the designated list entry 1208 is not being deleted or moved to another list 1106 . When the designated list entry 1208 is being deleted or moved to another list 1106 , the list cursor is set to zero.
List cursor maintained at next entry: When a list cursor update type of maintain cursor at next entry is specified and the list entry 1208 associated with the list cursor position is deleted or moved, the list cursor is updated to the list entry identifier of the next list entry 1208 as specified by the designated list entry 1208 and the cursor direction list control subject to the following boundary conditions:
1. When the designated list entry 1208 is the leftmost entry on the list 1106 and the cursor direction is right to left, the list cursor is reset to zero. 2. When the designated list entry 1208 is the rightmost entry on the list 1106 and the cursor direction is left to right, the list cursor is reset to zero.
When the list entry 1208 associated with the list cursor exists and is not being deleted or moved, the list cursor is not updated.
List cursor maintained at current entry: When a list cursor update type of maintain cursor at current entry is specified and the list cursor is zero, the list cursor is updated to the list entry identifier of the designated list entry 1208 , provided the designated list entry 1208 is not being deleted or moved to another list 1106 . When the designated list entry 1208 is being deleted or moved to another list 1106 , the list cursor remains zero.
When the list entry 1208 associated with the list cursor exists and is not being deleted or moved to another list 1106 , the list cursor is not updated. When the designated list entry 1208 is being deleted or moved to another list 1106 , the list cursor is reset to zero.
Registering a Monitor
A monitor is registered by means of the register list monitor or register event monitors command. A list structure user may register as a monitor when the user is attached with a nonzero list notification token.
The register list monitor command can be used to register any of the following four types of monitors: list, event queue, event monitors, and key range. The monitor request type operand is provided to specify the monitor type. The register event monitors command is used to register a number of event monitors.
When the monitor request type operand specifies a list monitor, the list monitoring active flag is set, and the list notification request type and list notification entry number are updated in the list monitor table entry 1304 of the specified list 1106 and user.
When the monitor request type operand specifies an event queue monitor, the event queue 1116 of the specified key type is initialized. The event queue monitoring active flag is set, and the event notification request type and event notification entry number are updated in the event queue controls.
When the monitor request type operand specifies an event monitor or a register event monitors command is executed, the event monitor controls object 1306 of the specified key type of each specified subsidiary list and user is created if it does not exist, and is updated if it does exist.
When the monitor request type operand specifies a key range monitor, the key range monitoring active flag is set, and the key range notification request type and the key range notification entry number are updated in the key range monitor table entry of the specified list 1106 and user.
Deregistering a Monitor
A monitor is deregistered by means of the deregister list monitor or detach list structure user command. The monitor request type operand is provided by the deregister list monitor command to specify the monitor type to be deregistered.
When a list monitor is deregistered, the list monitoring active flag is reset in the list monitor table entry 1304 of the specified list 1106 and user.
When an event queue monitor is deregistered, the event queue monitoring active flag, the event notification request type, and event notification entry number are reset for the event queue controls of the specified key type.
When an event monitor is deregistered the event monitor controls object 1306 associated with the user and the key type and the subsidiary list of the specified key type are deleted.
When a key range monitor is deregistered, the key range monitoring active flag is reset in the list monitor table entry 1304 of the specified list 1106 and user.
Handling of Event Monitor Controls
This section describes processes of creating, updating, queueing, dequeueing, deleting, and withdrawing an event monitor controls object 1306 .
Creating Event Monitor Controls: When a user registers interest in a subsidiary list by means of executing a register list monitor or register event monitors command, if the associated event monitor controls object 1306 does not exist, then an event monitor controls object 1306 is created for the user and the specified subsidiary list.
Updating Event Monitor Controls: When a user registers interest in a subsidiary list by means of executing a register list monitor or register event monitors command, if the associated event monitor controls object 1306 already exists, then the object is updated.
Queueing Event Monitor Controls: The event monitor controls queueing process may be a primary or secondary process, depending on its causing command. When an event monitor is registered by means of the register list monitor command, if the initial notification request type operand is active, the designated subsidiary list is not empty, and the designated event monitor controls object 1306 is not queued, then an event monitor controls queueing process is performed to queue the designated event monitor controls object 1306 to the event queue 1116 of the user as a primary process. When an event monitor is registered by means of the register event monitors command, if the initial notification request type operand is active, and the event monitor queue indicator control operand is inactive, the designated subsidiary list is not empty, and the designated event monitor controls object 1306 is not queued, then an event monitor controls queueing process is performed to queue the designated event monitor controls object 1306 to the event queue 1116 of the user as a primary process. When an event monitor is registered by means of the register event monitors command, if the initial notification request type operand is active, and the event monitor queue indicator control operand is active, the event monitor queue indicator operand is active, and the designated event monitor controls object 1306 is not queued, then an event monitor controls queueing process is performed to queue the designated event monitor controls object 1306 to the event queue 1116 of the user as a primary process.
When execution of a command causes an empty-to-not-empty or not-empty-to-not-empty subsidiary list state transition, an event monitor controls queueing process is initiated for the subsidiary list as a secondary process. All list structure commands capable of creating or moving a list entry 1208 may cause an empty-to-not-empty or not-empty-to-not-empty subsidiary list state transition. Execution of a pending event monitor controls queueing process queues every event monitor controls object 1306 that exists at that time and is associated with the designated subsidiary list to the event queue 1116 of the corresponding key type of the user specified in the event monitor controls object 1306 . No action is taken for those designated event monitor controls objects 1306 that are already queued. If no designated event monitor controls object 1306 exists, no action is taken and the process execution is complete. If there are two or more pending queueing and withdrawal processes for the same subsidiary list, only the most recently initiated process needs to be performed, and all previous queueing or withdrawal processes may be purged. Execution of an event monitor controls queueing process is complete before execution of a subsequent withdrawal process targeted to the same event monitor controls object 1306 begins.
Dequeueing Event Monitor Controls: The event monitor controls objects 1306 of a user are dequeued from the event queue 1116 by means of the dequeue event monitor controls command.
Deleting Event Monitor Controls: When a user deregisters an event monitor, the associated event monitor controls object 1306 is deleted and the event monitor controls deletion process performed is a primary process.
Withdrawing Event Monitor Controls: The event monitor controls withdrawal process may be a primary or secondary process, depending on its causing command. When an event monitor is registered by means of the register list monitor command, if the initial notification request type operand is active, the designated subsidiary list is empty, and the designated event monitor controls object 1306 is queued, then an event monitor controls withdrawal process is performed to withdraw the designated event monitor controls object 1306 from the event queue 1116 of the user as a primary process. When an event monitor is registered by means of the register event monitors command, if the initial notification request type operand is active, the event monitor queue indicator control operand is inactive, the designated subsidiary list is empty, and the designated event monitor controls object 1306 is queued, then an event monitor controls withdrawal process is performed to withdraw the designated event monitor controls object 1306 from the event queue 1116 of the user as a primary process.
When an event monitor is registered by means of the register event monitors command, if the initial notification request type operand is active, the event monitor queue indicator control operand is active, the event monitor queue indicator operand is inactive, and the designated event monitor controls object 1306 is queued, then an event monitor controls withdrawal process is performed to withdraw the designated event monitor controls object 1306 from the event queue 1116 of the user as a primary process.
When execution of a command causes a not-empty-to-empty subsidiary list state transition, an event monitor controls withdrawal process is initiated for the subsidiary list as a secondary process. All list structure commands capable of deleting or moving a list entry 1208 may cause a not-empty-to-empty subsidiary list state transition.
Execution of a pending event monitor controls withdrawal process removes every event monitor controls object 1306 that is associated with the designated subsidiary list from the event queue 1116 of the user specified in the event monitor controls object 1306 . No action is taken for those designated event monitor controls objects 1306 that are not queued. If no designated event monitor controls object 1306 is queued to any event queue 1116 , no action is taken and the process execution is complete. If there are two or more pending queueing and withdrawal processes for the same subsidiary list, only the most recently initiated process needs to be performed, and all previous queueing or withdrawal processes may be purged. Execution of an event monitor controls withdrawing process is complete before execution of a subsequent queueing process targeted to the same event monitor controls object 1306 begins.
Notifying an Event Queue Monitor
When an event queue state transition occurs, one or more list notification commands are generated for the event queue 1116 .
When registration of an event queue monitor is performed and the initial notification request type operand is active, one or more list notification commands are performed as primary processes for the user. When the specified event queue 1116 is empty, a list notification command indicating a not-empty-to-empty queue state transition is performed; when the specified event queue 1116 is not empty, a list notification command indicating an empty-to-not-empty queue state transition is performed.
Registration of an event queue monitor may receive an event queue notification even if the initial notification request type operand is inactive and no event queue state transition occurs. This is because the list notification command had been pending since before the last deregistration.
If performance of an event monitor controls queueing process or event monitor controls withdrawal process causes the designated event queue 1116 to change its state, and if the process is caused by executing a register list monitor or register event monitors command with the initial notification request type operand set to active, then one or more list notification commands are performed as primary processes. If the queueing or withdrawal process is caused by executing any other command, then one or more list notification commands are initiated as secondary processes.
If performance of an event monitor controls dequeueing process or event monitor controls deletion process causes the designated event queue 1116 to change its state, then one or more list notification commands are performed as primary processes. The only exception is that the event monitor controls deletion processes initiated by the detach list structure user command do not initiate any list notification command.
Notifying a List Monitor
When a list state transition occurs, one or more list notification commands are initiated for the list 1106 .
When registration of a list monitor is performed and the initial notification request type operand is active, one or more list notification commands are performed as primary processes for the user. When the specified list 1106 is empty, a list notification command indicating a not-empty-to-empty list state transition is performed; when the specified list 1106 is not empty, a list notification command indicating an empty-to-not-empty list state transition is performed.
Registration of a list monitor may receive a list notification even if the initial notification request type operand is inactive and no list state transition occurs. This is because the list notification command had been pending since before the last deregistration.
All commands capable of creating, deleting, or moving a list entry 1208 initiate list notification commands as secondary processes for the designated list 1106 that changes state.
Notifying a Key Range Monitor
When a key range state transition occurs, one or more list notification commands are initiated for the key range. When registration of a key range monitor is performed and the initial notification request type operand is active, one or more list notification commands are performed as primary processes for the user. When the specified key range is empty, a list notification command indicating a not-empty-to-empty key range state transition is performed; when the specified key range is not empty, a list notification command indicating an empty-to-not-empty key range state transition is performed.
Registration of a key range monitor may receive a list notification even if the initial notification request type operand is inactive and no key range state transition occurs. This is because the list notification command had been pending since before the last deregistration.
All commands capable of creating, deleting, or moving a list entry 1208 initiate list notification commands as secondary processes for the designated key range that changes state.
List Command Operands
Adjunct List Entry (ALE): A value that is read from or written to an adjunct list entry 1216 . This request operand 1010 is ignored unless the list structure 902 has adjunct list entries 1216 and (1) a create operation is requested, or (2) the list entry type specifies an adjunct list entry 1216 and a replace operation is requested.
Adjunct Format Control (AFC): A bit string consisting of adjunct format bits. Each bit is associated with a particular adjunct format. The adjunct format control bits include an adjunct secondary key indicator and adjunct lock entry indicator.
The bits are mutually exclusive; at most one bit is active. When all the bits are inactive, the adjunct is unformatted and contains the adjunct data list entry.
Allocation Type (AT): A four-bit value that indicates what action an allocate command should take. The first two bits are the ratio indicators (RI), the third bit is the structure size indicator (SSI), and the fourth bit is the user structure control indicator (USCI).
An allocation type of all inactive bits specifies that all list allocation processes are checkpointed and stopped.
The first bit of the ratio indicator is the monitor-to-entry storage ratio indicator (MTESRI), the second bit is the entry-to-element ratio indicator (ETELRI).
The monitor-to-entry storage ratio indicator is not meaningful at this granularity when inactive, but indicates when active to initiate or continue monitor-to-entry storage reapportionment as specified by the target monitor-to-entry storage ratio request operand, and, if ETELRI is inactive, resume entry-to-element reapportionment as specified by the pending entry-to-element ratio.
The entry-to-element ratio indicator is not meaningful at this granularity when inactive, but indicates when active to initiate or continue entry-to-element reapportionment as specified by the target entry-to-element ratio request operand, and, if MTESRI is inactive, resume monitor-to-entry storage reapportionment as specified by the pending monitor-to-entry storage ratio.
The structure size indicator in not meaningful at this granularity when inactive, but indicates when active to initiate or continue expansion or contraction as specified by the target structure size request operand, and resume each suspended reapportionment as specified by the associated pending ratio if the associated ratio indicator is zero.
The user structure control indicator indicates whether the user structure control is updated.
The structure authority is always compared and conditionally replaced. The allocation type is ignored unless the initial allocation process is complete. When the data indicator (DI) in the list structure type (LST) object is inactive, the entry-to-element ratio indicator (ETELRI) must be inactive; when the key indicator (KI) in the LST object is inactive, the monitor-to-entry storage ratio indicator (MTESRI) must be inactive.
Apportionment Priority Indicator (API): A flag directs the resolution of conflicts in the establishment of an accurate ratio in an expansion or contraction process or when the list 1106 is initially allocated. When active, it indicates that maintaining an accurate ratio is of higher priority than maximizing the amount of storage resources that are assigned to the structure. When inactive, it indicates that maximizing storage resources is of higher priority and a less accurate ratio will be tolerated.
This operand is ignored when a reapportionment process is specified and an expansion or contraction process is not specified, or when a list 1106 is initially allocated and the target counts priority indicator is active.
Assignment Key Increment (AKI): A four-byte unsigned binary integer that is added to the value of the assignment key when the assignment key is updated. This request operand 1010 is ignored unless the list entries 1208 are keyed, the assignment key request type indicates that the key is assigned, and the assignment key update type is increment.
Assignment Key Request Type (AKRT): A two-bit value that indicates when the list entry key is set to the value of the assignment key in the list controls 1202 . It may indicate that the list entry key is (1) not assigned, (2) assigned on move, (3) assigned on create, or (4) assigned on create or move.
Assignment Key Update Type (AKUT): A one-bit value that indicates how the assignment key is updated. It may indicate that the assignment key is (1) not updated or (2) incremented.
Comparative Global Lock Manager (CGLM): A value that is compared to the global lock manager object. This request operand 1010 is ignored unless the lock request type is valid and specifies a comparison of the global lock managers.
Comparative List Authority (CLAU): A value that is compared to the list authority object.
Comparative Structure Authority (CSAU): A value that is compared to the structure authority object.
Current Data Index (CDX): A value that indexes to the current list entry name or list entry identifier in the data block 1006 for the delete list entries command.
Current Event Index (CTX): A value that indexes to the current event in the data block 1006 for the register event monitors command.
Cursor Direction (CDIR): Indicates how the list cursor is updated (left to right or right to left) when the list cursor is maintained or initialized by a write list controls command.
Cursor Direction Type (CDT): Determines how the cursor direction and location is set for the write list controls command. When the cursor direction type bit is inactive, the list cursor is initialized to the leftmost or rightmost list entry 1208 based on the CDIR operand. When the cursor direction type bit is active, the list cursor is initialized based on the LEID and the CDIR operand. This operand is ignored if the list cursor bit in the LCT operand is inactive.
Data Block Size (DBS): Specifies the size of the data block 1006 as an integral multiple of 4096-byte units. Valid values range from 1 to 16 if the command is not read list structure controls. If the command is read list structure controls, valid values range from 0 to 16.
Data Entries Locator Type (DAELT): Indicates how a list entry 1208 is located for the move list entries command.
When the list structure 902 does not have list entry names, the operand may indicate locate by list entry identifier.
When the list structure 902 has list entry names, the operand may indicate (1) locate by list entry identifier or (2) locate by list entry name.
Data List Entry (DLE): A value that is read from or written to a data list entry 1212 .
Data List Entry Size (DLES): Specifies the size of the data list entry 1212 as an integral multiple of the list element size.
Delete Entries Locator Type (DELT): Indicates how a list entry 1208 is located for the delete list entries command.
When the list structure 902 does not have list entry names, the operand may indicate locate by list entry identifier.
When the list structure 902 has list entry names, the operand may indicate (1) locate by list entry identifier or (2) locate by list entry name.
Delete List Entries Count (DLEC): Specifies the number of deleted list entries 1208 .
Direction (DIR): indicates whether the positions of the list entries 1208 are numbered left to right or right to left relative to a designated position.
Element Toleration Factor (ELTF): When divided by 100, specifies the minimum number of data list elements 1214 that may still be assigned to list entries 1208 or retry data blocks, or both, after any checkpoint of a contraction, expansion, entry-to-element reapportionment, or monitor-to-entry storage reapportionment process as a percentage of the total number of existing data list elements 1214 .
Ending Data Index (EDX): Indexes to the last list entry name or list entry identifier in the data block 1006 for the delete list entries command.
Ending Event Index (ETX): Indexes to the last event in the data block 1006 for the register event monitors command.
Entry Locator Key Type (ELKT): Indicates the type of key (primary or secondary) that is used for locating a list entry 1208 when the entry locator type specifies locate by keyed position.
Event monitor queue indicator control (EMQIC): Controls EMC enqueueing or withdrawal. The EMQIC bit is ignored if the INRT bit is inactive. If the EMQIC bit is active and the INRT bit is active, the EMC is queued, not queued, withdrawn, or not withdrawn based on the EMQI bit. If the EMQIC bit is inactive and the INRT bit is active, the EMC is queued, not queued, withdrawn, or not withdrawn based on the state of the sublist.
Entry Locator Type (ELT): Indicates how a list entry 1208 is located for a read, replace, or delete operation, or as the source of a move operation.
When the list structure 902 does not have list entry names or list entry keys, the operand may indicate (1) locate by unkeyed position, (2) locate by list entry identifier, (3) locate by list cursor position.
When the list structure 902 has list entry names, the operand may indicate (1) locate by unkeyed position, (2) locate by list entry identifier, (3) locate by list entry name, or (4) locate by list cursor position.
When the list structure 902 has list entry keys, the operand may indicate (1) locate by unkeyed position, (2) locate by keyed position, (3) locate by list entry identifier, or (4) locate by list cursor position.
When a list entry 1208 is created, the entry locator type operand is ignored. Instead, for a create or move operation, the target list entry position is located by keyed position when the entries are keyed, or by unkeyed position when the entries are not keyed.
When a list set 1104 is not allocated, all ELTs are invalid.
Entry Toleration Factor (ETF): When divided by 100, specifies the minimum number of list entries 1208 that may still be created after any checkpoint of a contraction, expansion, entry-to-element reapportionment, or monitor-to-entry storage reapportionment process as a percentage of the total number of existing list entries 1208 .
Event Monitor Controls Dequeued Count (EMCDC): Specifies the number of event monitor controls objects 1306 dequeued by means of the dequeue event monitor controls command.
Event Monitor Toleration Factor (EMTF): When divided by 100, specifies the minimum number of event monitor controls 1306 that may still be created after any checkpoint of a contraction, expansion, entry-to-element reapportionment, or monitor-to-entry storage reapportionment process as a percentage of the total number of existing event monitor controls 1306 .
Event Notification Entry Number (ENEN): Specifies a list notification vector entry.
Event Notification Request Type (ENRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on a monitored event queue 1116 .
Event Queue Monitoring Active Bit (EQMAB): Specifies whether the user associated with the event queue 1116 is monitoring the event queue 1116 .
Failed Replacement Indicator (FRPI): When active, indicates that a replacement of the data list entry failed with a list set full condition and the size of the DLES operand is smaller than or equal to the size of the DLES object.
Granular Version Number Comparison (GVNC): indicates how the version number comparison is to be performed for move list entries and delete list entries commands. If the flag is active, the VCRT, VRT, CVN, and if applicable the VN in the data block 1006 are used to compare, and if applicable, replace, the version for the list entry 1208 , with each list entry 1208 in the data block 1006 having its own set of values. If the flag is inactive, the VCRT, VRT, CVN, in the MCB are used to compare the version for all list entries 1208 processed.
Halt on miscompare (HOM): Determines if the move list entries or delete list entries command stops processing on a miscompare. If the flag is active, processing of the command stops when a miscompare occurs. If the flag is inactive, processing of the command continues when a miscompare occurs.
Halt register event monitors (HREMS): Controls if an EMC is not registered and skipped or the registration process is halted. When the AOC bit is active and the HREMS bit is inactive, the EMC is skipped and processing continues if an EMC specifies a UID that is not assigned. When the AOC bit is active and the HREMS bit is active, processing is halted when an EMC that specifies a UID that is not assigned is processed. When the AOC bit is inactive and the HREMS bit is inactive, the EMC is skipped and processing continues if an EMC specifies a UID that is not attached. When the AOC bit is inactive and the HREMS bit is active, processing is halted when an EMC that specifies a UID that is not attached is processed.
Initial Notification Request Type (INRT): Indicates whether to notify a monitor of the initial state of the monitored object, except that when the request monitor type specifies an event monitor and the EMQIC bit is active, the initial state of the monitored object is ignored and the EMQI bit in the REMS registration block is used.
When the monitor request type specifies a list monitor, the initial notification request type indicates whether the list monitor is notified.
When the monitor request type specifies an event queue monitor, the initial notification request type indicates whether the event queue monitor is notified.
When the monitor request type specifies an event monitor, the initial notification request type indicates whether the event monitor controls object is queued or withdrawn, or no action taken.
When the monitor request type specifies a key range, the initial notification request type indicates whether the key range monitor is notified.
Key Comparison Type (KCT): Indicates whether key comparison is requested.
Key Range Empty Notification Threshold (KRENT): Specifies a number which is one less than the number of list entries 1208 that must remain in the key range to suppress a not-empty-to-empty list notification.
Key Range List Entry Key (KRLEK): Specifies the lower value of the key range.
Key Range Maximum List Entry Key (KRMLEK): Specifies the upper value of the key range.
Key Range Monitoring Active Bit (KRMAB): Specifies whether the user associated with the key range monitor table entry 1302 is monitoring the key range.
Key Range Not-empty Notification Threshold (KRNENT): Specifies one less than the number of list entries 1208 required in the key range in order to generate an empty-to-not-empty list notification.
Key Range Notification Entry Number (KRNEN): Specifies a list notification vector entry.
Key Range Notification Request Type (KRNRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on a monitored key range for the specified user identifier.
Key Request Type (KRT): Indicates how a keyed list entry 1208 is located when an entry is replaced, moved, read or deleted. For the read list command, when the key comparison type operand is active, the key request type operand also specifies how keys are compared. A two-bit value that indicates how a list entry 1208 is located when the entry locator type indicates location by keyed position, the entry locator key type is primary, and an entry is replaced, moved, read or deleted. When the key comparison type operand is active, the key request type operand also specifies how keys are compared.
The KRT operand is a dual purpose operand. When KCT is active, the KRT operand is used to control the type of list entry key comparison to be performed on a command. When the KCT is inactive, no list entry key comparison is performed. When ELT designates that an entry is located by keyed position, and the ELKT operand is primary, the KRT operand is used to control the type of entry location performed. When the ELT designates an entry location by a means other than keyed position, or the ELKT operand is secondary, the KRT has no effect on entry location. The type determines the relationship between the list entry key object and the list entry key and maximum list entry key operands. It may indicate a comparison for (1) equal to the list entry key operand, (2) less than or equal to the list entry key operand, (3) greater than or equal to the list entry key operand, or (4) within the range of the list entry key to the maximum list entry key operands, inclusive.
For the delete list entry, move and read list entry, move list entry, read and delete list entry, read list entry, write and move list entry, and write list entry commands the value “within the range” is invalid. For the delete list entries, delete list set, read list set, read list, delete list, and move list entries commands the value “within the range” specifies that the keyed list entry satisfies the search criterion or the key comparison criteria if it is within the range of the list entry key to the maximum list entry key operands, inclusive.
The key request type operand is ignored unless an entry is replaced, moved, read or deleted, and (1) the key comparison type is active, or (2) the entry locator type is locate by keyed position and the entry locator key type is primary.
Key Type (KT): Indicates the type of key (primary or secondary) that is used for selecting an event queue 1116 or the event monitor controls 1306 for a subsidiary list.
List Authority (LAU): A value that is conditionally updated.
List Authority Comparison Type (LAUCT): Indicates the procedure for comparing the list authority. It may indicate (1) do not compare list authorities, (2) compare list authority object and CLAU operand for being equal, or (3) compare list authority object for being less than or equal to the CLAU operand.
List Authority Replacement Type (LAURT): Indicates the procedure for updating the list authority. It may indicate (1) do not replace the list authority or (2) replace the list authority object with the LAU operand.
List Control Type (LCT): A bit string consisting of 16 consecutive list control update bits. Each bit is associated with a particular list control 1202 , and when active, causes the list control 1202 to be updated to a specified value. When the bit is inactive, the associated list control 1202 is not updated. The association of list control update bits to list controls 1202 is as follows:
Bit
List control
0-3
Invalid.
4
List state transition count
5
List empty notification threshold and List not-empty notification
threshold
6
Key range empty notification threshold and Key range not-empty
notification threshold
7
Key range maximum list entry key and Key range list entry key
8-10
Invalid
11
Assignment key.
12
Assignment key threshold.
13
List cursor and cursor direction.
14
User list control.
15
List element count limit or list entry count limit.
Bits 6, 7, 11 and 12 are ignored unless the list entries 1208 are keyed.
List Count (LC): Specifies the number of lists 1106 to be allocated.
List Cursor Request Type (LCURT): Indicates whether the list cursor is to be updated.
List Cursor Update Type (LCUT): Indicates how a list cursor is updated when list cursor update is requested. It may indicate (1) update cursor to next entry, (2) update cursor to current entry, (3) maintain cursor at next entry, or (4) maintain cursor at current entry.
List Element Characteristic (LELX): Specifies the number of bytes in each list element 1214 .
List Element Count Limit (LELCL): Specifies the maximum number of list elements 1214 in a list 1106 .
List Empty Notification Threshold (LENT): Specifies a number which is one less than the number of list entries 1208 that must remain on the list 1106 to suppress a not-empty-to-empty list notification.
List Not-empty Notification Threshold (LNENT): Specifies one less than the number of list entries 1208 required on the list 1106 in order to generate an empty-to-not-empty list notification.
List Entry Count Limit (LECL): Specifies the maximum number of list entries 1208 in a list 1106 .
List Entry Identifier (LEID): An integer that designates the list entry 1208 . The LEID is written into the LEID object when the entry is created and into the list cursor object when a write list controls command updates the list cursor and the cursor direction type is active.
For LEIDs when the program list entry identifier indicator is inactive and a list entry 1208 is being created, a nonzero list entry identifier that is unique to a list set 1104 for at least 100 years is assigned by the coupling facility.
For LEIDs when the program list entry identifier indicator is active and a list entry 1208 is being created, the LEID value in the MCB is written into the LEID object for the list entry 1208 . The LEID value is checked to ensure that it is unique in the structure. There is no requirement for the LEID value to be unique for any specific length of time and may be reused once the entry which has that LEID assigned to it is deleted.
For LEIDs when the program list entry identifier indicator is active and a list entry 1208 is being created, the LEID value may be any value except zero, which is invalid.
When the command is write list controls, the LEID operand may be zero or must designate a list entry 1208 that exists on the list 1106 specified by the LN operand. The LEID operand is ignored on write list controls unless the list cursor bit and the cursor direction type are both active.
List Entry Key (LEK): Partially specifies a list entry position or an event monitor controls object 1306 .
List Entry Name (LEN): Fully specifies a list entry position.
List Entry Type (LET): Indicates which list entries 1208 are read or replaced upon normal completion of the command execution. The first bit is a data indicator (DI) that indicates whether or not a data list entry is read or written, and the second is an adjunct indicator (AI) that indicates whether or not an adjunct list entry is read or written.
List Monitoring Active Bit (LMAB): Specifies whether the user associated with the list monitor table entry 1304 is monitoring the list 1106 .
List Notification Entry Number (LNEN): Specifies a list notification vector entry.
List Notification Request Type (LNRT): Indicates whether the list notification vector summaries are to be updated when an empty to not-empty state transition occurs on a monitored list 1106 .
List Notification Token (LNT): Specifies a list notification vector to the system.
List Number (LN): An integer that designates a list 1106 in a list set 1104 .
List Number Comparison Type (LNCT): Indicates whether list number comparison is requested.
List Scan Key Type (LSKT): Indicates the key order (primary or secondary) used by a list scan process in a delete list or read list command.
Lock Request Type (LRT): A value that indicates the type of lock request. When a single list entry command is issued, the lock request type may be: (1) no lock process requested; (2) compare the global lock managers; (3) replace the global lock manager; (4) replace a local lock manager; or (5) replace the global lock and local lock managers.
When a multiple list entry command is issued, the lock request type may be: (1) no lock manager comparison; (2) compare the local lock managers; (3) compare the global lock or local lock managers; or (4) compare the global lock managers.
Lock Table Entry (LTE): A value that is read from a lock table entry 1112 .
Lock Table Entry Characteristic (LTEX): Specifies the number of bytes in each lock table entry 1112 .
Lock Table Entry Count (LTEC): Specifies the number of lock table entries 1112 to be allocated.
Lock Table Entry Number (LTEN): Specifies an entry in a lock table.
Maintain Primary Key Position (MPKP): Indicates whether the list entry 1208 is moved from its current position on a primary subsidiary list when the target list number specifies the list 1106 that contains the list entry 1208 , and the list entry 1208 key is not changed by the move operation.
Maintain Secondary Key Position (MSKP): Indicates whether the list entry 1208 is moved from its current position on a secondary subsidiary list when the target list number specifies the list 1106 that contains the list entry 1208 , and the secondary list entry key is not changed by the move operation.
Maximum Data List Entry Size (MDLES): Specifies the maximum size of the data list entry 1212 as an integral multiple of the list element size.
Maximum List Entry Key (MLEK): Partially specifies the maximum value the list entry key can have when the key compare type indicates key comparison and the key request type compares the key within range, or entry location by key range is specified and the ELKT operand is primary.
Maximum Secondary List Entry Key (MSLEK): Partially specifies the maximum value the secondary list entry key can have when the secondary key comparison type indicates key comparison, the secondary key request type compares the key within range, or entry location by key range is specified and the entry locator key type is secondary.
Maximum Structure Size (MXSS): Specifies the maximum number of 4,096-byte units allocated.
Minimum Required Control Storage (MRCS): Specifies the minimum number of 4K-byte units that must be allocated from control storage.
Monitor Request Type (MRT): Indicates what type of monitor to register or deregister. It may indicate (1) a list monitor, (2) an event queue monitor, (3) an event monitor, or (4) a key range monitor.
Monitored Object State (MOS): Indicates the state of the monitored object: empty (0) or not empty (1).
Monitored Object State Vector (MOSV): A bit string where the bit positions start at 0 and increase sequentially to 1K−1. The bit at position (i) in the string is set to one when the corresponding event monitor as specified in the data block 1006 of the register event monitors command is registered as a result of the command execution and the corresponding subsidiary list is not empty (i equals the event index minus one). Bit positions CTX−1 to ETX−1, and, when STX is greater than one, bit positions 0 to STX−2 are zero regardless of the state of the corresponding subsidiary list. Bit positions ETX to 1K−1 are reserved.
Move Entry Locator Type (MELT): A value that specifies which key value the target key is set to when (1) a list entry is created or moved by executing a move list entry, move and read list entry, move list entries, or write and move list entry command and (2) the AKRT operand indicates that the key is not assigned or the conditions of setting the target key to the assignment key as specified by the AKRT operand with a nonzero value are not satisfied.
For a list entry creation process, the operand indicates (when inactive) set to the list entry key in the MCB or (when active) set to the target list entry key in the MCB.
For a list entry movement process, the operand indicates (when inactive) set to the list entry key in the list entry or (when active) set to the target list entry key in the MCB.
This request operand 1010 is ignored when the list entries 1208 are not keyed and the command is not MLES or when AKRT takes precedence over MELT in one of the following conditions:
1. A list entry creation process is performed and the AKRT operand is assigned on create or assigned on create or move, or 2. A list entry movement process is performed and the AKRT operand is assigned on move or assigned or create or move.
The operand must be zero if (1) the command is MLES, (2) the list entries 1208 are not keyed, and (3) AKRT does not take precedence.
For the move list entry, move and read list entry, move list entries, and write and move list entry commands, both MELT and AKRT are provided as input operands. However, AKRT takes precedence over MELT, and MELT takes effect only if AKRT indicates that the key is not assigned or the conditions specified by an AKRT that indicates that the key is assigned are not satisfied.
For a list entry creation process, the following table summarizes the target key assignment scenarios.
Target Key Assignment for Creating a List Entry
Write and Move List Entry
AKRT
MELT = LEK
MELT = TLEK
Write List Entry
Not assigned
LEK in MCB
TLEK in MCB
LEK in MCB
Assigned on
LEK in MCB
TLEK in MCB
LEK in MCB
move
Assigned on
Assignment Key
Assignment Key
Assignment Key
create
Ass'd on
Assignment Key
Assignment Key
Assignment Key
create/move
For a list entry move process, the following table summarizes the target key assignment scenarios.
Target Key Assignment for Moving a List Entry
Move List Entry, Move and Read List
Entry, Write and Move List Entry
AKRT
MELT = LEK
MELT = TLEK
Not assigned
LEK in the list entry
TLEK in MCB
Assigned on move
Assignment Key
Assignment Key
Assigned on create
LEK in the list entry
TLEK in MCB
Assigned on create or move
Assignment Key
Assignment Key
Target Key Assignment for Moving List Entries
Move List Entries
AKRT
MELT = LEK
MELT = TLEK
Not assigned
LEK in the list entry
TLEK in the Data
Block
Assigned on move
Assignment Key
Assignment Key
Assigned on create
LEK in the list entry
TLEK in the Data
Block
Assigned on create or move
Assignment Key
Assignment Key
Move List Entries Count (MLEC): Specifies the number of moved list entries 1208 .
Read List Entries Count (RLEC): Specifies the number of list entries 1208 read.
Read List Type (RLT): Indicates what values are read upon normal completion of the command execution. The first bit is a control indicator (CI) that indicates whether list entry controls are read, the second is a data indicator (DI) that indicates whether data list entries are read, and the third is an adjunct indicator (AI) that indicates whether adjunct list entries are read.
Restart Token (RT): Controls the reading or deleting of list entries on the read list set and delete list set commands.
Retry Index (RX): Designates a retry buffer.
Retry Version Number (RVN): Specifies the version number stored in the retry buffer.
Secondary Key Comparison Type (SKCT): Indicates whether secondary key comparison is requested.
Secondary Key Request Type (SKRT): A value that indicates how a list entry 1208 is located when the entry locator type indicates location by keyed position, the entry locator key type is secondary and an entry is replaced, moved, read or deleted. When the secondary key comparison type operand is active, the secondary key request type operand also specifies how secondary keys are compared.
The SKRT operand is a dual purpose operand. When SKCT is active, the SKRT operand is used to control the type of secondary list entry key comparison to be performed on a command. When the SKCT is inactive, no secondary list entry key comparison is performed. When ELT designates that an entry is located by keyed position, and the ELKT operand is secondary, the SKRT operand is used to control the type of entry location performed. When the ELT designates an entry location by a means other than keyed position, or the ELKT operand is primary, the SKRT has no effect on entry location.
The secondary key request type determines the relationship between the secondary list entry key object and the secondary list entry key operand. It may indicate a comparison for (1) equal to the secondary list entry key operand, (2) less than or equal to the secondary list entry key operand, (3) greater than or equal to the secondary list entry key operand, or (4) within the range of the secondary list entry key to the maximum secondary list entry key operands, inclusive.
For the delete list entry, move and read list entry, move list entry, read and delete list entry, read list entry, write and move list entry, and write list entry commands the value “within the range” is invalid. For the delete list entries, delete list set, read list set, read list, delete list, and move list entries commands the value “within the range” specifies that the secondary keyed list entry satisfies the search criterion or the secondary key comparison criterion if it is within the range of the secondary list entry key to the maximum secondary list entry key operands, inclusive.
The secondary key request type operand is ignored unless an entry is replaced, moved, read or deleted, and (1) the secondary key comparison type is active, or (2) the entry locator type is locate by keyed position and the entry locator key type is secondary.
Secondary List Entry Key (SLEK): Partially specifies a list entry position by secondary key or an event monitor controls object 1306 .
Secondary Move Entry Locator Type (SMELT): Specifies which key value the target secondary key is set to when a move list entries command is executed. When inactive it indicates do not change the SLEK; when active it indicates set to TSLEK in the move block.
Secondary Target Direction (STDIR): Indicates how the positions of the list entries 1208 are numbered relative to a designated target position in secondary key order for an entry moved by a move and read list entry, move list entries, move list entry, or write and move list entry command, or created by a write and move list entry or write list entry command.
Starting Data Index (SDX): Indexes to the first list entry name or list entry identifier in the data block 1006 for the delete list entries command.
Starting Event Index (STX): Indexes to the first event in the data block 1006 for the register event monitors command.
Structure Authority (SAU): A value that is conditionally updated.
Suppress List Count Comparison Control (SLCCC): When active, suppresses the comparison of the list entry count and the list element count with the list entry and list element count limit when a list entry 1208 is written or moved.
Target Direction (TDIR): Indicates how the positions of the list entries 1208 are numbered relative to a designated target position for a moved list entry 1208 .
Target List Entry Key (TLEK): Partially specifies the targeted position, in primary key order, to which a list entry 1208 is moved.
Target List Number (TLN): Designates the list 1106 to which a list entry is moved.
Target Secondary List Entry Key (TSLEK): Partially specifies the targeted position, in secondary key order, to which a list entry 1208 is moved by a move list entries command.
User Identifier (UID): An integer that identifies a user. When the lock request type specifies global lock manager and local lock managers replacement, the user identifier specifies a global lock manager. When the lock request type specifies global lock manager replacement, the user identifier specifies a global lock manager and, when local lock managers exist, it also specifies a local lock manager. When the lock request type specifies local lock manager replacement or local lock manager comparison, the user identifier specifies a local lock manager.
The UID must be assigned for a register event monitors command or register list monitor command when the attachment override control is active, the UID must be attached for a register event monitors command or register list monitor command when the attachment override control is zero, and must be attached for all other commands.
User List Control (ULC): A field per list 1106 defined by the user.
User Notification Control (UNC): A field per event monitor controls 1306 defined by the user.
User Structure Control (USC): A field per structure defined by the user.
Write event queue transition count (WEQTC): Controls if the EQTC object is written by the RLM command. When the WEQTC bit has a value of active and the monitor request type specifies register event queue monitor, the EQTC object is written. Otherwise, the EQTC object is not written.
Write Request Type (WRT): Indicates the type of write request. It may indicate (I) replace a list entry, (2) create a list entry, or (3) replace or create a list entry.
Write Result (WRES): A value that indicates whether a write completed by creating a new list entry 1208 or replacing an existing list entry 1208 .
List Commands
Delete List (DL)
Conditionally deletes all entries on a specified list 1106 that match the criteria of the version number comparison and/or key comparison requests starting from a designated position. Processing continues until the end of the list 1106 is reached or a designated time period has elapsed.
Description: When requested, the list authorities, the list numbers, global lock managers, local lock managers, or any combination, are compared before the first list entry 1208 is scanned. The list entries 1208 are scanned starting at the designated position and proceeding in the direction specified until a model dependent time period elapses or the last list entry 1208 is scanned. Each list entry 1208 is located and, when requested, the version numbers are compared, or the keys are compared, or any combination of the preceding processes is performed. In order for any list entries 1208 to be deleted, 1) the list authority comparison, 2) the list number comparison, and 3) the global lock manager or local lock manager comparison, when requested, must succeed. In order for a particular list entry 1208 to be deleted, the version number comparison and key comparison, when requested, must succeed.
When the list structure 902 supports secondary keys, the list order that is followed by the scan process is determined by the list scan key type operand. When the list scan key type is primary, the scan follows primary key order. When the list scan key type is secondary, the scan follows secondary key order.
When a list entry 1208 is deleted and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are withdrawn. If this causes event queue transitions, the event queue monitors are notified. The withdrawal of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When the last list entry 1208 is scanned, the delete list entries count equaling the number of list entries 1208 deleted during the final redrive of the DL command and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, then the delete list entries count equaling the number of list entries 1208 deleted, the list entry controls 1210 of the next list entry 1208 in the sequence to be scanned, and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the designated list entry 1208 , then the delete list entries count equaling the number of list entries 1208 deleted, the list entry controls 1210 of the list entry 1208 that caused the mismatch and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the located entry is not deleted and command execution continues to process the next list entry 1208 .
When the LRT operand indicates to compare the local lock managers and the local lock manager comparison fails during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails during the processing of the designated list entry 1208 , the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the located entry is not deleted and command execution continues to process the next list entry 1208 .
Delete List Entries (DLES)
Conditionally deletes a set of list entries 1208 specified in an input list 11106 that match the criteria of the version number comparison and/or key comparison requests. Processing continues until the end of the input list 1106 is reached or a designated time period has elapsed.
Description: The list entries 1208 within the list set 1104 are processed starting with the list entry 1208 specified by the starting data index and continuing in the order as specified in the data block 1006 .
As part of processing each list entry 1208 , the list authority comparison, and the global lock manager comparison or the local lock manager comparison, if requested, are performed before the entry is located. If any of these comparisons fails, command execution concludes with an appropriate response code. If all of these comparisons are successful, command execution proceeds.
The entry is then located. To determine if the located entry is to be deleted, the version number comparison, the list number comparison, the key comparison, and the secondary key comparison, if requested, are performed. If any of these comparisons fails, then the located entry is not deleted and command execution continues to process the next list entry 1208 . In order for the located list entry 1208 to be deleted, all of these comparisons must succeed.
When the granular version number comparison flag is active, the VCRT, VRT, and CVN in the data block 1006 are used to do a version number comparison for each entry, the comparison values in the data block 1006 for the entry is used only for that list entry 1208 . When the granular version number comparison flag is inactive, the VCRT, VRT, and CVN in the MCB is tested for the list entries 1208 to be deleted, the comparison values in the MCB are used for all list entries 1208 .
When the halt on miscompare flag is active, the designated list entry 1208 exists but the requested version number comparison fails, then the processing stops, and the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
When the halt on miscompare flag is active, the designated list entry 1208 exists but the requested list number comparison fails, then the processing stops, and the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
When the halt on miscompare flag is active, the designated list entry 1208 exists but the requested key comparison fails, then the processing stops, and the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
When a list entry 1208 is deleted and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are withdrawn. If this causes event queue transitions, the event queue monitors are notified. The withdrawal of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When the last list entry 1208 specified by the ending data index is processed, the delete list entries count equaling the number of list entries 1208 deleted and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, the delete list entries count equaling the number of list entries 1208 deleted, the current data index of the next list entry 1208 to be processed, and an appropriate response code are returned in the response operands 1014 . When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the one specified by the starting data index, the delete list entries count equaling the number of list entries 1208 deleted, the current data index of the entry that caused the mismatch, and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the local lock managers and the local lock manager comparison fails during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, the delete list entries count equaling the number of list entries 1208 deleted, the current data index of the nonexistent list entry 1208 , and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison fails during the processing of the entry specified by the starting data index, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
Delete List Entry (DLE)
Conditionally deletes a specified list entry 1208 that matches the criteria of the version number comparison and/or key comparison requests.
Description: The list entry 1208 is located and, when requested, the list authorities are compared, the list numbers are compared, the version numbers are compared, the keys are compared, or the global lock managers are compared, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for a list cursor to be updated, all of these processes, when requested, must succeed. In order for a list entry 1208 to be deleted, all of these processes, when requested, must succeed.
When a list entry 1208 is deleted and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are withdrawn. If this causes event queue transitions, the event queue monitors are notified. The withdrawal of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted, the designated list entry controls, the list set entry count, the list set element count, the list entry count or list element count, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
Delete List Set (DLS)
Conditionally deletes all entries in the list structure 902 that match the criteria of the version number comparison and/or key comparison requests starting from a designated position specified by a restart token. Processing continues until all lists 11106 in the list structure 902 have been scanned, or a designated time period has elapsed.
Description: The list entries 1208 within the list set 1104 are processed starting at the entry specified by the restart token until a model dependent time period elapses or the last list entry 1208 is processed, or until an unsuccessful list authority comparison, global lock manager comparison, or local lock manager comparison occurs. A zero restart token specifies that processing starts at the beginning of the list set 1104 , and a nonzero token designates the entry for restarting the processing.
As part of processing each list entry 1208 , the list authority comparison, and the global lock manager comparison or the local lock manager comparison, if requested, are performed before the entry is located. If any of these comparisons fails, command execution concludes with an appropriate response code. If all of these comparisons are successful, command execution proceeds.
The entry is then located. To determine if the located entry is to be deleted, the version number comparison, the list number comparison, or the key comparison, or the secondary key comparison, if requested, are performed. If any of these comparisons fails, then the located entry is not deleted and command execution continues to process the next list entry 1208 . In order for the located list entry 1208 to be deleted, all of these comparisons must succeed.
When a list entry 1208 is deleted and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are withdrawn. If this causes event queue transitions, the event queue monitors are notified. The withdrawal of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When the last list entry 1208 is scanned, the delete list entries count equaling the number of list entries 1208 deleted and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, the delete list entries count equaling the number of list entries 1208 deleted, the restart token designating the next list entry 1208 to be processed, and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the one specified by the restart token, the delete list entries count equaling the number of list entries 1208 deleted, the restart token designating the list entry 1208 that caused the mismatch, and an appropriate response code are returned in the response operands 1014 .
When the restart token operand is invalid, an appropriate response code is returned in the response operand 1014 .
When the LRT operand indicates to compare the local lock managers ad the local lock manager comparison fails during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison fails during the processing of the entry specified by the restart token, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
Dequeue Event Monitor Controls (DEMC)
Dequeues event monitor controls 1306 for a specified user from the event queue 1116 for a model dependent time period.
Description: The event monitor controls objects 1306 are dequeued from the event queue 1116 associated with the specified user and of the specified key type starting at the leftmost position and proceeding to the right until the model dependent time period elapses, the data area is filled, or the last event monitor controls object 1306 is dequeued.
The returned event monitor queued indicators are always active.
When an event monitor controls object 1306 is dequeued and an event queue state transition results, the event queue monitor is notified.
The dequeue of the event monitor controls objects 1306 and the generated list notification commands are primary processes.
When the last event monitor controls object 1306 is dequeued, the event monitor controls queued count is set to zero, the event monitor controls dequeued count is set to the number of event monitor controls objects 1306 dequeued and returned, and an appropriate response code are returned in the response operands 1014 .
When the data area is filled or a model dependent time period has elapsed, the event monitor controls queued count is set to the number of event monitor controls objects 1306 still queued, the event monitor controls dequeued count is set to the number of event monitor controls objects 1306 dequeued and returned, the dequeued event monitor controls, and an appropriate response code are returned in the response operands 1014 .
When the list structure 902 does not support keyed entries, the list structure type object is invalid and a request exception is recognized.
Deregister List Monitor (DLM)
Deregisters the specified list monitor.
Description: The deregister list monitor command deregisters the designated monitor. When an event monitor is deregistered, the designated event monitor controls object 1306 is deleted. If this causes an event queue transition, the event queue monitor is notified. The deletion of the event monitor controls object 1306 and the generated list notification commands are primary processes.
When the monitor is deregistered, an appropriate response code is returned in the response operand 1014 .
Move and Read List Entry (MRLE)
Reads a specified list entry 1208 that matches the input criteria and moves the entry to a target position.
Description: The list entry 1208 and the designated target position are located, the list entry counts or list element counts are compared, and, when requested, the list numbers are compared, the version numbers are compared, the list authorities are compared, the assignment key is updated, the keys are compared or the global lock managers are compared, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for the list cursor, version number, or assignment key to be updated, or any combination thereof, all of these processes, when requested, must succeed. In order for a list entry 1208 to be moved and read, these processes, when requested, must succeed.
When a list entry 1208 is moved and monitored list state transitions result, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is moved and monitored subsidiary list state transitions result, the associated event monitor controls objects 1306 are withdrawn, queued, or both. If this causes event queue transitions, the event queue monitors are notified. The withdrawal or queueing of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is moved and monitored key range state transitions result, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is moved, the designated list entry controls, the list set entry count, the list set element count, the target list entry count or list element count, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the list entry count matches or exceeds the list entry count limit or the list element count matches or exceeds the list element count limit, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When updating the assignment key fails, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code 12 are returned in the response operands 1014 .
Move List Entries (MLES)
Moves a set of list entries 1208 between source and target positions based on criteria in a set of move blocks.
Move Condition
SMELT
GVNC
MELT
Condition 1
Inactive
Inactive
B′0′ or AKRT presides over
MELT
Condition 2
Inactive
Active
any value
Condition 3
Inactive
any value
B′1′ and AKRT does not preside
Condition 4
Inactive
any value
any value
Notes:
1. SMELT is the secondary move entry locator type
2. GVNC is the granular version number control
3. MELT is the move entry locator type
4. AKRT is the assignment key request type
Description: When requested, the list authorities, the global lock managers, local lock managers, or any combination, are compared before the first list entry 1208 is processed. The list entries 1208 within the list set 1104 are processed starting with the list entry 1208 specified by the starting data index and continuing in the order as specified in the data block 1006 . Each list entry 1208 is located and, when requested, the version numbers are compared, the list numbers are compared, or the keys are compared, or any combination of the preceding processes is performed. In order for any list entries 1208 to be moved, the list authority comparison, and the global lock manager or local lock manager comparison, when requested, must succeed. In order for a particular list entry 1208 to be moved, the version number comparison, list number comparison, and key comparison, when requested, must succeed.
When the granular version number comparison flag is active, the VCRT, VRT, and CVN in the data block 1006 is used to do a version number comparison for each entry, the comparison values in the data block 1006 for the entry is used only for that list entry 1208 . When the granular version number comparison flag is active, the VN in the data block 1006 is used when the version number is replaced. When the granular version number comparison flag is inactive, the VCRT, VRT, and CVN in the MCB is tested for the list entries 1208 to be moved, and the comparison values in the MCB are used for all list entries 1208 .
If the halt on miscompare flag is active, the designated list entry 1208 exists but the requested version number comparison fails, the processing is stopped, the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
If the halt on miscompare flag is active, the designated list entry 1208 exists but the requested list number comparison fails, the processing is stopped, the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
If the halt on miscompare flag is active, the designated list entry 1208 exists but the requested key comparison fails, the processing is stopped, the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 . When an entry is moved, the TLN value in the data block 1006 is used as the target list number to which the entry is moved. If the structure is keyed, the LEK of the list entry 1208 being moved, the TLEK in the data block 1006 , or the assignment key value are used as the primary key value in the target entry based on the MELT value and the AKRT value. When an entry is moved, the TDIR in the data block 1006 is used as the direction for the entry to be placed in the target list 1106 in primary key order. If the structure supports secondary keys, the SLEK of the list entry 1208 being moved and the TSLEK in the data block 1006 are used as the secondary key value in the target entry based on the SMELT value. When an entry is moved, the STDIR in the data block 1106 is used as the direction for the entry to be placed in the target list 1106 in secondary key order.
If the structure is keyed, list entry key values are returned in the MRB when assignment keys are assigned. Otherwise, the list entry key values in the MRB are reserved and have a value of zeros.
When a list entry 1208 is moved and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is moved and a monitored subsidiary list state transition results for either the source location or the target location, the associated event monitor controls objects 1306 may be withdrawn or the event monitor controls objects 1306 notified that a monitored event has occurred. If this causes event queue transitions, the event queue monitors are notified. The withdrawal or notification of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is moved and monitored key range state transitions results, the key range monitors are notified. The generated list notification commands are secondary processes.
When the last list entry 1208 specified by the ending data index is processed the move list entries count, MLEC, equaling the number of list entries 1208 moved, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed or the LEK field in the MRB is full, the move list entries count equaling the number of list entries 1208 moved, the current data index of the next list entry 1208 to be processed, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the one specified by the starting data index, the move list entries count equaling the number of list entries 1208 moved, the current data index of the entry that caused the mismatch, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the local lock managers and the local lock manager comparison fails during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the entry specified by the starting data index, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When an invalid target list number is specified, the processing is stopped, the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, then the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison fails during the processing of the entry specified by the starting data index, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When updating the assignment key fails, then the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys for entries between SDX and CDX minus one, the assignment key, the assignment key threshold, and an appropriate response code is returned in the response operand 1014 .
When the list entry count matches or exceeds the list entry count limit, or the list element count matches or exceeds the list element count limit, then the move list entries count equaling the number of list entries 1208 moved, the current data index, list entry keys if the structure is keyed and keys are assigned to the entries using assignment keys, for entries between SDX and CDX minus one, and an appropriate response code is returned in the response operand 1014 .
Move List Entry (MLE)
Moves a specified list entry 1208 that matches the input criteria to a target position.
Description: The list entry 1208 and the designated target position are located, the list entry counts or list element counts are compared, and, when requested, the list numbers are compared, the version numbers are compared, the list authorities are compared, the assignment key is updated, the keys are compared, or the global lock managers are compared, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for the list cursor, version number, or assignment key to be updated, or any combination thereof, all of these processes, when requested, must succeed. In order for a list entry 1208 to be moved, all of these processes, when requested, must succeed.
When a list entry 1208 is moved and monitored list state transitions result, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is moved and monitored subsidiary list state transitions result, the associated event monitor controls objects 1306 are withdrawn, queued, or both. If this causes event queue transitions, the event queue monitors are notified. The withdrawal or queueing of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is moved and monitored key range state transitions result, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is moved, the designated list entry controls, the list set entry count, the list set element count, the target list entry count or list element count, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the list entry count matches or exceeds the list entry count limit, or the list element count matches or exceeds the list element count limit, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When updating the assignment key fails, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
Read and Delete List Entry (RDLE)
Reads and deletes a specified list entry 1208 that matches the input criteria.
Description: The list entry 1208 is located and, when requested, the list authorities are compared, the list number is compared, the version numbers are compared, the keys are compared, or the global lock managers are compared, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for a list cursor to be updated, all of these processes, when requested, must succeed. In order for a list entry 1208 to be read and deleted, all of these processes, when requested, must succeed.
When a list entry 1208 is deleted and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are withdrawn. If this causes event queue transitions, the event queue monitors are notified. The withdrawal of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is deleted and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is read and deleted, the designated list entry controls, the list set entry count the list set element count, the list entry count or list element count, and an appropriate response code are return ed in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
Read List Entry (RLE)
Reads a specified list entry 1208 that matches the input criteria.
Description: The list entry 1208 is located and, when requested, the list authorities are compared, the list numbers are compared, the version numbers are compared, the keys are compared, or the global lock managers are compared, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for a list cursor or version number to be updated, or any combination thereof, all of these processes, when requested, must succeed. In order for a list entry 1208 to be read, all of these processes, when requested, must succeed.
When a list entry 1208 is read, the designated list entry controls, the list set entry count, the list set element count, the list entry count or list element count, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls and an appropriate response code are returned in the response operands 1014 .
Read Event Monitor Controls (REMC)
Reads the event monitor controls 1306 for a specified user and subsidiary list.
Description: The event monitor controls of the specified key type and an appropriate response code are returned in the response operands 1014 .
When the specified event monitor controls 1306 do not exist, an appropriate response code is returned in the response operand 1014 .
When the list structure 902 does not support keyed entries and the key type is primary, or the list structure 902 does not support secondary keys and the key type is secondary, the list structure type object is invalid and a request exception is recognized.
Read Event Monitor Controls List (REMCL)
Reads a range of event monitor controls 1306 into a data block 1106 for a model dependent time interval.
Description: The event monitor controls 1306 of the specified key type with list numbers within the range of values starting at the starting list number up to and including the ending list number are read. The event monitor controls 1306 within the list set 1104 are scanned starting with the starting list number or the EMC restart token until a model dependent time period elapses, the data block 1106 is full of event monitor controls 1306 , or the last event monitor control 1306 is scanned. A zero restart token causes the entire list 1106 to be processed starting at the starting list number operand. A valid nonzero EMC restart token starts the processing at the event monitor control object 1306 designated by the EMC restart token.
The EMCs are scanned starting with the starting list number, then in ascending order by LN up to the ending list number. The EMCs in a list number are scanned in an unpredictable ordering for keys, and an unpredictable ordering for UIDs within a key value.
When the last EMC within the list number range is processed, the EMC processed count and an appropriate response code are returned.
When the command times out or the data block 1006 is full, the EMC processed count, EMC restart token, and an appropriate response code is returned.
When the EMC restart token operand is invalid, an appropriate response code is returned in the response code operand.
When the product of the value of the DBS operand and 4096 is larger than the message buffer size, there is insufficient message buffer space to contain the data block 1006 . In this case, the command is completed and an appropriate response code is returned.
When the list structure 902 does not support keyed entries and the key type is primary, or the list structure 902 does not support secondary keys and the key type is secondary, the list structure type object is invalid and a request exception is recognized.
Read Event Queue Controls (REQC)
Reads the event queue 1116 controls for a specified user and key type.
Description: The event queue controls of the specified key type and an appropriate response code returned in the response operands 1014 .
When the list structure 902 does not support keyed entries and the key type is primary, or the list structure 902 does not support secondary keys and the key type is secondary, the list structure type object is invalid and a request exception is recognized.
Read List (RL)
Reads the list entry controls 1210 , adjunct list entry 1216 , and data list entry 1212 for each list entry 1208 in a specified list 1106 that matches the input criteria for a model dependent time interval.
Description: The list entries 1208 are processed starting at the designated position and proceeding in the direction specified until a model dependent time period elapses, the data area is filled, or the last list entry 1208 is processed, or until an unsuccessful list authority comparison, global lock manager comparison, or local lock manager comparison occurs.
The size of the message buffer is compared to the data block size before the designated list entry 1208 is processed. When requested, the list number comparison is performed as part of processing the designated list entry 1208 . If any of these comparisons fails, command execution concludes with an appropriate response code. If all of these comparisons are successful, command execution proceeds.
As part of processing each list entry 1208 , the list authority comparison, and the global lock manager comparison or the local lock manager comparison, if requested, are performed before the entry is located. If any of these comparisons fails, command execution concludes with an appropriate response code. If all of these comparisons are successful, command execution proceeds.
When the list structure 902 supports secondary keys, the list order that is followed by the scan process is determined by the list scan key type operand. When the list scan key type is primary, the scan follows primary key order. When the list scan key type is secondary, the scan follows secondary key order.
The entry is then located. To determine if the located entry or list entry controls 1210 is to be read, the version number comparison and key comparison, if requested, and the list entry key comparison, if requested, are performed. If any of these comparisons fails, then the located entry or list entry controls 1210 is not read and command execution continues to process the next list entry 1208 . In order for the located list entry 1208 or list entry controls 1210 to be read, all of these comparisons must succeed.
The list entry controls 1210 and adjunct list entry 1216 for the first list entry 1208 that is read by the command execution are placed in the message response block 1004 . The data list entry 1212 for the first list entry 1208 that is read, and all subsequent list entry controls 1210 , adjunct list entries 1216 and data list entries that are read are placed in the data block 1006 .
When the last list entry 1208 is scanned, the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the list entry controls 1210 of the next list entry 1208 in the sequence to be scanned and an appropriate response code are returned in the response operands 1014 . When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the designated list entry 1208 , then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the list entry controls 1210 of the list entry 1208 that caused the mismatch and an appropriate response code are returned in the response operands 1014 .
When the specified data block size is not large enough to contain the information specified by the read list type for at least one list entry 1208 , an appropriate response code is returned in the response operand 1014 .
When the data block 1006 does not have enough space for the next entry, then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the list entry controls 1210 of the next list entry 1208 in the sequence to be scanned and an appropriate response code are returned in the response operands 1014 . When the LRT operand indicates to compare the local lock managers and the local lock manager comparison fails during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the designated list entry 1208 , the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails during the processing of the designated list entry 1208 , the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the located entry is not deleted and command execution continues to process the next list entry 1208 .
Read List Set (RLS)
Reads the list entry controls 1210 , adjunct list entry 1216 , and data list entry 1212 for each list entry 1208 in a list structure 902 that matches the input criteria for a model dependent time interval.
Description: The list entries 1208 within the list set 1104 are processed starting at the entry specified by the restart token until a model dependent time period elapses, the data area is filled, or the last list entry 1208 is processed, or until an unsuccessful list authority comparison, global lock manager comparison, or local lock manager comparison occurs. A zero restart token specifies that processing starts at the beginning of the list set 1104 , and a nonzero token designates the entry for restarting the processing.
As part of processing each list entry 1208 , the list authority comparison, and the global lock manager comparison or the local lock manager comparison, if requested, are performed before the entry is located. If any of these comparisons fails, command execution concludes with an appropriate response code. If all of these comparisons are successful, command execution proceeds.
The entry is then located. To determine if the located entry or list entry controls 1210 is to be read, the version number comparison, the list number comparison, and the key comparison, if requested, are performed. If any of these comparisons fails, then the located entry or list entry controls 1210 is not read and command execution continues to process the next list entry 1208 . In order for the located list entry 1208 or list entry controls 1210 to be read, all of these comparisons must succeed.
The list entry controls 1210 and adjunct list entry 1216 for the first list entry 1208 that is read by the command execution are placed in the message response block 1004 . The data list entry 1212 for the first list entry 1208 that is read and all subsequent list entry controls 1210 , adjunct list entries 1216 and data list entries that are read are placed in the data block 1006 .
When the last list entry 1208 is processed, the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the restart token designating the next list entry 1208 to be processed, and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison, the global lock manager comparison, or the local lock manager comparison fails during the processing of a list entry 1208 other than the one specified by the restart token, then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the restart token designating the list entry 1208 that caused the mismatch, and an appropriate response code are returned in the response operands 1014 .
When the specified data block size is not large enough to contain the information specified by the read list type for at least one list entry 1208 , an appropriate response code is returned in the response operand.
When the restart token is invalid, an appropriate response code is returned in the response operand.
When the data block 1006 does not have enough space for the next entry, then the read list entries count equaling the number of data or adjunct list entries or list entry controls 1210 stored in the message response block 1004 and data block 1006 , the restart token, and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the local lock managers and the local lock manager comparison fails during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock managers and the global lock manager comparison fails during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the LRT operand indicates to compare the global lock or local lock managers, and both the global lock manager comparison and local lock manager comparison fail during the processing of the entry specified by the restart token, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the list authority comparison fails during the processing of the entry specified by the restart token, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
Register Event Monitors (REMS)
Registers a set of event monitors based on an input list of event monitor controls 1306 for a model dependent time interval.
Description: The registration requests are processed starting with the event monitor controls object 1306 specified by the user identifier and starting event index and continuing in the order as specified in the data block 1006 . Each requested event monitor is registered. The user identifier that processes the event monitor control object 1306 is either the UID in the MCB if the UID location bit is B‘0’ or the user identifier in the event monitor control operand from the data block 1006 if the UID location bit is B‘1’.
If (1) the halt register event monitors bit is active, (2) the UID location is one, (3) the attachment override control bit is active, and (4) the user identifier is not assigned or (1) the halt register event monitors bit is active, (2) the UID location is one, (3) the attachment override control bit is inactive, and (4) the user identifier is not attached, or (1) the halt register event monitors bit is active, (2) the UID location is one, (3) the user identifier is attached, and (4) the list notification token is invalid, then the processing is stopped, the current event index of the EMC that failed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operands 1014 .
When the attachment override control bit is active and the halt register event monitors bit is inactive, the EMC is skipped and processing continues if an EMC specifies a UID that is not assigned. When the attachment override control bit is inactive and the halt register event monitors bit is inactive, the EMC is skipped and processing continues if an EMC specifies a UID that is not attached.
The EMC is queued, not queued, withdrawn, or not withdrawn based on the INRT bit, EMQIC bit, and the EMQI bit.
When the initial notification request type operand is active, a withdrawal or queueing of the event monitor controls object 1306 associated with each request event monitor may be performed. If this causes an event queue transition, the event queue monitor is notified. The withdrawal or queueing process and the generated list notification commands are primary processes.
When the last event monitor specified by the ending event index is processed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operands 1014 .
When a model dependent time period has elapsed, the current event index of the next event to be processed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operands 1014 .
When event monitor registration requiring event monitor controls creation is requested and the event monitor controls object space is full, the current event index of the event currently being processed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operands 1014 .
When the specified list structure user is attached with a zero list notification token and the UID locator bit is zero, an appropriate response code is returned in the response operand.
When the list number is invalid, the current event index of the event currently being processed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operand.
When the key type specified in the EMC is secondary and secondary keys are not supported in the structure, the current event index of the event currently being processed, the event monitor controls count, the maximum event monitor controls count, the monitored object state vector, and an appropriate response code are returned in the response operand.
When the list structure 902 does not support keyed entries, the list structure type object is invalid and a request exception is recognized.
Register List Monitor (RLM)
Registers a specified monitor: list, event queue, subsidiary list, or key range.
Description: The register list monitor command registers the designated monitor, as specified by the monitor request type and the key type.
When a list monitor is registered, the list entry count or the list element count, the monitored object state, and an appropriate response code are returned in the response operands 1014 . If the initial notification request type operand is active, the list monitor is notified. The generated list notification commands are primary processes.
When an event queue monitor is registered, the event monitor controls queued count, the monitored object state, and an appropriate response code are returned in the response operands 1014 . If the initial notification request type operand is active, the event queue monitor is notified. The generated list notification commands are primary processes.
When an event monitor is registered, the event monitor controls count, the maximum event monitor controls count, the monitored object state, and an appropriate response code are returned in the response operands 1014 . If the initial notification request type operand is active, a withdrawal or queueing of the designated event monitor controls object 1306 may be performed. If this causes an event queue transition, the event queue monitor is notified. The withdrawal or queueing process and the generated list notification commands are primary processes.
When a key range monitor is registered, the list entry count or the list element count, the monitored object state, and an appropriate response code are returned in the response operands 1014 . If the initial notification request type operand is active, the key range monitor is notified. The generated list notification commands are primary processes. When the write event queue transition count bit is active and the monitor register type specifies register event queue monitor, The event queue transition count object is written. Otherwise, the event queue transition count object is not written.
When the specified list structure user is attached with a zero list notification token, an appropriate response code is returned in the response operand 1014 .
When event monitor registration requiring event monitor controls creation is requested and the event monitor controls object space is full, the event monitor controls count, the maximum event monitor controls count, and an appropriate response code are returned in the response operands 1014 .
When the monitor request type specifies a key range monitor and key range initialization is in progress, the key range monitor is not registered and an appropriate response code is returned in the response operands 1014 .
Write and Move List Entry (WMLE)
Write and moves a specified list entry 1208 that matches the input criteria to a target position.
Description: The designated list entry 1208 or position is located, and, when requested, the list authorities are compared, the assignment key is updated, the keys are compared, the global lock managers are compared, or the list entry 1208 is replaced or created, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. When list entry creation is requested, the list set entry counts, the list set element counts, and the list entry counts or list element counts are compared. When list entry replacement is requested, the list number, the key, and version number comparisons, if requested, are compared, the list set element counts are compared, and, if the element count indicator is active, the list element counts are compared. When the global lock managers are compared, the lock table entry 1112 may be written. In order for a lock table entry 1112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for a list cursor, version number, or assignment key to be updated, or any combination thereof, all of these processes, when requested, must succeed. In order for a list entry 1208 to be written and moved, all of these processes, when requested, must succeed.
When a list entry 1208 is written and moved and monitored list state transitions result, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is written and moved and monitored subsidiary list state transitions result, the associated event monitor controls objects 1306 are withdrawn, queued, or both. If this causes event queue transitions, the event queue monitors are notified. The withdrawal or queueing of the event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is created or moved and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is written and moved, the list entry controls 1210 , the list set entry count, the list set element count, the target list entry count or list element count, the write result, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the list entry count matches or exceeds the list entry count limit, or the list element count matches or exceeds the list element count limit, an appropriate response code is returned in the response operand 1014 .
When the list set 1104 is full, and list entry creation or replacement is requested, an appropriate response code is returned in the response operand 1014 . If the requested operation is a replacement of an existing list entry 1208 and the value of the DLES request operand 1010 is smaller than or equal to the value of the DLES object in the list entry controls 1210 , the failed replacement indicator is set to active. Otherwise, the failed replacement indicator is set to inactive.
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the list entry name already exists and list entry creation is requested, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When updating the assignment key fails, an appropriate response code is returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the program list entry identifier indicator is active, the list entry identifier in the MCB has already been assigned for the list structure 902 , and list entry creation is requested, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
Write List Controls (WLC)
Updates a subset of the list control objects for a specified list 1106 , where the subset of controls is determined by the value of the list control type.
Description: The list authority is compared to the value of the CLAU operand and replaced with the value of the LAU operand when they are equal. When the list authority comparison and replacement is successful, the write list controls command writes the list controls 1202 , controls and initializes the key range, depending on the list control type.
When the list empty and the list not-empty notification thresholds are updated, the resulting state of the list 1106 is determined and the list monitors are notified. The list notification commands are primary processes.
When the key range empty and not-empty notification thresholds are updated and key range is not being initialized, the resulting state of the key range is determined and the key range monitors are notified. The list notification commands are primary processes.
If the list cursor bit is active and the cursor direction type bit is inactive, the list cursor is initialized to the LEID of the leftmost list entry 1208 when the value of the CDIR operand is left to right and is initialized to the LEID of the rightmost list entry 1208 when the value of the CDIR operand is right to left, and the CDIR object is set equal to the CDIR operand.
If the list cursor bit is active and the cursor direction type bit is active, the LEID operand is nonzero, and the entry designated by the LEID request operand 1010 exists on the list 1106 designated by the LN operand, the list cursor object is initialized to the LEID operand value and the CDIR object is set equal to the CDIR operand.
If the list cursor bit is active and the cursor direction type bit is active, the LEID operand is nonzero, but the entry designated by the LEID request operand 1010 does not exist on the list 1106 designated by the LN operand, the LEID operand is invalid and an appropriate response code is returned in the response operand 1014 .
If the list cursor bit is active, the cursor direction type bit is active and the LEID operand is zero, the list cursor object is initialized to zero and the CDIR object is set equal to the CDIR operand.
When the list controls 1202 are written, an appropriate response code is returned in the response operand 1014 .
The key range is initialized when the key range list entry key and the key range maximum list entry key are updated.
When the list controls 1202 are written and the key range is initialized, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When key range initialization is not complete, and the key range list entry key and the key range maximum list entry key are updated, an appropriate response code is returned in the response operands 1014 .
Write List Entry (WLE)
Writes a specified list entry 1208 that matches the input criteria.
Description: The designated list entry 1208 or position is located and, when requested, the list authorities are compared, the assignment key is updated, the keys are compared, the global lock managers are compared, or the list entry 1208 is replaced or created, or any combination of the preceding processes is performed. When the global lock managers are compared, the local lock managers may be compared. When list entry creation is requested, the list set entry counts, the list set element counts, and the list entry counts or list element counts are compared. When list entry replacement is requested, the list number and version number comparisons, the key is compared, if requested, are compared, the list set element counts are compared, and, if the element count indicator is active, the list element counts are compared. When the global lock managers are compared, the lock table entry 1112 may be written. In order for a lock table entry 11112 to be written, all of these processes except for local lock manager comparison, when requested, must succeed. In order for the list authority to be replaced, all of these processes, when requested, must succeed. In order for a list cursor, version number, or assignment key to be updated, or any combination thereof, all of these processes, when requested, must succeed. In order for a list entry 1208 to be written, all of these processes, when requested, must succeed.
When a list entry 1208 is created and a monitored list state transition results, the list monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is created and a monitored subsidiary list state transition results, the associated event monitor controls objects 1306 are queued. If this causes event queue transitions, the event queue monitors are notified. The queueing of event monitor controls objects 1306 and the generated list notification commands are secondary processes.
When a list entry 1208 is created and a monitored key range state transition results, the key range monitors are notified. The generated list notification commands are secondary processes.
When a list entry 1208 is written, the list entry controls 1210 , the list set entry count, the list set element count, the list entry count or list element count, the write result, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are no other local lock managers, when a local lock manager is replaced with the opposite value, or when the global lock and the local lock managers are replaced, an appropriate response code is returned in the response operand 1014 .
When the list authority comparison fails, the list authority, the user list control, and an appropriate response code are returned in the response operands 1014 .
When a global lock manager is replaced and there are one or more other local lock managers, or when a local lock manager is replaced with the same value, then the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When global lock manager comparison fails, the lock table entry value and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested version number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the list entry count matches or exceeds the list entry count limit, or the list element count matches or exceeds the list element count limit, an indcative response code is returned in the response operand 1014 .
When the list set 1104 is full, and list entry creation or replacement is requested, an appropriate response code is returned in the response operand 1014 .
If the requested operation is a replacement of an existing list entry 1208 and the value of the DLES request operand 1010 is smaller than or equal to the value of the DLES object in the list entry controls 1210 , the failed replacement indicator is set to active. Otherwise, the failed replacement indicator is set to inactive.
When the designated list entry 1208 exists but the requested list number comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the designated list entry 1208 does not exist, an appropriate response code is returned in the response operand 1014 .
When the list entry name already exists and list entry creation is requested, the designated list entry controls 1210 and an appropriate response code are returned in the response operand 1014 .
When updating the assignment key fails, an appropriate response code is returned in the response operands 1014 .
When the designated list entry 1208 exists but the requested key comparison fails, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
When the program list entry identifier indicator is active, the list entry identifier in the MCB has already been assigned for the list structure 902 , and list entry creation is requested, the designated list entry controls 1210 and an appropriate response code are returned in the response operands 1014 .
MQSeries Shared Queue List Structure
Each list structure 902 created to support an MQSeries shared queue 106 is allocated with a list set 1104 where each list entry 1208 contains both an adjunct list entry 1216 and a data list entry 1212 and each list 1106 has a specified list entry count limit. In addition, a one-byte wide lock table 1110 is created where the number of lock table entries 1112 matches the number of list headers 202 (or, equivalently, lists 1106 ), making a one-to-one association between lock table entries 1112 and list headers 202 . The list entry-related commands use a single global lock manager value and global lock manager comparison and replacement rules to govern their operations. This provides basic fetch and hold/store and release serializaton primitives on each list 1106 . List authority values are used to provide state controls for each list 1106 , such as the put inhibited state for a list authority value of 1. List authority comparison operations are used to enforce the states.
The lists 1106 are also created with both primary and secondary keys and key range monitoring is supported with one key range for each list 1106 . In addition, list monitoring and sublist monitoring is supported and user controls 1108 are established to support notification operations.
MQSeries Put Processing
A new message 204 is put to the uncommitted portion 210 of the list header 202 assigned to the shared queue 106 by invocation of the following OS/390 service:
?IXLLIST
Entry type (New)
ASSIGNENTRYID (pleid = Priority|STCK(8)|LN|MgrID)
LISTNUMBER (LN)
LOCKOPER (Not Held)
LOCKINDEX (LN)
CONTOKEN (Strb_Connect_Token)
ADJUNCTAREA (=SLEK|SADE)
ELEMNUM (parm_buffer_length/CSQE_element_size)
Buffer (parm_buffer)
BuffSize (buffer_size)
Assign (key)
ENTRYKEY (entry_key =
X‘F6’|MgrID|Priority|UOW ID|LN|zeros)
AuthCompare (Yes)
AuthCompareType (Equal)
AUTHCOMP (SCB_LHQC_List_Authority)
AnsArea
AnsLen
RetCode
RsnCode
VersionUpdate (Set)
NEWVERS (version_number
=
UOW ID
=
MgrID|STCK(7))
Mode (SyncSuspend)
The OS/390 service routine converts this to a Write List Entry (WLE) command with the following request operands:
Acronym
Operand
Contents
CC
Command code
Command Code for
WLE
SID
Structure identifier
List Structure ID for
ConToken
DLES
Data list entry size
ELEMNUM
LRT
Lock request type
Compare global lock
managers
CGLM
Comparative global lock manager
=B‘00’
LTEN
Lock table entry number
=X‘0000’|
LISTNUMBER
KCT
Key comparison type
ignored
KRT
Key request type
ignored
LEK
List entry key
ENTRYKEY
VRT
Version request type
Set version number on
create
VCRT
Version comparison request type
ignored
VN
Version number
NEWVERS
CVN
Comparative version number
ignored
DIR
Direction
Left to right
ELT
Entry locator type
Ignored - locate by keyed
position is default for
create operations
ELKT
Entry locator key type
Locate by primary key
LNCT
List number comparison type
ignored
LCURT
List cursor request type
Do not update the list
cursor
LET
List entry type
Write data and adjunct
WRT
Write request type
Create a new list entry
LN
List number
LISTNUMBER
LEID
List entry
ASSIGNENTRYID
AKRT
Assignment key request type
List entry key not
assigned
AKUT
Assignment key update type
ignored
LAUCT
List authority comparison type
Compare for equal
LAURT
List authority replacement type
Do not replace list
authority
LCUT
List cursor update type
ignored
STDIR
Secondary target direction
Left to right
SKCT
Secondary key comparison type
Ignored
SKRT
Secondary key request type
ignored
UID
User identifier
ignored
LAU
List authority
ignored
CLAU
Comparative list authority
AUTHCOMP
AKI
Assignment key increment
ignored
ALE
Adjunct list entry
ADJAREA with first
32 bytes set to 0
The message buffer address (Buffer) and length (Buffsize) are used to create a message buffer address list (MBAL) which accompanies the message command block 1002 for the Write List Entry (WLE) command to the selected coupling facility structure 902 . The coupling facility and structure identifier for the list structure 902 are obtained through controls associated with the ConToken.
When the coupling facility 104 receives the message command block 1002 and message address list for the Write List Entry (WLE) command, the following actions are taken.
1. The value of AUTHCOMP is compared against the list authority object to ensure that the list 1106 is not put-inhibited. If the comparison shows the values are not equal, the command ends without creating a list entry 1208 and an appropriate response code is returned. If the comparison shows the values are equal, the command continues. 2. The value of the global lock manager field in the lock table entry 1112 associated with the list 1106 (i.e. Lock table entry number=LISTNUM) is compared against a value of zero. If the global lock manager field is not zero, the list 1106 is locked and cannot be changed. In this case the command ends without creating a list entry 1208 and an appropriate response code is returned. If the global lock manager field is zero, the command continues. 3. The list entry (or element) count limit is checked against the current list entry (or element) count to ensure that creation of a new list entry 1208 will not cause the count of list entries 1208 to exceed the limit. If this is the case, the command ends without creating a list entry 1208 and an appropriate response code is returned. If the list entry (or element) count limit is not exceeded by the creation of a list entry 1208 , the command continues. 4. Creation of a new list entry 1208 is attempted by obtaining free storage resources for the list entry controls 1210 , adjunct list entry 1216 and data list entry 1212 . The data list entry size is the value of ELEMNUM. If insufficient resources are available, the command ends without creating a list entry 1208 and an appropriate response code is returned. If storage resources are available, the list entry 1208 is created. 5. The list entry 1208 is created by writing the buffer contents (actual message) to the data list entry 1212 , setting the adjunct list entry 1216 equal to the ADJAREA, and setting the list entry controls 1210 to the input values. The list entry controls 1210 are set as follows:
Adjunct format control is set to adjunct secondary key indicator Data list entry size is set to the value of ELEMNUM List entry identifier is set to the value of ASSIGNENTRYID List entry key is set to the value of ENTRYKEY List number is set to the value of LISTNUMBER Version number is set to the value of NEWVERS Secondary list entry key is set to zero.
6. The list entry 1208 is inserted in the target position for the primary key ordering based on the value of the list entry key. 7. The list entry 1208 is inserted in the target position for the secondary key ordering based on the value of zero. (Note that the OS/390 service sets the first 32 bytes of the adjunct area, which represents the secondary key, equal to zero.) 8. The list entry count or list element is incremented. 9. The command is completed and an appropriate response code is returned.
MQSeries Get Processing
A message 204 is read from a nonindexed shared queue 106 by invocation of the following OS/390 service. This invocation will move the highest priority message 204 from the put queue 202 to the requesting shared queue manager 108 's uncommitted get queue 206 and read the contents into the requester's buffer.
?IXLLSTE
Request (MOVE)
LISTNUM (Scb_Put_List_Number)
LOCKOPER (Not Held)
MOVETOLIST (STRB_SQM_Uncommitted_Get_List_Header)
MOVETOKEY (TARGETENTRYKEY)
TARGETKEY (uncommitted_getq_key)
ENTRYTYPE (OLD)
LOCATOR (UNKEYPOS)
DIRECTION (HEADTOTAIL)
KEYCOMPARE (YES)
ENTRYKEY (Key_of_Message_to_MOVE = X‘0A0000 . . . 000’)
KEYREQTYPE (LESSOREQUAL)
AUTHCOMPARE (YES)
AUTHCOMP (Scb_LHQC_List_Authority)
AUTHCOMPTYPE (EQUAL)
ADJAREA (Adjunct)
ACTION (READ)
Buffer (parm_buffer)
BufSize (buffer_length)
CONTOKEN (Strb_Connect_Token)
Ansarea
AnsLen
Retcode
RsnCode
Mode (SyncSuspend)
The OS/390 service routine converts this to a Move and Read List Entry (MRLE) command with the following request operands:
Acronym
Operand
Contents
CC
Command code
Command Code for
MRLE
SID
Structure identifier
List Structure ID for
ConToken
LRT
Lock request type
Compare global
lock managers
CGLM
Comparative global lock manager
=B‘00’
LTEN
Lock table entry number
=X‘0000’|
LISTNUMBER
KCT
Key comparison type
Compare list entry
keys
KRT
Key request type
Compare for less
than or equal
LEK
List entry key
ENTRYKEY
VRT
Version request type
No action
VCRT
Version comparison request type
ignored
VN
Version number
ignored
CVN
Comparative version number
ignored
DIR
Direction
Right to left
ELT
Entry locator type
Locate entry by
unkeyed position
ELKT
Entry locator key type
ignored
LNCT
List number comparison type
Don't compare list
numbers
LCURT
List cursor request type
Do not update the
list cursor
TDIR
Target direction
Left to right
MELT
Move entry locator type
Set key to target list
entry key
TLEK
Target list entry key
TARGETKEY
TLN
Target list number
MOVETOLIST
LET
List entry type
Read data and
adjunct
LN
List number
LISTNUMBER
LEID
List entry
ignored
SLCCC
Suppress list count comparison control
Check list entry
count limit
AKRT
Assignment key request type
List entry key not
assigned
AKUT
Assignment key update type
ignored
LAUCT
List authority comparison type
Compare for equal
LAURT
List authority replacement type
Do not replace list
authority
LCUT
List cursor update type
ignored
STDIR
Secondary target direction
Left to right
SKCT
Secondary key comparison type
ignored
SKRT
Secondary key request type
ignored
MPKP
Maintain primary key position
Ignored
MSKP
Maintain secondary key position
ignored
UID
User identifier
ignored
LAU
List authority
ignored
CLAU
Comparative list authority
AUTHCOMP
AKI
Assignment key increment
ignored
SLEK
Secondary list entry key
zero
The message buffer address (Buffer) and length (Buffsize) are used to create a message buffer address list (MBAL) which accompanies the message command block 1002 for the Move and Read List Entry (MRLE) command to the selected coupling facility structure 902 . The coupling facility and structure identifier for the list structure 902 are obtained through controls associated with the ConToken.
When the coupling facility 104 receives the message command block 1002 for the Move and Read List Entry (MRLE) comma nd, the following actions are taken.
1. The value of AUTHCOMP is compared against the list authority object with the last known value of the list authority. If the comparison shows the values are not equal, the command ends without moving or reading a list entry 1208 and an appropriate response code is returned. If the comparison shows the values are equal, the command continues. 2. The value of the global lock manager field in the lock table entry 11112 associated with the list 1106 (i.e. Lock table entry number=LISTNUM) is compared against a value of zero. If the global lock manager field is not zero, the list 1106 is locked and cannot be changed. In this case the command ends without moving or reading a list entry 1208 and an appropriate response code is returned. If the global lock manager field is zero, the command continues. 3. The topmost list entry 1208 on the designated list 1106 is located and the list entry key is compared with the ENTRYKEY=X‘0A000 . . . 0’. If the list entry key is less than or equal to the ENTRYKEY value, then the list entry 1208 represents a committed message and the command continues. If the list entry key is greater than the ENTRYKEY value, then the list entry 1208 represents an uncommitted message (List entry key=X‘F6xxxxx’) and the command completes without moving or reading the list entry 1208 and an appropriate response code is returned. 4. The list entry (or element) count limit is checked against the current list entry (or element) count to ensure that moving the list entry 1208 to the target list 1106 will not cause the count of list entries 1208 to exceed the limit. If this is the case, the command ends without moving or reading the list entry 1208 and an appropriate response code is returned. If the list entry (or element) count limit is not exceeded by the movement of the list entry 1208 , the command continues 5. The list entry 1208 is removed from the source list 1106 and the list entry (or element) count for the source list 1106 is decremented. 6. The list entry 1208 is inserted in the target position for the primary key ordering for the specified target list 1106 based on the value of the target list entry key and the target direction. 7. The list entry 1208 is inserted in the target position for the secondary key ordering based on the value of zero. (Note that the OS/390 service sets the first 32 bytes of the adjunct area equal to zero.) 8. The list entry (or element) count for the target list 1106 is incremented. 9. The adjunct data is returned in the message response block 1004 and the data list entry 1212 is returned to the user's buffer. 10. The command is completed and an appropriate response code is returned.
GetWait Request
When no committed messages 204 exist on the put list 202 , the CF Manager (a component of shared queue manager 108 as described in the referenced related application) is instructed to monitor the committed range 208 of the put list for transitions from the empty to the nonempty state by invocation of the following OS/390 service:
?IXLLSTC
Request (MONITOR_KEYRANGE)
CONTOKEN (Strb_Connect_Token)
LISTNUM (List_Number_to_Process)
ACTION (Start)
VECTORINDEX (Scb_Put_List_Number)
DRIVEEXIT (Yes)
RETCODE
RSNCODE
ANSAREA
ANSLEN
MODE (SyncSuspend)
The OS/390 service establishes an internal bind between the CF Manager routine and the list notification vector index value equal to LISTNUM and then issues a Register List Monitor (RLM) command to the coupling facility 104 to register the CF Manager as a key range monitor for the key range associated with the put list 202 . The RLM command is issued with the following request operands:
Acronym
Operand
Contents
CC
Command code
Command Code for
RLM
SID
Structure identifier
List Structure ID for
ConToken
KT
Key type
ignored
MRT
Monitor request type
Register key range
monitor
INRT
Initial notification request type
ACTION = Start
ANENI
Aggressive not-empty notification
=Inactive
indicator
WEQTC
Write event queue transition count
ignored
AOC
Attachment override control
Check for attachment
KRNRT
Key range notification request type
Update the vector
summaries
KRNEN
Key range notification entry
VECTORINDEX
number
UID
User identifier
User ID for ConToken
LN
List number
LISTNUM
LEK
List entry key
ignored
SLEK
Secondary list entry key
ignored
UNC
User notification control
ignored
EQTC
Event queue transition count
ignored
When the coupling facility 104 receives the message command block 1002 for the Register List Monitor (RLM) command, the following actions are taken.
1. The attachment status of the specified user identifier is checked. The user must be attached with a nonzero list notification in the user controls 1108 . If the user is not attached the command ends in error. If the user is attached, but the list notification token is zero, the user is not registered and the command completes with an appropriate response code. If the user is validly attached, the command continues. 2. The monitor request type is decoded and indicates that the requested function is key range monitoring. If the key range for the list 1106 is in the process of being initialized, the user is not registered and the command completes with an appropriate response code. If the key range is not being initialized, then the command continues. 3. The user is registered as a key range monitor by setting the key range monitor active bit (KRMAB) to active in the entry 1302 of the key range monitor table 1204 for the specified list 1106 indexed by the UID. The entry 1302 is further initialized by storing the key range notification request type (KRNT) and the key range notification entry number (KRNEN) request operands into the table entry. 4. If the key range is not empty, a notification signal is sent to the user, specifying the list notification token in the user controls 1108 , and setting the LNEN and LNRT controls to the values of the KRNT and KRNEN objects respectively. 5. The command is completed and an appropriate response code is returned.
The key range for the put list 202 had been previously established by the CF Manager when the structure 902 was allocated by invocation of the following OS/390 service:
?IXLLSTC
Request (WRITE_LCONTROLS)
CONTOKEN (parm_Connect_Token)
LISTNUM (parm_List_Header)
AUTHCOMP (Current_List_Authority)
NEWAUTH (New_Authority_Value)
KEYRANGE (SET)
KEYRANGESTART (csqe_key_all_zeros = X‘000000......0000’)
KEYRANGEEND (Key_Range_End = X‘09FFFFFFFF....FFFFF’)
KEYRANGESTATE (Define)
KREMPTY (TrigDepth = 0)
KRNOTEMPTY (TrigDepth = 0)
DRIVEEXIT (Yes)
RETCODE
RSNCODE
ANSAREA
ANSLEN
MODE (SyncSuspend)
Acronym
Operand
Contents
CC
Command code
Command Code for
WLC
SID
Structure identifier
List Structure ID for
ConToken
LCT
List control type
Update key range/
thresholds
CDIR
Cursor direction
ignored
CDT
Cursor direction type
ignored
LN
List number
LISTNUM
LECL
List entry count limit
ignored
LEID
List entry identifier
ignored
CLAU
Comparative list authority
AUTHCOMP
LAU
List authority
NEWAUTH
ULC
User list control
ignored
AKT
Assignment key threshold
ignored
AK
Assignment key
ignored
LSTC
List state transition count
ignored
KRLEK
Key range list entry key
KEYRANGESTART
KRMLEK
Key range maximum list entry key
KEYRANGEEND
KRENT
Key range empty notification
KREMPTY = ‘0’
threshold
KRNENT
Key range not-empty not. threshold
KRNOTEMPTY = ‘0’
LENT
List empty notification threshold
ignored
LNENT
List not-empty notification
Ignored
threshold
When the coupling facility 104 receives the message command block 1002 for the Write List Controls (WLC) command, the following actions are taken.
1. The value of AUTHCOMP is compared against the list authority object with the last known value of the list authority. If the comparison shows the values are not equal, the command ends without updating the list controls 1202 and an appropriate response code is returned. If the comparison shows the values are equal, the value of NEWAUTH is placed in the list authority object and the command continues. 2. The list control type is decoded and it is determined that the key range and key range thresholds are to be updated and no other controls are changed. 3. The key range and key range thresholds are updated by storing the values of the KRLEK, KRMLEK, KRENT, and KRNENT operands into the list controls 1202 and initializing the key range. 4. If key range initialization completes the resulting key range state is set and the key range monitors are notified of the resulting state. The command completes after the notifications have completed and an appropriate response code is returned. 5. If key range initialization does not complete within a model dependent time period, an appropriate response code is returned. Key range initialization remains active.
SMQ Recovery—Deletion of Uncommitted Messages
A two-phase recovery protocol is executed for any shared queue manager (SMQ) 108 that fails. A step in the second phase a recovery process deletes all uncommitted list entries 1208 written by the shared queue manager 108 that is being recovered. This is accomplished by using the new Delete List (DL) command with key range processing. The start of the range is the begin key, which is set to X‘F6’.QMID.(14 bytes of zeros) and the end key is set to X‘F6’.QMID.(14 bytes of ones). The QMID is the identifier of the failed SMQ 108 and the range identifies all possible puts to the uncommitted put queue portion 210 by the failed SMQ 108 . Specifying the range ensures that all the uncommitted message will be deleted without the recovering process needing to know the number or exact key values of list entries 1208 being deleted.
This function is accomplished by issuing the following OS/390 service.
?IXLLSTM
Request (DELETE_LIST)
CONTOKEN (Strb_Connect_Token)
LOCATOR (KEYPOS)
LISTNUM (List_Number_to_Process)
KEYTYPE (ENTRY)
ENTRYKEY (begin_key = X‘F6’|QMID|0000000000...0000)
KEYREQTYPE (Range)
KEYCOMPARE (YES)
KEYRANGEEND (end_key = X‘F6’|QMID|FFFFFFFF...FFFF)
RETCODE
RSNCODE
ANSAREA
ANSLEN
The OS/390 service converts this to a Delete List (DL) command with the following request operands:
Acronym
Operand
Contents
CC
Command code
Command Code for DL
SID
Structure identifier
List Structure ID for
ConToken
LRT
Lock request type
No lock comparison
CGLM
Comparative global lock manager
ignored
LTEN
Lock table entry number
ignored
KCT
Key comparison type
Compare list entry keys
KRT
Key request type
Compare within key
range
LEK
List entry key
ENTRYKEY = X‘F6|
QMID|00..00’
VRT
Version request type
No action
VCRT
Version comparison request type
ignored
VN
Version number
ignored
CVN
Comparative version number
ignored
DIR
Direction
Right to right
ELT
Entry locator type
Locate entry by keyed
position
ELKT
Entry locator key type
Locate by list entry key
LNCT
List number comparison type
Don't compare list
numbers
LN
List number
LISTNUMBER
LEID
List entry
ignored
LAUCT
List authority comparison type
Compare for equal
LSKT
List scan key type
Left to right
SKCT
Secondary key comparison type
ignored
SKRT
Secondary key request type
ignored
UID
User identifier
ignored
MLEK
Maximum list entry key
KEYRANGEEND =
X‘F6|QMID|FF....FF’
CLAU
Comparative list authority
AUTHCOMP
MSLEK
Maximum secondary list entry key
ignored
SLEK
Secondary list entry key
ignored
When the coupling facility 106 receives the message command block 1002 for the Delete List (DL) command, the following actions are taken.
1. The value of AUTHCOMP is compared against the list authority object with the last known value of the list authority. If the comparison shows the values are not equal, the command ends without deleting a list entry 1208 and an appropriate response code is returned. If the comparison shows the values are equal, the command continues. 2. The list 1106 is searched in primary key order. The leftmost list entry 1208 within the specified key range is located and deleted from the list 1106 . The list entry count is also decremented. 3. Step 2 is repeated until either a model-dependent timeout is exceeded or all the list entries 1208 in the specified range are deleted. If a model-dependent timeout is exceeded, the command is completed and an appropriate response code is returned. If all the list entries 1208 in the specified range are deleted, an appropriate response code is returned.
While a particular embodiment has been shown and described, various modifications will be apparent to those skilled in the art. While the invention has particular application in a message queuing environment, it is not limited to such an environment and may be used in other environments as well. | Various enhancements are made to the architecture of a list processor to facilitate its use in implementing a message queue that is shared by queue managers residing across a multisystem complex. A new list structure control—a program list entry identifier indicator, or PLEIDI—is defined to allow the user to specify whether user-defined entry IDs are used when the list is allocated. A new delete list (DL) command is added that sequentially processes list entries in the order in which they exist on the specified list. A new move list entries (MLES) command provides a performance-optimized means to process an input list of entries. New key comparison functions and list monitoring enhancements have also been added. A new type of key called a secondary list entry key (SLEK) allows the user to specify a secondary key value as a means to identify a list entry. | 8 |
FIELD OF THE INVENTION
The invention pertains to a method for determining the equivalent fracture permeability of a fractured network in a subsurface fractured multi-layered medium useful for creating more realistic modeling of a fractured subsurface geological structure. The method can be implemented for example by reservoir engineers for obtaining reliable oil flow predictions.
BACKGROUND OF THE INVENTION
Fractured reservoirs are an extreme kind of heterogeneous reservoirs, with two contrasted media, a matrix medium containing most of the oil in place and having a low permeability, and a fracture medium usually representing less than 1% of the oil in place and being highly conductive. The fracture medium itself may be complex, with different fracture sets characterized by their respective fracture density, length, orientation, tilt and aperture. 3D images of fractured reservoirs are not directly usable as a reservoir simulation input. Representing the fracture network in reservoir flow simulators was long considered as unrealistic because the network configuration is partially unknown and because of the numerical limitations linked to the juxtaposition of numerous cells with extremely-contrasted size and properties. Hence, a simplified but realistic modeling of such media remains a concern for reservoir engineers.
The "dual-porosity approach" as taught for example by Warren, J. E. et al "The Behavior of Naturally Fractured Reservoirs", SPE Journal (September 1963), 245-255, is well-known in the art to interpret the single-phase flow behavior observed when testing a fractured reservoir. According to this basic model, any elementary volume of the fractured reservoir is modeled as an array of identical parallelepipedic blocks limited by an orthogonal system of continuous uniform fractures oriented along one of the three main directions of flow. Fluid flow at the reservoir scale occurs through the fracture medium only and locally fluid exchanges occur between fractures and matrix blocks.
Numerous fractured reservoir simulators have been developed using such a model with specific improvements concerning the modeling of matrix-fracture flow exchanges governed by capillary, gravitational, viscous forces and compositional mechanisms, also the consideration of matrix to matrix flow exchanges (dual permeability dual-porosity simulators). Various examples of prior art techniques are referred to in the following references.
Thomas, L. K. et al: "Fractured Reservoir Simulation," SPE Journal (February 1983) 42-54;
Quandalle, P et al: "Typical Features of a New Multipurpose Reservoir Simulator", SPE 16007 presented at the 9th SPE Symposium on Reservoir Simulation held in San Antonio, Tex., Feb. 1-4, 1987;
Coats, K. H.: "Implicit Compositional Simulation of Single-Porosity and Dual-Porosity Reservoirs," paper SPE 18427 presented at the SPE Symposium on Reservoir Simulation held in Houston, Tex., Feb. 6-8, 1989.
A problem met by reservoir engineers is to parameterize this basic model in order to obtain reliable flow predictions. In particular, the basic fracture and matrix petrophysical properties as well as the size of matrix blocks have to be known for each cell of the flow simulator. Whereas matrix permeability can be estimated from cores, the permeability of the fracture network contained in the cell, i.e. the equivalent fracture permeability, cannot be estimated in a simple way and requires taking the geometry and properties of the actual fracture network into account.
A direct method is known for determining steady-state flow in a fracture network. It involves use of conventional fine regular grids discretizing both the fractures and the matrix blocks of the parallelepipedic fractured rock volume considered. For several reasons this known method does not provide reliable results except if the fractured rock volume is discretized using a grid with a drastically-high number of cells, which requires huge computing ressources.
Other specific models which compute equivalent permeabilities of 2D or 3D fracture networks, are also known for example from:
Odling, N. E.: "Permeability of Natural and Simulated Fracture Patterns," Structural and Tectonic Modelling and its Application to Petroleum Geology NPF Special Publication 1, 365-380, Elsevier. Norwegian Petroleum Society (NPF) 1992;
Long, J. C. S., et al; "A Model for Steady Fluid Flow in Random Three-Dimensional Networks of Disc-Shaped Fractures," Water Resources Research (August 1985) vol. 21, No. 8, 1105-1115;
Cacas, M. C. et al; "Modeling Fracture Flow With a Stochastic Discrete Fracture Network: Calibration and Validation. 1. The Flow Model," Water Resources Research (March 1990) vol. 26, No. 3;
Billaux, D.: <<Hydrogeologie des milieux fractures. Geometrie, connectivite et comportement hydraulique>> PhD Thesis, presented at the Ecole Nationale Superieure des Mines de paris; Document du BRGM N°186, Editions du BRGM, 1990;
Robinson, P. C.: <<Connectivity, Flow and Transport in networks Models of Fractured Media>>, PhD Thesis, St Catherine's College, Oxford University, Ref.: TP1072, May 1984.
SUMMARY OF THE INVENTION
The invention deals with a method for determining the equivalent fracture permeability of a fractured network in a subsurface multi-layered medium.
The method distinguishes in that it comprises the steps of:
discretizing the fracture network in fracture elements (such as rectangles for example) and defining nodes representing interconnected fracture elements in each layer of the medium; and
determining fluid flows through the discretized network while imposing boundary pressure conditions, and fluid transmissivities to each couple of neighboring nodes.
The method can be more precisely defined as including the steps of:
partitioning the medium in a set of parallel layers each extending in a reference plane perpendicular to a reference axis and defined each by a co-ordinate along said axis;
partitioning each fracture in a series of rectangles limited along said reference axis by two adjacent layers and itemizing the rectangles by associating therewith geometrical and physical attributes such as co-ordinates and sizes of the rectangles and hydraulic conductivities of the fractures;
positioning nodes in each layer for all the interconnected fractures; and
for all the couples of neighboring nodes, calculating transmissivity factors and solving flow equations to determine the equivalent permeabilities of the medium in three orthogonal directions.
In a preferred embodiment, equivalent permeability of the medium includes directly determining equivalent permeability anisotropy tensor and calibrating absolute values of permeability from well tests results.
The method as summarized allows for systematically linking fractured reservoir characterization models and dual-porosity simulators in order to create a more realistic modeling of a fractured subsurface geological structure. The method can be implemented for example in oil production by reservoir engineers for obtaining reliable flow predictions.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the method according to the invention will be clear from reading the description hereafter of embodiments given by way of non limitative examples, with reference to the accompanying drawings where:
FIG. 1 shows for example a 3D image of a fracture network stochastically generated from observations of and measurements on a sandstone outcrop;
FIGS. 2, 3 show a fracture partitioned in a series of rectangles R;
FIG. 4 shows the input data structure itemizing the fracture attributes;
FIG. 5 shows the preferred mode to discretize a fracture plane;
FIGS. 6, 7, 8, and 9 schematically illustrate computation of transmissivity factors for different positions of nodes with respect to one another or with a boundary.
FIGS. 10A and 10B illustrate the method of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The equivalent permeabilities of a 3D fracture network is determined hereafter by using a numerical technique based on the known "resistor network" method as shown for example in the prior reference to Odling, N. E. In the present method the matrix is supposed to be impermeable in order to be consistent with the dual-porosity approach. In reservoir simulators, matrix-to-fracture and matrix-to-matrix flows are actually computed separately from fracture flows.
The 3D fracture network considered is assumed to represent in a volume equal to a reservoir cell the real distribution of fractures given by integration of fracture attributes of the field in a characterization model. The main objective of single-phase flow computations on the 3D fracture network is to evaluate the equivalent permeability anisotropy (Kv/Kh and Ky/Kx) of the fracture cell considered, which is an important parameter controlling reservoir multiphase flow behavior. The equivalent permeability values drawn from such computations would in practice be compared with the results of well tests in order to calibrate fracture attributes such as fracture hydraulic conductivities (or equivalent hydraulic apertures), which may be poorly defined a priori.
In addition, equivalent permeability results can be used to determine a permeability tensor, the main directions of which enable an optimal orientation of the reservoir model grid. However, to obtain such information, specific boundary conditions are required. Lateral no-flow boundary conditions imposed on the four lateral faces of the parallelepipedic volume studied do not give access to non-diagonal terms of the equivalent permeability tensor, whereas linearly-varying potentials (or pressures) on lateral faces enable to impose the direction of potential gradient within the anisotropic medium and to directly derive non-diagonal permeability terms from lateral flow rates.
The techniques to integrate natural fracturing data into fractured reservoir models are well known in the art. Fracturing data are mainly of a geometric nature and include measurements of the density, length, azimuth and tilt of fracture planes observed either on outcrops, mine drifts, cores or inferred from well logging. Different fracture sets can be differentiated and characterized by different statistical distributions of their fracture attributes. Once the fracturing patterns have been characterized, numerical networks of those fracture sets can be generated using a stochastic process respecting the statistical distributions of fracture parameters. Such process are disclosed for example in patents FR-A-2,725,814, 2,725,794 or 2,733,073 of the applicant.
The method according to the invention is applied to images of fractured geological structures of various size or volume and/or at various locations which are generated by a fracture model generator. Such an image is shown on FIG. 1.
INPUT DATA
Before developing the procedures recommended to determine equivalent hydraulic parameters of 3D fracture images, an important step is to define first a common input data structure for these images, so that they can be processed independently of the processing tool used to generate them.
As shown on FIGS. 2, 3, fractures F are assumed to be substantially vertical (i.e. perpendicular to the layer limits). However, a same data structure can be applied to fractures slightly deviating from the vertical direction. The 3D image is discretized vertically complying with the actual geological layering if such information is available. If not, any arbitrary discretisation is applied to the image. Each horizontal layer L is characterized by its vertical coordinate zL in the reference system of coordinates (OX, OY, OZ).
For each layer L, a series of rectangles R has to be defined. Each rectangle consists in a fracture plane element comprised between the limits of a given layer. Hence, each natural fracture consists in a set of superimposed rectangles R and is assigned an origin (fracture origin). Each rectangle is defined by:
the three coordinates (xO, yO, zO) of the rectangle origin O. For a given natural fracture, all the origin points of the constitutive rectangles are situated on the same vertical (or highest dip) line drawn from the fracture origin;
the co-ordinates of the horizontal unit vector i (xH, yH) and of the vertical unit vector j (xV, yV) defining the orientation of the rectangle in the reference system of co-ordinates, with x Vertical and y Vertical being zero in case of vertical fractures but considered as input data to be able to deal with non-vertical fractures;
the two algebraic horizontal lengths l- and l+ separating the origin of the rectangle and the two lateral (vertical) limits of this rectangle;
the height h of the rectangle, that is the length of the rectangle along direction j which is the layer thickness if discretisation along direction j fits the geology;
the hydraulic conductivity c derived from the application of Darcy's law to fracture flow (for a pressure gradient ##EQU1## the flow rate in the fracture with a height h is ##EQU2## μ being the fluid viscosity). The conductivity c is given by the relation c=k.a where k=a 2 /12 (using Poiseuille's idealized representation of fractures) is the intrinsic permeability of the fracture and a its equivalent hydraulic aperture a. The hydraulic conductivity c is a reference value given for a direction of the maximum horizontal stress parallel to the fracture direction;
the two upper and lower neighboring rectangles UR, LR;
the fracture set FS to which the rectangle considered belongs to;
the orientation angle α O of the direction of maximum horizontal stress taken from (OX) axis in the reference system of coordinates;
for each fracture set, a correlation table correlating 1) the angle between the direction of maximum horizontal stress and fracture direction (azimuth) with 2) the hydraulic conductivity c or equivalent hydraulic aperture α previously defined. "Horizontal" and "vertical" stand in the context for directions respectively parallel and perpendicular to the limits of layers which here are assumed horizontal. Layer limits discretise fracture planes in the <<vertical>> direction. It must be pointed out that the aforesaid input data 1) are suitable for all the existing software tools used for characterizing and generating fracture and 2) could be used to discretise a network of slightly non-vertical fractures, i.e. not perpendicular to layer limits.
OPERATING PROCEDURES
Starting from the so-codified 3D image, operating procedures and validation tests of the method for computing permeability anisotropy of the fracture network taken as a whole, will be hereafter presented. The numerical procedure to calculate the equivalent permeabilities of a 3D fracture network is described.
The problem is to find the flow rate distribution in the network for the following boundary conditions on the limits of the studied parallelepipedic volume i.e. fixed pressures imposed on two opposite faces and pressures varying linearly on the four lateral faces (between the values imposed on the two other faces).
The main steps are summarized hereafter:
1). Network Discretization
Using the definitions given for the input data structure, the fracture network is discretized as a series of "nodes" N each node being placed at the middle of the intersection segments IS of two rectangles R (i.e. of two fracture planes within a given layer). As shown on FIG. 5, additional nodes AN are placed above and below the preceding nodes N to represent other rectangles discretizing the fractures and to minimize flow lengths within a given fracture. BL on FIG. 5 is a lateral limit of two neighboring fracture cells.
Once discretized, a screening procedure is applied to this fracture network in order to eliminate isolated nodes or groups of nodes with no connection with any of the lateral limits FL of the 3D volume studied, because such <<screened>> fractures do not contribute to fluid transport and may impede the solving procedures used to find pressures at fracture nodes during a steady-state flow through the network.
2) Calculation of Transmissivities
A transmissivity factor T is calculated for each pair of connected nodes using the relation: ##EQU3## where c is the fracture hydraulic conductivity, k, the fracture intrinsic permeability, a, the fracture aperture; h, the fracture height, and l, the distance between two fracture nodes.
Different situations have to be considered according to the respective position of the two nodes. For nodes within the same layer (FIG. 6), the horizontal transmissivity factor T is obtained directly as the distance (11+12) separating the two nodes in the flow direction (FIG. 7). For nodes in two different layers (FIG. 9), the vertical transmissivity factor is the arithmetic sum of the transmissivity factors (T'+T") referring to the two fracture plane elements of the superimposed fracture cells. It involves a flow length equal to the half sum of the two layer thicknesses .h1 and h2. For additional nodes as previously defined, connected via a single fracture plane, a single transmissivity factor is calculated for this fracture plane element.
The transmissivity factor T between a node and a limit of the 3D volume studied is expressed in a similar way as between two nodes, with the following two cases.
For a lateral vertical limit, the transmissivity factor T can be expressed directly for a single fracture plane element (FIG. 8), and as the sum of two transmissivities if two fracture planes link the node and the limit.
For a horizontal bottom or top limit, the vertical transmissivity factor can be expressed considering a flow length equal to half the layer thickness (FIG. 9).
3) Flow Equations
At steady state, an incompressible single-phase flow through the fracture network is determined by solving a set of n equations. one for each node, as well known in the art. Each equation expresses that the total flow rate is zero at each fracture node. For calculating a permeability tensor, it is considered a constant pressure is imposed on each of the upstream and downstream limits. A pressure varying linearly as a function of the position between upstream and downstream limits is imposed.
The matrix of equivalent permeability (Kij) previously determined is diagonalized to calculate the principal directions of flow with the respective equivalent permeabilities in these directions.
In practice, the problem is often limited to that of finding the principal horizontal directions of flow U and V since the direction perpendicular to layer limits (generally vertical) is always taken as z axis. In such a case, only the extra-diagonal terms K xy and K yx need to be calculated which can be obtained with the following mixed boundary conditions:
horizontal flows are computed with impermeable bottom and top faces, and linearly-varying pressures on the vertical faces parallel to flow direction;
vertical flow is computed with all lateral faces being impermeable.
Thus, a simplified permeability tensor is obtained from which the principal horizontal directions of flow U and V are easily derived: ##EQU4## Validation
The method has been successfully validated against the already mentioned reference single-phase flow computations performed with a conventional reservoir simulator. The reference computations were obtained on fine regular grids discretizing the fractures as well as the matrix blocks of the parallelepipedic fractured rock volume considered. For a given low direction, fixed injection pressure and production pressure were imposed on the inlet and outlet faces and the resulting flow rate was calculated with lateral no-flow conditions.
Three steps were followed, to validate the computation of:
the equivalent vertical permeability of a rock volume crossed by a single fracture, the latter being represented by several nodes corresponding to the intersections with small disconnected fractures;
equivalent horizontal permeabilities (in a 2D flow geometry) and the main flow directions;
equivalent permeabilities and permeability anisotropy in a simple network involving 3D flow geometry.
The results obtained for the third step (for a 3D flow geometry) are given in the following table. For th horizontal flow directions a reference analytical solution can also be calculated since the flow geometry is a 2D flow in these directions (3D flow geometry concerns the z direction).
______________________________________Equivalent FINE GRID PRESENT ANALYTICALpermeabilities (md) simulation METHOD solution______________________________________Kx 0.119 0.120 0.120Ky 0.224 0.227 0.226Kz 0.255 0.267Anisotropy 1.56 1.62Kz/(KxKy).sup.0.5______________________________________
It is the clear that the results obtained by the disclosed method are very close to the corresponding values obtained with the analytical solution and the fine grid simulation for directions X and Y.
In addition, the difference in the vertical equivalent permeability values involving 3D flow remains acceptable. Hence, the anisotropy ratio, equal to 1.6, is satisfactorily predicted by the method with a very limited number of cells.
The method according to the invention which provides easily transposed representation of a natural fracture network, is well adapted for fracture flow computations. It can also be useful for improving the original image of the fracture network. Such image is actually obtained form a stochastic fracture generator using as input results of integration of filed fracturing data in a fracture characterization model as shown in the already cited patents FR-A-2,725,814, 2,725,794 or 2,733,073 to the applicant. Such images once discretized with the procedure of the invention can be easily modified tofit with geological rules. For example systematic interruption of a given fracture against another fracture set can be accounted for in the original image by canceling fracture plane elements of a given set which extends beyond the intersected fractures of the other set.
FIG. 10A illustrates the basic method of the present invention. The method proceeds from starting point 100 to point 102 where discretizing each fracture (F) of the fracture network in fracture elements and defining nodes (N) representing interconnected fracture elements in each layer of the medium occurs. The method proceeds to point 104 where determining fluid flows through the fractured network while imposing boundary pressure conditions, and fluid transmissivities to each couple of neighboring nodes occurs. The method proceeds to endpoint 106.
FIG. 10B illustrates a more specific aspect of the method of the present invention. The method proceeds from point 200 to point 202 where petitioning the medium in a set of parallel layers (L) each extending in a reference plane (Ox, Oy) perpendicular to a reference axis (Oz) and defined each by a coordinate (Zo) along said axis occurs. The method proceeds to point 204 where petitioning each fracture in a series of rectangles (R) limited along said reference axis by two adjacent layers (L) and itemizing rectangles by associating therewith geometrical and physical attributes (co-ordinates and sizes of the rectangles and hydraulic conductivities of the fractures) occurs. The method proceeds to point 206 where positioning nodes (N) and each layer for all the interconnected fractures (F) for all the couples of neighboring nodes, calculating transmissivity factors and solving flow equations to determine the equivalent permeabilities of the medium in three orthogonal directions occurs. The method proceeds to endpoint 208. | Method for determining the equivalent fracture permeability of a fracture network in a subsurface multi-layered medium from a known representation of this network. The equivalent fracture permeability of a fractured network in a subsurface multi-layered medium, is determined by discretizing with a specific procedure each fracture (F) of the fracture network in fracture elements (R) (such as rectangles for example) and defining nodes N representing interconnected fracture elements in each layer of the medium and determining fluid flows (steady-state flows e.g.) through the discretized network while imposing boundary pressure conditions and fluid transmissivities to each couple of neighboring nodes. The method allows for a systematic linking of fractured reservoir characterization models with dual-porosity simulators in order to create a more realistic modeling of a fractured subsurface geological structure. The method can be implemented for example in oil production by reservoir engineers for obtaining reliable flow predictions. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION(S)
This is an ordinary application of U.S. Provisional Application Ser. No. 60/564,809, filed on Apr. 22, 2004, the content of which is expressly incorporated herein by reference as if set forth in full herein.
FIELD OF THE INVENTION
This invention relates to the composition, preparation and applications of dibenzodiazocine polymers.
BACKGROUND OF THE INVENTION
Organic materials that can be induced to undergo a shape change have recently attracted a great deal of interest in mechanical actuator applications. These materials convert chemical, electrical, or electromagnetic energy into mechanical work. Electromechanical actuators are of particular interest as synthetic muscle materials. While a few clever approaches and materials have been proposed for emulating the action of muscles, this research area is still in its infancy and synthetic muscles remain an unattained goal of material scientists.
Electromechanical actuators based on redox-active polymers have been the most extensively studied systems for mimicking the action of muscles. The actuation mechanism in these materials is based on bulk volume changes that result from the uptake and expulsion of counterions during the redox cycle as shown in FIG. 1 . Since the counterions in these systems have specific volumes, their introduction and removal from a bulk polymer result in the respective increase and decrease of the overall volume of the material. Unfortunately, slow cycle times and limited cycle lifetimes have prohibited the use of redox-active polymers as synthetic muscles. These limitations have fueled the search for new materials that are capable of electromechanical actuation via different mechanisms.
One of the more interesting approaches for achieving electromechanical actuation is based on [8]annulenes, which are eight-membered macrocycles with alternating single-and-double carbon bonds. These systems have tub-like structures in their neutral state that can undergo redox-induced tub-to-planar conformational changes. For example, the parent [8]annulene, cyclooctatetraene, undergoes a reversible conformation change from a contracted structure to a planar structure upon two-electron reduction described in Scheme 1 below. This conformation change also results in an increase
in distance between nonadjacent carbon atoms (e.g., d planar and d tub Scheme 1) that can be used to mimic the expansion and contraction of muscle tissue.
A useful way of harnessing the tub-to-planar geometry change of [8]annulenes in electomechanical actuators is to incorporate such ring systems into polymer structures, since polymers allow for facile processing into useful shapes. However, for such polymer materials to be useful in these applications they must also exhibit stable and reversible redox chemistry and be conjugated to facilitate long-range redox communication between repeat units. It is also highly desirable that their synthesis be facile and allow for structural variation so that the properties of the materials can be tailored to the needs of specific applications.
It turns out that these requirements place severe limitations on the use of polymers containing [8]annulene units in electromechanical actuation. For example, conjugated polymers incorporating cyclooctatetraene units are not useful in these applications because they are exceedingly difficult to prepare and can only be reduced under inert atmospheric conditions. While the redox stability of conjugated polymers containing [8]annulenes are dramatically improved by fusing six-membered rings to the cyclooctatetraene units such as in 1, 2,5,6-dibenzocyclooctatetraene 1 and tetra benzocyclooctatetraene 2, conjugated polymers incorporating these units have not been reported (presumably because they are also difficult to prepare). Additionally, the steric hindrance of the adjacent phenyl rings in 2 prevents its tub-to-planar conformation change. These restrictions have severely limited the ability to prepare useful polymer materials for electromechanical actuation based on the redox-induced conformational change of [8]annulene units.
SUMMARY OF THE INVENTION
In one aspect, the present invention is directed to a polymer comprising repeat units selected from the group consisting of:
where R 1 –R 8 are independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, halogen, —CN, —CHO, —COR a , —CR a ═NR b , —OR a , —SR a , —SO 2 R a , —POR a R b , —PO 3 R a , —OCOR a , —CO 2 R a , —NR a R b , —N═CR a R b , —NR a COR b , —CONR a R b in which R a and R b are independently selected from the group consisting of H, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl and two or more of R 1 –R 8 , R a , and R b may or may not be linked to form a ring structure.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a conceptual illustration of the mechanism of electromechanical actuation in a redox-active polymer in which two individual polymer chains (ribbons) undergo a reversible displacement (Δd) on the intercalation of the counter ions (ovals) upon oxidation.
DETAILED DESCRIPTION OF THE INVENTION
This invention deals with the composition, preparation, and applications of dibenzodiazocine polymers. In one embodiment the dibenzodiazocine polymers provided in accordance with practice of the present invention comprise either or both of the following repeat units:
The dibenzodiazocine repeat units are diazo derivatives of [8]annulenes, and are therefore expected to be promising in electromechanical actuation applications. Set forth below are a number of polymer architectures and synthetic methodologies for the preparation of dibenzodiazocine-containing polymers. Additionally, several applications of these materials are described.
The polymers provided in accordance with the present invention are useful for high temperature applications. Polymers that are used in high temperature applications generally have maximum use temperatures of 200–250° C. While there are very few materials that tolerate maximum use temperature in excess of 250° C., their cost and/or their difficult processing protocols generally limit their widespread application. Derivatives of the dibenzodiazocine polymers provided in accordance with the present invention have exceedingly high glass transition temperatures (T g s), which is a rough indicator of the use temperature for amorphous polymers. For example, 3, 4, and 5 are amorphous polymers comprising n number of repeat or recurring units and having glass transition temperatures of 269° C., 310° C., and 329° C., respectively (as measured by differential scanning calorimetry, DSC). Moreover, these materials readily succumb to melt processing (see Examples, below).
EXAMPLES
Example 1
Preparation of 6: To a mechanically stirred solution of potassium hydroxide (148 g, 2.64 mol), phenylacetonitrile (16.7 mL, 0.126 mol mol), and methanol (300 mL) at 0° C. was added a solution of 4-bromonitrobenzene (25.4 g, 0.126 mol) in a 1:2 tetrahydrofuran:methanol solution (300 mL). The mixture was stirred for 4.5 h at 0° C. and then poured into water (1 L). The resulting precipitate was collected by filtration, and the product was purified by recrystallization from methanol. Yield 20.5 g (59.4%).
Preparation of 5-Bromo-2-aminobenzophenone: To a solution of 6 (27.4 g, 0.10 mol) in acetic acid (200 mL) at 80° C. was added water (50 mL) and iron powder (28 g, 0.5 mol) in ten portions over a two-hour period under nitrogen. The resulting mixture was stirred at 80° C. for an additional hour. The solution was cooled to room temperature and diluted with ether (1 L) and extracted with water (1 L). The organic layer was separated, dried, and condensed, and the product was recrystallized from methanol. Yield 22.38 g (81%).
Preparation of 3,3′Dibenzoylbenzidine (7): To a slurry of bis(1,5-cyclooctadiene)nickel(0) (22.5 g, 81.5 mmol) in dry dimethylformamide (200 mL) was added 5-bromo-2-aminobenzophenone (15 g, 54 mmol) in dry dimethylformamide (150 mL) under nitrogen. The slurry was stirred for 15 min at room temperature, stirred for 90 min at 42° C., and then poured in a 2% aqueous hydrochloric acid solution (500 mL). The solution was extracted with methylene chloride and the organic layer was filtered, dried, and condensed. The product was purified by chromatography. Yield 5.0 g (50%).
Preparation of 8: A 100 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser was charged with 7 (1.96 g, 5 mmol), toluene sulfonic acid monohydrate (0.19 g, 1 mmol), and 1,3-dichlorobenzene (20 mL). The mixture was heated at reflux for 2 h. The mixture was then cooled to room temperature, neutralized with triethylamine (0.5 mL), and the product was coagulated in methanol (75 mL) and dried in vacuo. Yield 0.77 g, molecular weight was 12,000 by GPC (relative to polystyrene standards).
Example 2
Preparation of 9: To a mechanically stirred solution of sodium hydroxide (100 g, 2.5 mole) in methanol (500 mL) was added phenylacetonitrile (64.4 g, 0.55 mol) at room temperature. The mixture was stirred for 5 min and then 4,4′-dinitrodiphenyl ether (65.1 g, 0.25 mol) was added. The solution was heated at 70° C. for 9 h and was then cooled to room temperature. The mixture was diluted with 50% aqueous methanol (250 mL) and cooled to approximately 0° C. The resulting precipitate was collected by filtration and purified by Soxhlet extraction with methanol. The product was dried in vacuo to give the product. Yield 38.4 g (38%).
Preparation of 4,4′-Diamino-3,3′-dibenzoyldiphenyl ether (10): A suspension of 9 (40.4 g, 0.10 mol) and 10% palladium on charcoal (2.12 g) in dry tetrahydrofuran (400 mL) was stirred under nitrogen at room temperature for 7.5 h. The reaction mixture was then filtered through Celite and the mother liquor was condensed. The resulting oil was mixed with methanol to afford the crystalline product, which was dried in vacuo. Yield 31.0 g (76%).
Preparation of 11: A 50 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser was charged with 10 (2.04 g, 5.0 mmol), p-toluenesulfonic acid monohydrate (190 mg, 1 mmol), and 1,3-dichlorobenzene (20 mL). The mixture was heated at reflux for 22 h during which additional solvent was added to keep the reaction volume at 20–30 mL. The reaction was cooled to room temperature and poured into methanol (125 mL) to give a greenish-gray precipitate. The solid was collected by filtration, dried, and dissolved in dichloromethane (50 mL). The resulting solution was washed with 1 M aqueous sodium hydroxide (2×10 mL) and water (10 mL). The organic layer was separated, concentrated, and poured into methanol to give the light gray solid, which was collected by filtration. The solid was dried in vacuo at 80° C. (16 h). Yield 1.36 g; bimodal molecular weight peaks at 5,000,000 and 29,000 by GPC (relative to polystyrene standards).
Example 3
Preparation of 12: A 22 L round-bottomed flask was charged with isatoic anhydride (2.0 kg, 12.3 mol), thionyl chloride (14.7 kg, 123 mol), and pyridine (5 mL), and the mixture was stirred under nitrogen for 8 days. The excess thionyl chloride was removed under vacuum and the product was distilled from the reaction flask. Yield 1.98 kg (89%).
Preparation of 2-amino-4′-fluorobenzophenone: A 12 L round-bottomed flask was charged with aluminum trichloride (2.79 kg, 20.9 mol) and fluorobenzene (3.0 kg, 31 mol) and the resulting solution was cooled to −5° C. under nitrogen. A solution of 12 (1.52 kg, 8.4 mol) in fluorobenzene (1.0 kg, 10 mol) was slowly added, and the mixture was allowed to stir for an additional hour, before being poured over 10 kg of ice. The resulting solid was collected by filtration and dissolved in methylene chloride (6 L). The solution was filtered and the mother liquor was dried over magnesium sulfate and filtered through silica gel. The mother liquor was condensed to give the product, which was purified by chromatography. Yield 630 g (35%).
Preparation of 13: A 100 mL round-bottomed flask fitted with a Dean-Stark condenser was charged with 2-amino-4′-fluorobenzophenone (40 g, 0.19 mol), toluene sulfonic acid monohydrate (1.8 g, 0.01 mol), and xylene (40 mL). The mixture was heated at reflux for 16 h, before being cooled to room temperature. The resulting solid was purified by recrystallization from methylene chloride/hexane to give the product, which was dried in vacuo. Yield 32.75 g (89%).
Example 4
Preparation of 3: A 125 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser was charged with bis-phenol-A f (4.267 g, 12.7 mmol), potassium carbonate (2.629, 19.1 mmol), N-methylpyrrolidinone (48 mL), and toluene (29 mL). The system was purged with nitrogen (0.5 h) and heated to reflux (16 h). A solution of 13 (5.0 g, 12.7 mmol) in toluene (29 mL) was added to the reaction mixture and 20–30 mL of toluene was removed by distillation. The resulting solution was heated at approximately 160° C. for 24 h. The reaction mixture was then diluted with N-methylpyrrolidinone (50 mL), cooled to room temperature, and poured into methanol (300 mL). The resulting gray solid was collected by filtration and dried in vacuo for 16 h. Dissolution in N-methylpyrrolidinone (100 mL) and filtration (1.2μ) was used to further purify the polymer. The filtrate was poured into methanol (600 mL), and the resulting solid was collected by filtration and washed with fresh methanol (100 mL). The solid was suspended in boiling methanol (300 mL, 2 h) before being collected by filtration and dried in vacuo at 65° C. for 6 h and then 165° C. for 16 h. Yield 7.16 g (82%); bimodal molecular weight peaks at 1,400,000 and 66,000 by GPC (relative to polystyrene standards).
Example 5
Preparation of 4: A 125 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser was charged with biphenol (2.362 g, 12.7 mmol), potassium carbonate (2.629, 19.1 mmol), N-methylpyrrolidinone (48 mL), and toluene (29 mL). The system was purged with nitrogen (0.5 h) and heated to reflux (16 h). A solution of 13 (5.0 g, 12.7 mmol) in toluene (29 mL) was added to the reaction mixture and 20–30 mL of toluene was removed by distillation. The resulting solution was heated at approximately 160° C. for 10 h. The reaction mixture was then diluted with N-methylpyrrolidinone (100 mL), cooled to room temperature, and poured into methanol (600 mL). The resulting gray solid was collected by filtration and dried in vacuo for 16 h. Dissolution in N-methylpyrrolidinone (100 mL) and filtration (1.2μ) was used to further purify the polymer. The filtrate was poured into methanol (600 mL), and the resulting solid was collected by filtration and washed with fresh methanol (100 mL). The solid was suspended in boiling methanol (300 mL, 2 h) before being collected by filtration and dried in vacuo (65° C. for 6 h, then 165° C. for 24 h). Yield 5.70 g (83%); molecular weight is 100,000 by GPC (relative to polystyrene standards).
Example 6
Preparation of 14: A 250 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser is charged with biphenol (19.5 mmol), 4-hydroxybiphenyl (0.5 mmol), potassium carbonate (30 mmol), N-methylpyrrolidinone (75 mL), and toluene (45 mL). The system is purged with nitrogen (0.5 h) and heated to reflux for 16 h. A solution of 13 (5.0 g, 12.7 mmol) in toluene (25 mL) is added to the reaction mixture and 30–40 mL of toluene is removed by distillation. The resulting solution is heated at reflux for 10 h. The reaction mixture is then diluted with N-methylpyrrolidinone (150 mL), cooled to room temperature, and poured into methanol (1 L). The resulting solid is collected by filtration and dried in vacuo for 16 h. The solid is dissolved in N-methylpyrrolidinone (200 mL), filtered, and precipitated into methanol (600 mL). The solid is suspended in boiling methanol (400 mL, 2 h) and then filtered and dried in vacuo.
Example 7
Preparation of 5: A 1 L, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser was charged with fluorene bisphenol (22.3 g, 63.5 mmol), potassium carbonate (13.1, 95.2 mmol), N-methylpyrrolidinone (257 mL), and toluene (128 mL). The system was purged with nitrogen (0.5 h) and heated to reflux for 16 h. The mixture was cooled slightly and 13 (25.0 g, 63.5 mmol) was added. The resulting solution was heated at reflux for 24 h. The reaction mixture was then diluted with N-methylpyrrolidinone (100 mL), cooled to room temperature, and poured into methanol (2 L). The resulting solid was dried in vacuo for 16 h. The polymer was dissolved in N-methylpyrrolidinone (900 mL), filtered (1.2μ), and the polymer was precipitated in water (3.6 L). The solid was collected and was suspended in boiling methanol (500 mL) before being collected by filtration and dried in vacuo (110° C. for 16 h. Yield 40.7 g (91%); molecular weight is 90,000 by GPC (relative to polystyrene standards).
Example 8
Preparation of 15: A 250 mL round-bottomed flask fitted with a Dean-Stark condenser was charged with 2-amino-4′-chlorobenzophenone (25 g, 0.11 mol), toluene sulfonic acid monohydrate (1.0 g, 0.005 mol), and xylene (90 mL). The mixture was heated at reflux for 16 h, before being cooled to room temperature. The resulting solid was purified by chromatography. Yield 18.5 g (80%).
Example 9
Preparation of 16: A 40 mL vial was charged with 15 (1.71 g, 4 mmol), 2,5-dichlorobenzophenone (1.0 g, 4 mmol), activated zinc powder (0.75 g, 12 mmol), nickel bromide (0.033 g, 0.15 mmol), triphenylphosphine (0.38 g, 0.15 mmol), sodium bromide (0.070 g, 0.68 mmol), and dry N-methylpyrrolidinone (10 mL) under nitrogen. The vial was sealed and the mixture was heated in an orbital shaker at 70° C. for 20 h. The mixture was then diluted with N-methylpyrrolidinone (20 mL) and filtered. The filtrate was poured into methanol (150 mL), and the resulting solid was collected by filtration. The solid was boiled in methanol (200 mL) and then dried in vacuo at 80° C. Yield 1.15 g (54%); molecular weight is 61,000 by GPC (relative to polystyrene standards).
Example 10
Preparation of 1,4-dihexylbenzene: A 2 L round-bottomed flask is charged with 1,4-dichlorobenzene (118 g, 0.80 mol), [1,3 -bis(diphenylphosphino)propane]Ni(II) chloride (500 mg, 0.9 mmol), and dry ether (600 mL). The mixture is cooled to 0° C. and a 2 M solution of n-hexylmagnesium bromide in ether (1 L) is added dropwise. The cooling bath is removed, and the solution is slowly heated to reflux and allowed to boil for 24 h. The mixture is cooled to 0° C. and diluted with water (50 mL) and then with a 2 M aqueous hydrochloric acid solution (500 mL). The aqueous layer is separated, extracted with ether (2×200 mL), and the combined organic layers are washed with water (100 mL) and dried over magnesium sulfate. The solvent is removed in vacuo and the product is purified by distillation.
Preparation of 2,5-dibromo-1,4-dihexylbenzene: To a mixture of 1,4-dihexylbenzene (0.16 mol) and iodine (0.2 g, 1.6 mol) is added bromine (0.34 mol) dropwise in the dark. After 1 day at room temperature, a 20% aqueous potassium hydroxide solution (100 mL) is added, and the resulting mixture is shaken under slight warming until the color disappears. The mixture is then cooled to room temperature, the aqueous solution is decanted, and the product is crystallized from ethanol.
Preparation of 17: To a solution of 2,5-dibromo-1,4-dihexylbenzene (33 mmol) in tetrahydrofuran is added magnesium turnings (1.9 g, 80 mmol) under argon. The resulting Grignard reagent solution is slowly dropped into a stirred solution of trimethyl borate (38 mL, 330 mmol) in tetrahydrofuran at −78° C. for 2 h, and the resulting solution is warmed to room temperature and stirred for 2 days. The reaction mixture is poured over a 5% sulfuric acid/crushed ice solution while stirring, and the mixture is extracted with ether. The organic layer is separated and condensed, and the resulting solid is recrystallized from hexane-acetone. This solid is then stirred with 1,2-ethanediol (50 mmol) in toluene for 10 h, and the product is purified by chromatography.
Preparation of 2-amino-4′-bromobenzophenone: A 1 L round-bottomed flask is charged with aluminum trichloride (2.1 mol) and bromobenzene (3.1 mol) and the resulting solution is cooled to −5° C. under nitrogen. A solution of 12 (1.52 kg, 8.4 mol) in bromobenzene (1.0 kg, 10 mol) is slowly added and the mixture is allowed to stir for an additional hour, before being poured over 1 kg of ice. The resulting solid is collected by filtration and dissolved in methylene chloride (600 mL). The resulting solution is filtered and the mother liquor is dried over magnesium sulfate and filtered through silica gel. The mother liquor is condensed, and the product is purified by chromatography.
Preparation of 18: A 250 mL round-bottomed flask fitted with a Dean-Stark condenser is charged with 2-amino-4′-bromobenzophenone (0.11 mol), toluene sulfonic acid monohydrate (1.0 g, 0.005 mol), and xylene (90 mL). The mixture is heated at reflux for 16 h, before being cooled to room temperature. The resulting solid is purified by chromatography.
Preparation of 19: A 40 mL vial is charged with 17 (1.1 mmol), 18 (1.0 mmol), tetrakis(triphenylphosphine)palladium(0) (0.02 mmol), Aliquat (0.7 mL of a 60% solution), toluene (1.5 mL) under nitrogen. This solution is mixed with a 2 M aqueous potassium carbonate solution (1.6 mL), and the resulting solution is stirred under nitrogen for 16 h. The mixture is diluted with toluene (10 mL) and the organic layer is filtered. The solution is coagulated into a 9/1 methanol/water solution, and the resulting product is dried in vacuo.
Example 11
Preparation of 20: To a solution of fluorobenzene (50 g, 0.52 mol) and carbon disulfide (500 mL) is added aluminum trichloride (86.8 g, 0.651 mol). The resulting suspension is heated to reflux and fumaryl chloride (28.2 mL, 0.26 mol) is added over a 15-min period. The resulting solution is heated at reflux for 18 h and then cooled to room temperature and poured into an ice (1 kg)/concentrated hydrochloric acid (15 mL) mixture. The resulting solid is collected by filtration and recrystallized from toluene.
Preparation of 21: To a cooled solution of 1,3-butadiene (1.19 g, 22.1 mmol) in toluene (50 mL) is added 20 (3 g, 11 mmol). The mixture is heated at reflux in high pressure apparatus for 12 h. The solvent is removed under pressure, and the product is recrystallized from ethanol.
Preparation of 22: To a mixture of 21 (25 g) in hot acetic acid is added concentrated phosphoric acid (0.5 g). The mixture is heated at reflux for 10 min, cooled, and the resulting product is collected by filtration.
Preparation of 23: To a boiling solution of 22 (10.9 g, 35.4 mmol) in glacial acetic acid (500 mL) is added bromine (11.3 mL, 70.8 mmol) in glacial acetic acid (60 mL). The mixture is heated at reflux for 15 min, cooled, and sodium acetate (23.2 g, 283 mmol) is added. The resulting mixture is heated at reflux for an additional 15 min. The mixture is cooled, diluted with water (150 mL), and stirred at room temperature for several hours. The resulting white precipitate is collected by filtration and recrystallized from ethanol.
Preparation of 24: A 100 mL round-bottomed flask fitted with a Dean-Stark condenser is charged with 23 (0.2 mol), toluene sulfonic acid monohydrate (1.8 g, 0.01 mol), and mesitylene (40 mL). The mixture is heated at reflux for 16 h and then cooled to room temperature. The resulting solid is purified by chromatography.
Example 12
Preparation of 25: A 125 mL, round-bottomed flask fitted with a stirring bar and a Dean-Stark trap attached to a condenser is charged with biphenol (12.7 mmol), potassium carbonate (19.1 mmol), N-methylpyrrolidinone (48 mL), and toluene (29 mL). The system is purged with nitrogen (0.5 h) and heated to reflux (16 h). A solution of 24 (12.7 mmol) in toluene (20 mL) is added to the reaction mixture and 20–30 mL of toluene is removed by distillation. The resulting solution is heated at reflux for 10 h, diluted with N-methylpyrrolidinone (100 mL), cooled to room temperature, and poured into methanol (600 mL). The resulting solid is collected by filtration and dried in vacuo for 16 h. The solid is redissolved in N-methylpyrrolidinone (100 mL), filtered, precipitated in methanol (100 mL), and the resulting solid dried in vacuo.
Example 13
Solution Film Casting of 4: A solution of 4 (1.29 g) in N-methylpyrrolidinone (10 mL) was poured on a glass plate. The solvent was removed in vacuo (100° C., 16 h) to give a transparent, yellow film.
Example 14
Compression Molding of 3: A 40 mm×12 mm mold was charged with 3 (0.75 g). The mold was placed between the platens of a heated press (320° C.) with the application of 1,000 lbs. of force (0.5 h). The heating source was turned off, and the mold was allowed to cool slowly to approximately 50° C. The resulting compression molded panel was translucent brown in appearance.
Example 15
Compression Molding of 4: A 40 mm×12 mm mold was charged with 4 (0.75 g). The mold was placed between the platens of a heated press (360° C.) with the application of 1,000 lbs. of force (0.5 h). The heating source was turned off, and the mold was allowed to cool slowly to approximately 50° C. The resulting compression molded panel was dark brown in appearance.
Example 16
Preparation of Glass Fiber Composite of 4 by Compression Molding: A 10% solution of 4 in N-methylpyrrolidinone was poured onto a 3 inch×3 inch glass fabric (2 g) and the solvent was removed in vacuo. The fabric was cut into five equal pieces and the pieces were layered on top of one another in a compression mold. The mold was heated in a hot press at 350° C. at 5,000 psi for 30 min. The mold was then cooled to room temperature and the composite was removed.
Example 17
Preparation of Carbon Fiber Composite of 4 By Vacuum Bagging: A 10% solution of 4 in N-methylpyrrolidinone is poured onto a 3 inch×3 inch carbon fabric and the solvent is partially removed in vacuo. The fabric is draped over a mold that is covered with a release film and a bleeder layer, and the layered structure is placed in a vacuum bag. The vacuum bag set up is placed in an autoclave at 350° C. and 200 psi for 2 h and a vacuum of 740 torr is established, which is then cooled to room temperature to yield the final part.
Compositions containing 0.1% or more by weight of one or more polymers or copolymers provided in accordance with practice of the present invention and up to 99.9% by weight of other polymers or additives are contemplated.
Examples of additives that can be mixed or compounded with the dibenzodiazocine polymers provided in accordance with practice of the present invention include the following:
Light stabilizers (e.g., 2-hydroxybenzophenones, 2-hydroxyphenylbenzotriazoles, hindered amines, salicylates, cinnamate derivatives, resorcinol monobenzoates, oxanilides, p-hydroxybenzoates, etc.); plasticizers (e.g., phthalates, etc.); high-polymeric additives for improving impact strength; fillers (carbonates, glass fibers, aluminum hydroxide, kaolin, talc, silicon dioxide, wallastonite, glass spheres, mica, carbon fibers, and carbon whiskers, etc.); colorants; flame retardants (e.g., aluminum hydroxide, antimony oxides, boron compounds, bromine compounds, chlorine compounds, etc.); antistatic additives; biostabilizers; and blowing agents.
Additionally, it is envisioned that the dibenzodiazocine polymers may be blended with any other polymers including but not limited to polyetheretherketones, polyetherimides (e.g., Ultem™), polyamideimides (e.g., Torlon™), polyphenylenes (e.g., Parmax®), polysulfones (e.g., Udel™ and Radel™), polyimides, polyamides, polyesters, polycarbonates, polyureas, liquid crystalline polymers, polyolefins, styrenics, polyvinylchloride, phenolics, polyethylene terephathalates, and acrylics.
Devices such as radios, television sets and computers can employ electrical wiring coated with one or more polymers or copolymers of the present invention or can employ the polymer or copolymer of the present invention as a dielectric material. Furthermore the polymers or copolymers of the present invention can be used as dielectrics in various electronic applications including but not limited to printing wiring boards, semiconductors, and flexible circuitry. Additionally, dibenzodiazocene polymers and copolymers can be used in various electronic adhesive applications including but not limited to lead-frame adhesives.
The above descriptions of the exemplary embodiments of dibenzodiazocine polymers including their preparation and applications of use are for illustrative purposes. Because of variations which will be apparent to those skilled in the art, the present invention is not intended to be limited to the particular embodiments described above. The scope of the invention is defined in the following claims. | Dibenzodiazocine polymers, methods for producing dibenzodiazocine polymers, products formed from dibenzodiazocine polymers, and uses for such dibenzodiazocine polymers are provided. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. application Ser. No. 11/460,539, entitled PERIMETER PEST CONTROL SYSTEM, filed Jul. 27, 2006; a continuation-in-part of U.S. application Ser. No. 11/551,691, entitled PERIMETER PEST CONTROL SYSTEM FOR USE ON BRICK STRUCTURES, filed Oct. 20, 2006; and a continuation-in-part of U.S. application Ser. No. 11/697,723, entitled METHOD AND APPARATUS FOR PERIMETER PEST CONTROL, filed Apr. 7, 2007 by the present inventor, all by the present inventor, the priority of which are claimed, and the contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for sealing the lower portion of an exterior wall system which also acts as a chemical (termiticide and/or pesticide) application appliance and to a method for applying chemicals to a structure. In particular, the present invention is intended to be used both to mechanically seal the exposed area created at the lower portion of the exterior walls of a structure, such as a residence, while simultaneously providing a means for facilitating the injection of chemicals (termiticides and/or pesticides) between the inner and outer portions of the exterior wall system, thereby providing a perimeter pest control system which extends around the periphery of the structure.
In the past there have been efforts to provide chemical (termiticide and/or pesticide) treatment to protect structures at the time that they are constructed. While it has been common practice in the construction of new buildings to pre-treat the fill or soil area which is to underlie the foundation with a termiticide, the initial termite barrier does not last indefinitely, so there is a need to supplement this barrier during the life of the building by providing an efficient and inexpensive means at the points where termites or other insects can gain access to wooden structural members. While termites do not bore holes through concrete, they can gain entry into the areas where wood is used in the construction of the building by forming earthen tunnels from ground level over the surfaces of concrete foundations, slabs, and walls. A common problem in buildings clad with exterior surfacing materials such as lap siding, which includes, but is not limited to wood, cement-fiber, composites, vinyl, and aluminum, is that even if the siding itself is made of a material which resists rotting, cracking, damage from rain or hail, or insect penetration, the exterior board siding is installed in lapped layers over the exterior portion of the internal wall structure, whereby an exposed area is formed behind the lowest board, e.g., between the rear (inner) surface of the lowest board and the outer surface of the foundation wall, which would permit insects to climb from the ground up and gain access to the structure via the exposed area. For example, even such popular construction materials as cement board siding, e.g., those sold by James Hardie Building Products, called “Hardie Board”, while themselves impervious to insect penetration, permit insects to gain access in the exposed area formed behind the lowest board.
In particular, termites are able to build tunnels in the tiny spaces between the walls and the surfacing material, and their tunneling activity will not be detected because it is behind the cement board exterior surfacing material. Thus, while the exterior surfacing material will prevent termites or other insects from gaining access through them, the lack of a seal between the exterior portion of the internal structural wall and the interior portion of the exterior surfacing material provides a path through which termites or other insects can enter the structure from behind the exterior surfacing material.
This situation can be made worse if landscaping activities decrease the vertical space between the ground and the upper portion of the foundation wall following construction which make it even easier for termites and other insects to gain access by climbing up the edges of a foundation slab and between the structural walls and the exterior siding material without being detected until after severe damage has been done to wooden structural members of the building.
Prior methods for preventing termites and other insects from entering between the structural walls and the exterior siding material involve saturating the soil adjacent to the perimeter of the structure with chemicals (termiticides and/or pesticides) at the point of termite entry. This is accomplished by trenching or rodding. In the first of these methods, a trench is dug around the perimeter and filled with termiticide, e.g., at the rate of about four gallons of chemical (termiticide and/or pesticide) per linear foot of trench. In the other method, chemical (termiticide and/or pesticide) is injected through a hollow rod jammed into the soil and against the foundation about every six inches or so. Usually the soil adjacent the foundation is relatively dry. Since dry soil does not absorb liquids easily, it is not uncommon for chemicals (termiticides and/or pesticides) applied in this manner to drain away very quickly, thereby making it ineffective at the point of termite or insect entry, and, instead, creating an environmental detriment to the surrounding soil. Further, these methods are quite labor intensive, so they are costly to use. Thus, there has been an ongoing need for an efficient, labor-saving chemical (termiticide and/or pesticide) delivery system for providing an effective perimeter pest control system to create a barrier between the exterior cladding of a building and its foundation and exterior structural walls, whereby the area between them can be sealed from insect intrusion while also providing a means for easily treating the structure on a periodic basis.
While a number of fluid distribution systems for chemicals (termiticides and/or pesticides) comprised of conduit capable of emitting chemicals through apertures or valves have been developed for incorporation in or under a building foundation, these prior systems are typically quite elaborate in construction, requiring extensive modification of traditional and conventional building methods, expensive pumps and reservoirs, and substantial increases in building costs. Such issues have been previously noted, for example, in U.S. Pat. No. 3,513,586 to Meyer et al. which discloses and teaches a distribution system comprising tube means disposed within a building footer constructed of conventional concrete building blocks, requiring additional support members and plate members, among other things, that but for the distribution system, would not be required as part of the footer.
U.S. Pat. No. 3,209,485 to Griffin discloses a pesticide distribution system comprised of multiple, independent, branched circuits, intended to be installed within and under a foundation at the time of construction. The system comprises many parts, and its installation requires multiple steps at different stages of construction of the building.
U.S. Pat. No. 3,602,248 to Peacock discloses a distribution system comprised of a plurality of parallel connected pipe branches, each branch thereof short enough so that fluid pressure is maintained along the entire piping, with at least two inlets into each branch. Each branch requires a closure fitting at the end opposite the inlet end. Multiple pumps are required to maintain uniform pressure in the branch lines.
There are also a number of related systems for distributing pesticide within the walls of buildings. In U.S. Pat. No. 3,676,949 of Ramsey, pipes with emitter nozzles pass through the studs of the walls with a nozzle disposed between each set of studs. In U.S. Pat. No. 3,782,026 of Bridges et al., pipes extend within the walls or, alternatively, beneath baseboard moldings on the interior walls, permitting injection of insecticide gas within the walls. In U.S. Pat. No. 4,028,841 to Lundwall an insecticide storage and pressurizing system is installed in the attic, and perforated pipes carry pest control fluid into the building walls, while U.S. Pat. No. 4,742,641 to Cretti describes a built-in reservoir which is installed within a building wall from which pesticide is distributed whenever the pump is operated (which can be done by a timing device for injecting predetermined amounts at predetermined spaced intervals).
U.S. Pat. No. 3,330,062 to Carter is another pest control system utilizing pipes installed through holes drilled through the wall studs of a building with the pipes requiring threaded caps at their distal ends. U.S. Pat. No. 4,944,110 to Sims relates to a method for applying pesticide into the concealed areas of a building, by injecting pressurized chemicals through perforated preinstalled tubing. U.S. Pat. No. 5,347,749 to Chitwood et al. discloses a system for reapplication of termiticide to the fill dirt underlying the foundation slab of a building at potential termite entry points: junction of foundation block with slab, and openings in the slab for penetration of bundles of utility connections.
While none of the foregoing patents teaches or discloses a system adapted to deliver a termiticide barrier to the exterior walls of a building underneath its surface coating or siding materials, an effort to disclose such a system was made in U.S. Pat. No. 5,819,466 to Aesch, et al., in which a peripheral termiticide delivery system using flexible apertured tubing was described. That system was designed to simply saturate the exterior foundation walls of a new structure, with the treatment going down to the soil.
U.S. Pat. No. 6,301,849 which issued to Roth describes a flashing article used to seal out moisture and to drain moisture away from a stucco coated exterior wall surface. In order to provide chemical treatment, the article uses one or more tubes, an internal conduit, and connectors, all of which prevent the article from being made as an extruded item. Further, the installation of the article is considerably more labor intensive than would be desirable, as each installation requires custom fitting the article to each wall section of the structure. In addition, the flashing overlies the lower portion of the exterior wall which prevents a good seal without caulking, which adds yet another complexity and expense to the installation. Notably, if the caulk seal between the outer surface of the flashing and the structure were to fail, the flashing would actually act like a gutter system, and funnel water under the exterior wall system, thereby creating potential damage to the exterior wall system and introducing moisture between the exterior and interior wall systems.
SUMMARY OF THE INVENTION
In that no combination of the known prior art devices provides a means for accomplishing the results of sealing the exposed area between the foundation and the exterior wall system while providing an efficient, easily installed and easily used, means and method for termiticide and/or pesticide treatment the need for such a system is met by the present invention.
The present invention is an elongated article designed to be used in a structure having an exterior surface made of aluminum siding, vinyl siding, real or artificial stucco, or stone. The invention is designed to be installed directly below the siding, and it attaches to both the underside of the exterior siding and the outside of the foundation. The invention includes an elongated internal aperture having fill ports formed at spaced intervals along its exterior portion, means for sealing the article against the foundation wall formed along the side intended to abut the foundation wall, and a flexible seal formed along the upper portion which is designed to facilitate sealing the article to the lower edge of the exterior siding. The invention thereby provides an elongated sealing and delivery apparatus through which pesticides or termiticides can be introduced to provide a continuous chemical barrier against ground source pest infestation while simultaneously sealing the exposed area between the foundation and the exterior wall system.
In various embodiments, the cross-section of the inventive apparatus is modified such that the seal, which is preferably made of a material, such as flexible polyvinyl chloride (“FPVC”), is able to be flexibly attached against the lower surface or the exterior siding.
The present invention further includes a method for perimeter pest control in a structure having a siding material which is affixed to the inside wall and foundation of the structure at the lowest point of the siding material. The method comprises the steps of providing a sealing apparatus to substantially seal the space between the lower portion of the siding material and the outer portion of the foundation wall to thereby form a pest treatment zone between the lower portion of the siding material and the outside of the foundation wall, with the pest treatment zone being formed within the sealing apparatus. The method further includes forming a series of injection openings which allow communication from outside of the pest treatment zone into the pest treatment zone, and then injecting an insecticide (or termiticide) through the openings into the pest treatment zone.
BRIEF DESCRIPTION OF THE DRAWING
In the Drawing:
FIG. 1 is a perspective view of an exterior wall system to which the apparatus of the first embodiment of the present invention has been attached;
FIG. 2 is a side cross-sectional view of the first embodiment of the invention of FIG. 1 further illustrating the manner in which the article looks when it is formed;
FIG. 3 is a side cross-sectional view of a second embodiment of the invention;
FIG. 4 is a side cross-sectional view of a third embodiment of the invention; and
FIG. 5 is a side cross-sectional view of a fourth embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIGS. 1 and 2 , the present invention relates to an apparatus 10 designed to be used as a pesticide or termiticide application appliance and to a seal the exposed area formed beneath the lower surface 12 of an exterior wall made of a material such as aluminum siding, vinyl siding, real or artificial stucco, or stone, such as the stone wall 14 and the exterior surface 16 of the foundation 18 of a structure 20 , as illustrated. The structure 20 further includes a structural wall system 22 including a sheathing layer 24 and an outer “wrap” 26 . The wall system 22 further comprises wood “sill” members 28 and vertical members, such as stud 30 , to which the exterior “sheathing” 24 , which is typically foam, particle board, or plywood, is attached, with the wrap 26 overlying the sheathing 24 , as shown.
The appliance 10 is preferably manufactured using an extrusion process whereby the elongated appliance 10 will have a substantially sickle shaped cross-section, with an upper wall 32 , an outer wall 34 , a lower wall 36 , and a lower extension 38 , as shown. As shown in FIG. 1 , the upper wall 32 acts as a means for sealing the appliance 10 against the lower portion 12 of the stone exterior wall 14 . Similarly, the lower extension 38 is used to seal the appliance 10 against the outside wall 16 of the foundation 18 , using a series of screws 40 (See, FIG. 1 ) which extend through holes 42 (See, FIG. 2 ) formed in the appliance 10 . A “V”-shaped cut 46 in the appliance 10 acts as a “flap hinge” to facilitate the top wall 32 to act like a seal. A series of openings 48 act as injection ports through which insecticides or termiticides can be injected into the open space 50 formed between the outer foundation wall 16 and the inside of the upper, outer, and lower walls 32 , 34 , 36 of the appliance 10 .
With reference to FIGS. 2-5 , alternative embodiments 60 , 80 , 100 of the appliance 10 are shown in cross-section. In each case, the alternative embodiments 60 , 70 , 80 include an upper wall 62 , 82 , 102 , an outer wall 64 , 84 , 104 , a lower wall 66 , 86 , 106 , and a lower extension 68 , 88 , 108 , respectively, whereby each of the embodiments 10 , 60 , 80 , 100 can operate in the same manner as was explained above with respect to the first embodiment 10 , shown in FIG. 1 . Similarly, each embodiment includes screw holes 70 , 90 , 110 and injection ports 72 , 92 , 112 . However, as shown the configurations of the respective bottom walls 66 , 86 , 106 can differ, as can the locations of the “V” shaped hinges 74 , 94 , 114 .
Each of the embodiments 10 , 60 , 80 , 100 is designed to have an overall height of about 2.125 inches prior to installation, so that when they are installed they can be compressed against the lower portion of the outer wall such that their overall height is decreased to about 1.875 inches. However, these dimensions are not critical. Similarly, they each have a nominal width of about 0.875 inches, which can preferably be in the range of about 0.5 to 1.0 inches.
The general overall manner in which the present invention 10 is used and installed has been described. In order to manufacture the invention, one would preferably use a flexible material which can be formed using an extrusion process. While the particular material is subject to variation depending upon environmental, and other, factors, materials which have been found to be suitable include various types of plastic composites, LPDE, and industrial vinyl, such as flexible polyvinyl chloride (“FPVC”). Advantages of FPVC are that it can be produced in clear or various colors, it is paintable, and it can have mold and mildew retardants incorporated into it during production. Also, the material is flexible, within the durometer range of about 70 to about 90.
While the invention may be formed by extrusion, it has been found to be preferable for shipping, storage, and other purposes to limit the length of each extrusion to about 8 feet, whereby the lengths may be stored without bending which makes their handling, storage, and installation easier, although longer or shorter lengths could be formed.
In order to use the apparatus 10 following its installation, one injects a foamed pesticide through the pesticide fill ports 48 , whereby a treated zone 50 is formed beneath the outer wall 14 and between the appliance 10 and the foundation wall 16 .
The use of the inventive apparatus has resulted in an inventive method for providing perimeter pest control for use in a structure having a siding material which is not spaced horizontally from the inside wall and foundation of the structure at the lowest point of the siding material. The method comprises the steps of providing a sealing apparatus to substantially seal the space between the lower portion of the siding material and the outside of the foundation wall to form a pest treatment zone between the lower portion of the siding material and the outside wall of the foundation, with the pest treatment zone being formed between the sealing apparatus and the foundation wall. As used herein, the term “pest treatment zone” is intended to refer to an area into which chemicals, including both termiticides and pesticides, can be injected. The method further includes forming a series of injection openings which allow communication from outside of the pest treatment zone into the pest treatment zone, and then injecting an insecticide (or termiticide) through the openings into the pest treatment zone.
The present invention can be installed on existing structures or new construction, and it is intended to allow a pest control service company to periodically apply a uniform chemical barrier around the exterior of a home or other structure in an area which protects the chemical (termiticide and/or pesticide) against degradation from exposure to the elements. It also minimizes the amount of chemical that would come in contact with the exterior of the building. As will be understood by those skilled in the art, the invention can be used with any type of aluminum siding, vinyl siding, real or artificial stucco, and on stone siding.
The present invention can be used as a stand-alone pest control treatment, or it can be used in conjunction with other traditional pest or termite treatment products and protocols. Its design allows for the application of pesticide or termiticide without requiring entry into the home, so it is not necessary to schedule treatments only when someone can be present to provide access.
Although the system creates a mechanical barrier against infestation of pests, such as termites and other insects, the primary effectiveness of the invention is determined by the efficacy of the chemical used in the system. In that regard, various chemicals (termiticides and/or pesticides) can be used. One which has been used in a foam supplied through the use of a portable foam generator of the type produced by NPD Products Limited (formerly NoHowe Product Development Ltd.) of Midhurst Ontario and described in U.S. Pat. No. 6,755,400 to Howe, using their ProFoam Platinum product, has been Termidor, although other types of chemicals (termiticides and/or pesticides), such as those made by Dupont or FMC, could also be used in any suitable foam carrier.
While there are industry distinctions between “pesticides” and “termiticides” those skilled in the art will recognize that the present invention, described herein, can be used with any pesticide or termiticide which can be injected through it in a foam carrier as described above. As the efficacy of the treatment will be determined by the specific chemical (termiticide and/or pesticide) which is used, the present invention should be regarded as an appliance which makes such treatment possible. Accordingly, nothing in the descriptions set forth above should be regarded as limiting the use of the present invention to either a pesticide or a termiticide, or to any particular pesticide or termiticide.
While the invention has been described in connection with specific embodiments and applications, the inventors do not intend to restrict the description to the examples shown. Persons skilled in the art will recognize that the above methods may be modified or changed without departing from the general scope of this description. The inventors also intend to include all such modifications and alterations in so far as they come within the scope of the appended claims or the equivalents thereof. | The method and apparatus include an elongated pesticide administration system is designed to fit between the foundation wall of a structure and the lowest portion of an exterior wall system, such as aluminum siding, vinyl siding, real or artificial stucco, or stone. The elongated seal is attached to the bottom surface of the exterior wall system, and it includes an extended, flexible, resilient seal which seals it against the outside of the foundation wall, thereby creating a pest treatment zone between the foundation wall and the lowest portion of said exterior siding material. Pesticide foam is injected into the pest treatment zone through holes which are spaced along the bottom of the seal or which extend through the exterior siding. The pesticide foam fills the pest treatment zone to provide perimeter protection. | 0 |
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