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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application 60/844,207, filed Sep. 12, 2006. The disclosure of the prior application is considered part of (and is incorporated by reference in) the disclosure of this application.
BACKGROUND
Data compression allows storing more data in a smaller space, and later reconstructing the original data. The use of data compression may allow improved use of limited bandwidth over channels such as cellular networks.
It is important that many different clients be able to decompress video which has been compressed using various techniques. Accordingly, the decompression process typically is kept simple to avoid the requirement of special hardware to decompress. However, the compression process can be extremely complicated, since specialized hardware can be used for the compression.
SUMMARY
The present application teaches a compression process intended to be used on a cellular phone over a cellular network.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A illustrates the host login screen;
FIG. 1B illustrates a selection menu;
FIG. 2 illustrates an exemplary screen;
FIG. 3 illustrates how a cable television feed can be selected;
FIG. 4 illustrates a flowchart of the operation of customer interaction; and
FIG. 5 illustrates a hardware diagram.
DETAILED DESCRIPTION
The general structure and techniques, and more specific embodiments which can be used to effect different ways of carrying out the more general goals, are described herein.
The present application operates by allowing users to connect to a host website using their cellular phone. While attached to the host website, the users can view motion pictures of streaming video on the display of the cellular phone. In an embodiment, the cellular phone has a special adapter that is externally attached to the data port of the cellular phone. This special adapter uses very large scale integration “VLSI” chips to carry out decompression of the received information.
An embodiment uses extremely aggressive motion estimation algorithms for the compression and decompression, in order to attempt to obtain a ratio as high as 1000:1 compression ratio. The wavelet transform decomposes the image into different resolutions (or scales). One usually refers to these as averages and details. However, there are different levels of detail resolution and one of the parameters that we can select is the number of levels we decompose the image. One usually refers to the details to describe “the finest scale”, hierarchically down to the “coarsest” scale. In order to reconstruct the image it is necessary to transmit information about not only the magnitude of the wavelet transform coefficients, but also the position of the significant transform coefficient. This means that for each wavelet coefficient, we need to provide three numbers; magnitude plus the location in x and y. One of the challenges for transmitting wavelet transformed data efficiently is to use redundancy in the location description such that not each individual position has to be transmitted independently. A challenge in streaming media is to transmit the most significant pieces of information first. By doing this, all is not lost even if the bitstream is interrupted pre-maturely. This also provides an easy way to adjust the protocol for different bit budgets. This is referred to as progressive transmission, and may also be used in this system.
Since the decoder is a single purpose device, separate from the phone, it can be of any level of complexity.
In an embodiment, a cellular phone display may have the ability to view images that have many different forms, for example, 245×320 pixels. Such a phone requires 76,800 pixels per frame. If the streaming video is sent at a refresh rate of 24 frames per second, this means that about 442 million pixels of streaming data is necessary. Taking the Verizon™ network of CDMA networks as an example, which has a baud rate of 400,000 bits per second, this would require about 18½ minutes. At a compression rate of 250:1, this could be accomplished in about 4½ seconds and would require much less bandwidth and memory storage.
In addition, the module may store a number of images, which can be displayed as part of the displayed video. In addition, the module stores compression and decompression algorithms that allow more efficient transferring of large images over the network.
An operating system can also be downloaded to the attachment module.
FIG. 1A indicates the host login screen, that requires the user to connect. FIG. 1 shows entering (or otherwise obtaining) a user's mobile telephone number, and, their cellular provider 105 , and type of phone 110 . This information may also be automatically detected.
Other information about the phone and/or its connection may also be obtained, for example, whether the phone has GPRS.
Once connected, the user is provided with a selection menu shown in FIG. 1B . This requires selecting both the input source from the selection menu: High definition TV, DVD, cellular, PDA and other. The output destination can also be selected from high definition TV, DVD, cellular, and other. Once selected, the website will carry out a conversion operation.
FIG. 2 illustrates an exemplary screen. This shows the owners personal information 200 including name, cellular phone number, and the like. A ‘ CREATE NEW VIDEOS ’ menu 205 is also shown. The ‘ CREATE NEW VIDEOS ’ selects an import path from which the videos can be created. Once created, the videos are resident on the website, shown by the section 210 , which also shows how many video clips the user has, and allows sending them to the cellular phone, viewing or deleting. A preview screening 220 can also be provided.
In operation, the user can select a video from any desired source to be sent to the website, converted, and eventually sent to the telephone. For example, FIG. 3 illustrates how a cable television feed can be selected, received by the website at 305 , converted by the VLSI board into a motion compensated and aggressively compressed video image, and then sent over the cellular carrier 322 to the cellular phone 325 . This architecture allows any feed—such as from a cable television—to be selected by a user on a website, aggressively compressed, and sent to the mobile phone for later usage.
According to one aspect, much of the compression is done in VLSI circuitry, thereby enabling more aggressive compression of that information.
FIG. 4 illustrates a flowchart of the operation of customer interaction. At 400 , the user logs on to a website, and identifies the preferences at 405 , using for example the screens shown in FIGS. 1A and 1B . The user can change preferences at 410 , which preferences are then stored in the user database at 415 . Alternatively, the user can choose to upload or download video clips at 420 . If the download is selected, flow passes to 425 , where the user selects a video, and selects download to cellular at 430 . The user profile is then used to determine the number of pixels at 435 . An aggressive data compression 440 is carried out, which passes control to the download process 460 .
If the user selects uploading clips, the user then selects a source at 450 , which may be, for example, a DVD at 455 . Alternatively, the source may be cable television, or any other source. Uploading begins at 456 , followed by a data compression stage at 457 where the data is aggressively compressed. Flow then passes to the upload/download process which allows the data to be downloaded.
FIG. 5 illustrates a hardware diagram which shows the phone 500 and the attachment module 510 attached thereto. In the embodiment, the attachment module is connected by a hook and eye part 509 such as Velcro™ to the side of the phone. The attachment module has a cable 511 which is attached to a USB or other format data port 512 . The VLSI module has a processor 520 , a logical gate array 521 of flash memory storage 522 , and a cellular phone interface 525 . The logical gate array 521 may either be a programmable logic array that is reconfigurable according to downloaded instructions, or may be dedicated logic gates. Because dedicated hardware can be used to decompress the data, the data may be more aggressively compressed prior to sending to the cellular phone.
Although only a few embodiments have been disclosed in detail above, other embodiments are possible and the inventors intend these to be encompassed within this specification. The specification describes specific examples to accomplish a more general goal that may be accomplished in another way. This disclosure is intended to be exemplary, and the claims are intended to cover any modification or alternative which might be predictable to a person having ordinary skill in the art. For example, the external module is optional and others could be used.
Also, the inventors intend that only those claims which use the words “means for” are intended to be interpreted under 35 USC 112, sixth paragraph. Moreover, no limitations from the specification are intended to be read into any claims, unless those limitations are expressly included in the claims. The computers described herein may be any kind of computer, either general purpose, or some specific purpose computer such as a workstation. The computer may be an Intel (e.g., Pentium or Core 2 duo) or AMD based computer, running Windows XP or Linux, or may be a Macintosh computer. The computer may also be a handheld computer, such as a PDA, cellphone, or laptop.
The programs may be written in C or Python, or Java, Brew or any other programming language. The programs may be resident on a storage medium, e.g., magnetic or optical, e.g. the computer hard drive, a removable disk or media such as a memory stick or SD media, wired or wireless network based or Bluetooth based Network Attached Storage (NAS), or other removable medium. The programs may also be run over a network, for example, with a server or other machine sending signals to the local machine, which allows the local machine to carry out the operations described herein.
Where a specific numerical value is mentioned herein, it should be considered that the value may be increased or decreased by 20%, while still staying within the teachings of the present application, unless some different range is specifically mentioned. Where a specified logical sense is used, the opposite logical sense is also intended to be encompassed. | Video clips are stored and converted on a website into different formats which are compatible with different cellular phones. The source for the video can be sources such as DVDs, other cellular phones, or broadcast television. The system can automatically store profiles from multiple different phones and automatically carry out a conversion based on information stored in the profile. | 7 |
This application is a continuation of application Ser. No. 07/852610 filed Mar. 17, 1992, now abandoned, which is a divisional of application Ser. No. 07/650265 filed Feb. 4, 1991, now U.S. Pat. No. 5,122,244.
The invention concerns a method for the electrochemical determination of an analyte in the presence of an oxidoreductase and a reducible substance which transfers electrons which arise during the course of the determination reaction from the oxidoreductase onto an electrode and thus leads to a signal which is a measure for the analyte to be determined, whereby the reducible substance is enzymatically reduced and oxidized at the electrode, or a corresponding process for the electrochemical determination of an oxidoreductase in the presence of an enzyme substrate and a reducible substance as characterized above.
In addition, the invention concerns a sensor electrode system for the electrochemical determination of an analyte in a sample containing at least two electrically conductive agents each of which are present isolated from one another and which can be brought into electrical contact with the sample to be examined by means of an electrically conductive surface in which at least one of the electrically conductive surfaces contacts an oxidoreductase and a reducible substance which is capable of transferring electrons between the oxidoreductase and the electrically conductive surface, or a corresponding sensor electrode system for the determination of an oxidoreductase in which at least one of the electrically conductive surfaces contacts an oxidoreductase substrate and a reducible substance as characterized above.
Finally the invention concerns the use of certain compounds as electron carriers between an oxidoreductase and an electrode in an electrochemical system.
Compared to colorimetric methods for the determination of an analyte in a liquid which are evaluated visually or photometrically, a corresponding electrochemical determination offers the advantage that the electrochemical reaction yields current directly which can be converted into a concentration. In contrast the path in colorimetric methods is indirect via a battery→current→light→residual light (remission or transmission)→current→measured value.
For electrochemical methods of determination it is necessary to oxidize the analyte to be determined or to convert it into a substance which can be oxidized by means of chemical or enzymatic methods. The direct electrochemical oxidation of an analyte or of a substance derived therefrom at the surface of an electrode requires high overvoltages i.e. potentials. This method is very unselective. Many other substances which can also be in the sample to be examined are also oxidized in this process. Such a method can therefore hardly be used analytically.
Thus, the oxidizable analyte or the oxidizable substance derived from the analyte is usually reacted with a corresponding oxidoreductase and a reducible substance whose reduced form can be reoxidized at the electrode.
In this case the oxidizable analyte or the oxidizable substance derived from the analyte is selectively oxidized by the enzyme. The enzyme reduced in this way is oxidized by the reducible substance which is present and the reduced reducible substance is oxidized at the electrode. The reducible substance thus serves as a carrier of electrons from the enzyme onto the electrode. It is therefore a prerequisite that the reducible substance is so chosen that it is converted rapidly and specifically by the enzyme and by the electrode.
In "Theory and applications of enzyme electrodes in analytical and clinical chemistry", Publisher Wiley, New York (1980), pages 197-310, P. W. Carr et al describe the reaction of glucose with oxygen as the reducible substance catalysed enzymatically by glucose oxidase and detection of the hydrogen peroxide formed at an electrode. Disadvantages of this method are side reactions of the hydrogen peroxide which is itself a strong oxidizing agent and side reactions at the electrode surface as a result of the high positive potential used. This method therefore requires special prior separations to exclude interfering components in the samples to be examined. A further disadvantage is the oxygen requirement. The oxygen diffusion from air into the sample, and within the sample, becomes rate determining especially at high glucose concentrations and may thus in certain circumstances falsify the results of the method.
A sensor electrode system for the determination of a component of a mixture of substances is described in EP-A-0 125 137 which has at least two electrically conductive agents which are each present isolated from one another and which can be brought into electrical contact with the sample to be examined by means of an electrically conductive surface whereby one of the electrically conductive surfaces contacts an oxidoreductase and a so-called "mediator compound" which transfers electrons between this enzyme and the electrically conductive surface. An organometallic substance is used as the mediator compound which has at least two organic rings of which each has at least two conjugated double bonds and in which a metal atom shares its electrons with each of these rings. Ferrocene or ferrocene derivatives are used, just as in EP-A-0 078 636, as preferred mediator compounds. In this connection, it should be taken into account that such compounds must first be oxidized, for example to a ferrocinium ion, before they are ready to accept electrons from the oxidoreductase. This leads to so-called "starting currents" which already occur in the absence of an analyte which of course interferes with an amperometic method in which the resulting current is a measure for the amount of the analyte to be determined. In addition, the sparing solubility of such metalloorganic compounds is disadvantageous since this leads to an oxygen preference for example when oxidases such as glucose oxidase are used as the oxidoreductase and this therefore leads to a current which is only small and to an oxygen dependence especially at two enzyme substrate concentrations. When using these electron carriers in a reduced form, a sparing solubility and/or the use of low concentrations are necessary in order to obtain starting currents which are just acceptable.
Electron carriers for electrochemical methods of determination which are well-known from the state of the art are in general characterized in that they are reduced in the presence of the analyte to be determined by an oxidoreductase and are reoxidized to the initial compound at an electrode. If the concentration of the reducible substance functioning as the electron carrier is substantially smaller than the concentration of the analyte to be determined then only kinetic methods can be carried out. For end-point determinations it is necessary that the reducible substance functioning as the electron carrier is present dissolved in an excess compared to the analyte to be determined in order that the analyte to be determined is completely reacted. In this process an amount of reducible substance is reacted which is proportional to the analyte to be determined. Advantages over the kinetic measurement are in particular the extended range of linearity of the current/concentration relation in amperometric methods and the improved competitiveness of the more highly concentrated reducible substance compared to oxygen when using oxidases as oxidoreductases. However, a disadvantage is that, for a complete reaction, it is necessary to use a reducible substance, i.e. an oxidizing agent, as the electron carrier with a potential which is substantially higher than that of the enzyme substrate and that, in the electrochemical determination, it is in addition necessary to use an excess of oxidizing agent which even further increases the necessary potential. However, high working potentials favour unspecific electrode reactions in particular when samples have to be investigated which contain a multitude of components in addition to the analyte to be determined.
In this respect there are still no satisfactory solutions for the electrochemical determination of an analyte via an enzymatic redox reaction. There is a lack of reducible substances functioning as electron carriers which can be applied universally, which react rapidly with oxidoreductases and which exhibit an uninhibited reaction at electrode surfaces at low potential.
The object of the present invention was to solve this problem. In particular reducible substances should be found which can function as electron carriers between an oxidoreductase and an electrode in an electrochemical system. This object is achieved by the invention characterized by the patent claims.
SUMMARY OF THE INVENTION
The invention provides a method for the electrochemical determination of an analyte in the presence of an oxidoreductase and a reducible substance which transfers electrons which arise during the course of the determination reaction from the oxidoreductase onto an electrode and thus leads to a signal which is a measure for the analyte to be determined whereby the reducible substance is eznymatically reduced and oxidized at the electrode which is characterized in that the substance which forms at the electrode by oxidation is different from the reducible substance used initially.
The invention also provides a method for the electrochemical determination of an oxidoreductase in the presence of a corresponding enzyme substrate and a reducible substance which is capable of transferring electrons from the oxidoreductase onto an electrode and thus leads to a signal which is a measure for the enzyme to be determined whereby the reducible substance is enzymatically reduced and oxidized at the electrode which is characterized in that the substance which forms by oxidation at the electrode is different from the reducible substance used initially.
In addition, the invention provides the use of a substance, which can accept electrons from an oxidoreductase with formation of an electron-rich aromatic amine, as an electron carrier between an oxidoreductase and an electrode in an electrochemical system.
The invention also provides a sensor electrode system for the determination of an analyte in a liquid sample containing at least two electrically conductive agents which are present isolated from one another and which each can be brought into electrical contact with the sample to be examined by means of an electrically conductive surface in which at least one of the electrically conductive surfaces contacts an oxidoreductase and a reducible substance which is capable of transferring electrons between the oxidoreductase and the electrically conductive surface which is characterized in that a compound is used as the reducible substance which, after reduction by the oxidoreductase, is oxidized at the electrically conductive surface to a substance which is different from the reducible substance used initially. conductive surface which is characterized in that a compound is used as the reducible substance which, after reduction by the oxidoreductase, is oxidized at the electrically conductive surface to a substance which is different from the reducible substance used initially.
Finally the invention provided the use of a substance which can accept electrons from an oxidoreductase with formation of an electron-rich aromatic amine for the production of a sensor electrode system according to the present invention.
It has turned out that the disadvantages of the known prior-art methods for the electrochemical determination of an analyte in the presence of an oxidoreductase and a reducible substance which are caused by the high potential which is necessary, in particular when using an excess of the reducible substance functioning as the electron carrier over the analyte to be determined, can be in the main avoided by a non-reversible reaction. Since an oxidized substance is formed at the electrode which is different from that used initially as the reducible substance, the electrochemical determination can be carried out at a particularly low potential and thus without risk of interfering reactions. The advantage of this low potential can then also be utilized when the reducible substance functioning as the electron carrier is only used in a small amount compared to the analyte to be determined, namely when the reducible substance used initially as well as the substance formed by oxidation at the electrode are reduced by the oxidoreductase which is necessary for the electrochemical method. If the reducible substance used initially as well as the substance formed by oxidation at the electrode are reduced by the oxidoreductase to the same substance, then the reducible substance used initially acts as a storage form for the second reducible substance which is recycled between the electrode and enzyme and which is different from the reducible substance used initially.
The advantages of the method according to the present invention are a consequence of the fact that substances can be selected as reducible substances from which a compound is formed by enzymatic reduction which can be oxidized at low voltage at the electrode. During the oxidation at the electrode there is still only a negligible concentration of this newly oxidized substance present. Hitherto, the enzymatically reduced compound had to be oxidized at the electrode back to the reducible substance used initially which was already present in a high concentration. An increased positive potential was necessary for this.
Compounds which can be used advantageously as reducible substances in the sense of the invention are those which, during oxidation of a suitable substrate for the oxidoreductase used, accept electrons which arise from the enzyme and form an electron-rich aromatic amine in this process. In this connection an electron-rich aromatic amine is understood as a compound which is richer in electrons than aniline and which because of its richness in electrons can be oxidized at the electrode at a low potential. For example all those aniline derivatives come into consideration which carry one or several +I or/and +M substituents such as hydroxy, alkyl, alkoxy, aryloxy, alkylthio, arylthio, amino, mono-alkylamino and dialkylamino residues on the aromatic ring or on the aniline nitrogen.
Alkyl, alkoxy, alkylthio, mono-alkylamino and dialkylamino residues are residues in which alkyl represents a hydrocarbon residue with 1 to 6 carbon atoms which itself can be substituted by a hydroxy group, an amino group which is substituted, if desired, once or several-fold by alkyl with 1 to 6 carbon atoms, PO 3 H 2 , SO 3 H or CO 2 H. The acid residues PO 3 H 2 , SO 3 H and CO 2 H can be present as such or in a salt form as ammonium, alkaline or alkaline-earth salts.
Aryloxy and arylthio residues are aromatic residues with 6 to 10 carbon atoms in which phenoxy and phenylthio residues are particularly preferred.
Ammonium salts are those which contain the ammonium ion NH 4 + or those which contain ammonium cations which are substituted once or several-fold by alkyl, aryl or aralkyl residues. Alkyl in alkyl and aralkyl residues denotes a hydrocarbon residue with 1 to 6 carbon atoms. Aryl in aryl and aralkyl residues is an aromatic ring system having 6 to 10 carbon atoms in which phenyl is preferred. A preferred aralkyl residue is benzyl.
Alkaline salts are preferably those of lithium, sodium or potassium. Alkaline-earth salts are preferably those of magnesium or calcium.
Aniline derivatives are also understood to include compounds which carry an unsubstituted amino group or an amino group substituted once or several-fold by +I or/and +M substituents, such as for example alkyl, on an aromatic ring system which is anelated with one or several aromatic or/and alicyclic rings. In this connection hydrocarbon-aromatic systems as well as heteroaromatics come into consideration as aromatic rings. Examples are anellated benzene or naphthaline rings or an anellated pyridine ring.
Alicyclic rings are understood as saturated or unsaturated cycloaliphatics with 5 to 7 carbon atoms, preferably 5 or 6 carbon atoms.
Possible alkyl substituents of the amino group can be hydrocarbon residues with 1 to 6 carbon atoms which can themselves be substituted by a hydroxy group, an amino group substituted, if desired, once or several-fold by alkyl with 1 to 6 carbon atoms, PO 3 H 2 , SO 3 H and CO 2 H. The acid residues PO 3 H 2 , SO 3 H and CO 2 H can be present as such or in a salt form as ammonium, alkaline or alkaline-earth salts for which the definition given above also applies.
The examples of +I or/and +M substituents given above is not to be considered to be complete. Those skilled in the art will know whether a given substituent is a +I or/and +M substituent and all these substituents shall be understood as possible substituents in the electron-rich aromatic amines as useful according to the present invention.
Particularly preferred as reducible substances which, when accepting electrons from the oxidoreductase, lead to an electron-rich aromatic amine that can then be oxidized at an electrode at low potential are compounds from the group of compounds of the general formula I
X--R (I)
in which
R represents an electron-rich aromatic residue and
X represents NO or NHOH, and compounds of the general formula II
NO--N=Y (II)
in which
Y represents a quinoid system which can, after reduction, be denoted electron-rich in the aromatic state.
In this connection an electron-rich aromatic residue is understood as the alternatives listed above for electron-rich aromatic amines.
Such reducible substances according to the present invention are reduced to aromatic amines when accepting electrons from oxidoreductase and are not oxidized to the initial reducible substances on oxidation at an electrode. As is well known to one skilled in the art, electrons are removed from the aryl residue during the electrochemical oxidation of electron-rich aromatic amines resulting in radicals or quinoid systems. However, quinoid oximes, hydroxylamines and nitroso compounds do not form.
The electrochemically oxidized compounds can often again accept electrons themselves from oxidoreductases and are in this way reduced back to electron-rich aromatic amines. It is therefore also possible to use reducible substances according to the present invention in a low concentration when compared with the analyte to be determined. In this way they act as a storage form for the electron-rich aromatic amines which are formed when electrons are accepted from the oxidoreductase and can be recycled as electron carriers between the oxidoreductase and electrode.
Outstanding examples of electron carriers according to the present invention have proven to be N-(2-hydroxyethyl)-N'-p-nitrosophenyl-piperazine, N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline, o-methoxy-[N,N-bis-(2-hydroxyethyl)]-p-nitrosoaniline, p-hydroxynitrosobenzene, N-methyl-N'-(4-nitrosophenyl)-piperazine, p-quinone dioxime, N,N-dimethyl-p-nitrosoaniline, N,N-diethyl-p-nitrosoaniline, N-(4-nitrosophenyl)-morpholine, N-benzyl-N-(5'-carboxypentyl)-p-nitrosoaniline, N,N-dimethyl-4-nitroso-1-naphthylamine, N,N,3-trimethyl-4-nitrosoaniline, N-(2-hydroxyethyl)-5-nitrosoindoline, N,N-bis-(2-hydroxyethyl)-3-chloro-4-nitrosoaniline, 2,4-dimethoxy-nitrosobenzene, N,N-bis-(2-methoxyethyl)-4-nitrosoaniline, 3-methoxy-4-nitrosophenol, N-(2-hydroxyethyl)-6-nitroso-1,2,3,4-tetrahydroquinoline, N,N-dimethyl-3-chloro-4-nitrosoaniline, N,N-bis-(2-hydroxyethyl)-3-fluoro-4-nitrosoaniline, N,N-bis-(2-hydroxyethyl)-3-methylthio-4-nitrosoaniline, N-(2-hydroxyethyl)-N-(2-(2-methoxyethoxy)-ethyl)-4-nitrosoaniline, N-(2-hydroxyethyl)-N-(3-methoxy-2-hydroxy-1-propyl)-4-nitrosoaniline, N-(2-hydroxyethyl)-N-(3-(2-hydroxyethoxy)-2-hydroxy-1-propyl)-4-nitrosoaniline, N-(2-hydroxyethyl)-N-(2-(2-hydroxyethoxy)-ethyl)-4-nitrosoaniline.
A particularly preferred reducible substance according to the present invention is N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline. N-(2-hydroxyethyl)-N-(2-(2-hydroxyethoxy)-ethyl)-4-nitrosoaniline is especially preferred.
Many compounds of the general formula I which can be used according to the present invention are well-known. Nitrosoaniline derivatives of the general formula III are new ##STR1## in which
R 1 denotes hydrogen, halogen, alkoxy or alkylthio,
R 2 represents an alkyl residue and
R 3 represents an hydroxyalkyl residue or
R 2 and R 3 are the same or different and each represents a dialkylaminoalkyl residue, an hydroxyalkoxyalkyl or alkoxyalkyl residue substituted, if desired, by OH in the alkyl moiety or a polyalkoxyalkyl residue which is substituted, if desired, by an hydroxy residue in the alkyl moiety or
R 2 and R 3 form an alkylene residue interrupted by sulphur or nitrogen in which nitrogen is substituted by an alkyl, hydroxyalkyl, hydroxyalkoxyalkyl, alkoxyhydroxyalkyl, dioxanylyl-alkyl or polyalkoxyalkyl residue each of which is itself substituted, if desired, in the alkyl moiety by a hydroxy residue or
if R 1 is in the ortho position to NR 2 R 3 , R 2 also together with R 1 represents an alkylene residue whereby R 3 then represents a hydroxyalkyl residue or, if the alkylene residue contains 3 carbon atoms, it also represents, if desired, an alkyl residue or if R 1 is not hydrogen, R 2 and R 3 are the same or different and each represents an hydroxyalkyl residue or a salt of this derivative.
In this connection halogen denotes fluorine, chlorine, bromine or iodine. Fluorine and chlorine are particularly preferred. Alkyl, alkoxy or alkylthio are residues with 1-6 carbon atoms, those with 1-3 carbon atoms are particularly preferred. The foregoing definition for alkyl also applies to the alkyl moiety in hydroxyalkyl, dialkylaminoalkyl, hydroxyalkoxy-alkyl, alkoxyalkyl, polyalkoxyalkyl, alkoxy-hydroxyalkyl and dioxanylyl-alkyl residues.
A dioxanylyl-alkyl residue is a residue in which a dioxan ring system is bound to an alkyl residue. It is preferably a 1,4-dioxan ring system, i.e. ##STR2##
A polyalkoxyalkyl residue is an -alkyl-(alkoxy) n -alkoxy residue in which n=1-10. It is preferred that n=1-4. It is particularly preferred that n=1-3. An alkylene residue is a straight-chained or branched, --preferably straight-chained-, saturated or unsaturated, --preferably saturated-, hydrocarbon chain consisting of 2-5, preferably 2-4 C-atoms with two free binding sites. Within the meaning of an alkylene residue of R 2 and R 3 which is interrupted by sulphur or nitrogen, a thiomorpholine or piperazine residue formed by the inclusion of the nitrogen atom of the general formula III is preferred. The piperazine residue is especially preferred.
Within the meaning of an alkylene residue formed from R 1 and R 2 , the indoline or 1,2,3,4-tetrahydroquinoline residue formed by the inclusion of the aromatic ring of the general formula III is preferred.
As the salt of a nitrosoaniline derivative according to the present invention of the general formula III, those of strong acids, in particular mineral acids such as hydrochloric acid, sulphuric acid, nitric acid and phosphoric acid are preferred. Hydrochlorides are especially preferred, these are salts of hydrochloric acid.
The following new nitrosoaniline derivatives are especially preferred according to the present invention:
a) 2,2'-[(3-fluoro-4-nitrosophenyl)imino]bis-ethanol,
b) 2,2'-[(3-chloro-4-nitrosophenyl)imino]bis-ethanol,
c) 2,2'-[(3-methoxy-4-nitrosophenyl)imino]bis-ethanol,
d) 2,2'-[(3-methylmercapto-4-nitrosophenyl)imino]bis-ethanol,
e)2-[(2-hydroxyethoxy)ethyl-(4-nitrosophenyl) amino]ethanol,
f) 2-[(2-methoxyethoxy)ethyl-(4-nitrosophenyl) amino]ethanol,
g) 1-[N-(2-hydroxyethyl)-(4-nitrosoanilino)]-3-methoxy-2-propanol,
h) 1-[N-(2-hydroxyethyl)-(4-nitrosoanilino)]-3-(2-hydroxyethoxy)-2-propanol,
i) 1-methyl-4-(4-nitrosophenyl)-piperazine,
j) 4-(4-nitrosophenyl)-1-piperazino-ethanol,
k) 5-nitroso-1-indoline ethanol,
l) 1-methyl-6-nitroso-1,2,3,4-tetrahydroquinoline,
m) 6-nitroso-3,4-dihydro-1(2H)quinoline ethanol and their salts.
Of these the compounds a), d), e), f), g) and h) as well as their salts are particularly preferred. Compound e) or its salts, in particular the hydrochloride, is especially preferred.
The compounds of the general formula III can be produced be reacting a compound of the general formula IV, ##STR3## in which R 1 , R 2 and R 3 have the same meaning as in compounds of the general formula III, with nitrite. An analogous process is known from J. J. D'Amico et al., J. Amer. Chem. Soc. 81, 5957 (1959).
Alkali nitrite is preferably used as the nitrite, in which lithium, sodium, potassium, rubidium or caesium are possible as the alkali metal; sodium nitrite and potassium nitrite are preferably used. Sodium nitrite is especially preferred. The reaction preferably takes place in an acid medium at low temperature. It is advantageous when the temperature is below 10° C., preferably between -10° and +5° C.
It is advantageous when the reaction of a compound of the general formula IV with nitrile takes place in an aqueous medium. The pH should be preferably less than 3, particularly preferably less than 2.
In a preferred embodiment for the reaction, a compound of the general formula IV or a salt thereof, preferably a salt of a mineral acid such as hydrochloric acid, sulphuric acid, nitric acid or phosphoric acid, is first added to an aqueous acidic medium and cooled.
Then, nitrite, preferably in a dissolved form, is added while maintaining the reaction mixture at a low temperature. It is advantageous when an aqueous medium is also used as the solvent for the nitrite. After addition of the nitrite the reaction mixture is kept at a low temperature until the reaction is completed. In order to process the reaction mixture it is preferably extracted with an organic solvent and the product is isolated from the extract.
Compounds which can be used according to the present invention as electron carriers can be stored and used in an oxidized form. Starting currents are avoided by this means and end-point determinations can be carried out with an excess of electron carriers. Compounds which can be used according to the present invention as electron carriers are stable on storage and can react rapidly with oxidoreductases. Above all they are able to compete with oxygen when using oxidases and can be used in excess over the highest analyte concentration to be determined. It is especially the latter property which is made possible by the good solubility of the electron carriers according to the present invention in an aqueous medium.
In the electrochemical determination of analytes in body fluids a particular advantage of the compounds which can be used according to the present invention as electron carriers is their property of not being non-enzymatically reduced, or only to a negligible extent, by substances in body fluids which act reductively. The electron carriers according to the present invention are rapidly oxidized at the electrode surface and are not sensitive to oxygen in their reduced form. With these compounds a low potential can be used for the oxidation at the electrode.
In the present invention a substance to be determined is referred to as analyte. In this connection it is usually a component of a mixture of substances. The process according to the present invention offers particular advantages in this connection when determining an analyte in a body fluid such as blood, plasma, serum or urine because in this situation it is especially important that a specific reaction takes place with only one component of the biological multicomponent system.
The method according to the present invention for the electrochemical determination of an analyte is based on the fact that the analyte is itself oxidized by an oxidoreductase and therefore constitutes a corresponding enzyme substrate, or the analyte is converted in one or several previous reactions, preferably enzymatic reactions, into a compound which can be oxidized by an oxidoreductase. The electrons which arise during such an oxidation are proportional to the amount of the analyte to be determined. If these electrons are transferred onto an electrode by a reducible substance according to the present invention this then leads to a signal which is a measure for the analyte to be determined. Amperometric methods are possible in which a current is measured or potentiometry i.e. measurement of a voltage.
As oxidoreductases for the method according to the present invention are preferred oxidases, non-NAD(P)-dependent dehydrogenases or diaphorase. For example, according to the present invention glucose can be determined with glucose oxidase, lactate with lactate oxidase, glycerol phosphate by means of glycerol phosphate oxidase or cholesterol by means of cholesterol oxidase. As a non-NAD(P)-dependent dehydrogenase, glucose-dye oxidoreductase can for example be used for the determination of glucose. Diaphorase which can also be denoted NADH:dye oxidoreductase can be used advantageously for the detection of NADH.
In cases in which an analyte, which does not itself serve as a substrate for an oxidoreductase, has to be determined electrochemically, this analyte can be converted by one or several preliminary reactions, in particular enzymatic reactions, into a compound which is accepted by an oxidoreductase as substrate. For example, tryglycerides can be determined in that they are cleaved by means of an esterase into glyerol and acid residues, glycerol is converted to glycerol phosphate with glycerol kinase and ATP, and this is finally oxidized by means of glycerol phosphate oxidase; the electrons which are produced in this latter step are transferred by an electron carrier according to the present invention to an electrode whereby a current is produced which is proportional to the amount of triglycerides in the sample to be determined.
Total cholesterol can also for example be determined in an analogous manner by cleaving cholesterol esters with cholesterol esterase and the cholesterol formed in this manner is determined by means of cholesterol oxidase. Also in this case the amount of cholesterol formed thus and the electrons released in the oxidation by means of cholesterol oxidase, which are transferred onto an electrode by means of a reducible substance according to the present invention and thus produce a current, are proportional to the amount of total cholesterol to be determined.
The enzyme diaphorase may be used for the determination of NADH. Electrons from diaphorase can also be transferred onto an electrode by means of reducible substances according to the present invention. Since very many biological substances can be reacted enzymatically with formation of NADH, it is possible in this way to convert many analytes into NADH by enzymatic reaction sequences and then finally to determine this at an electrode by means of diaphorase and a reducible substance used according to the present invention.
From the aforementioned it goes without saying that according to the present invention oxidoreductases can of course also be determined if a corresponding compound which is accepted as the enzyme substrate and a reducible substance according to the present invention are employed. Thus, for example glucose oxidase can be determined electrochemically if glucose and an electron carrier according to the present invention are contacted with the sample to be determined in the presence of a corresponding sensor electrode system.
A special feature of the method according to the present invention is that the reducible substance used to transfer electrons from an oxidoreductase onto an electrode is stable on storage in its oxidized form and in addition is readily water soluble which is particularly important for the determination of analytes in body fluids such as blood, plasma, serum and urine. The reducible substances capable of being used according to the present invention react rapidly with oxidoreductases and are capable of competing very well with oxygen, in particular in reactions with oxidases. Because of their solubility they can be used very well for amperometric end-point methods in which an excess is required over the highest analyte concentration to be determined. Since the reducible substances capable of being used according to the present invention are reduced non-enzymatically only to a negligible extent in body fluids by reducing agents which are present there, are oxidized rapidly at the electrode surface and are hardly oxygen sensitive in their reduced form, these substances are very well suited to the specific, interference-free electrochemical determination of analytes. Moreover, the specific electrochemical determination of analytes without interference is above all a consequence of the fact that the reducible substances capable of being used according to the present invention only require a small electrode potential.
The method according to the present invention for the electrochemical determination of an analyte is not limited to particular electrochemical devices. For example state-of-the-art sensor electrode systems may be used for this. In principle for the determination of an analyte in a liquid sample those sensor electrode systems are suitable which contain at least two electrically conductive agents as electrodes which are present isolated from one another and which each can be brought into electrical contact with the sample to be determined by means of an electrically conductive surface. In this connection it is conceivable that only two electrodes, namely a working electrode and a reference electrode are used. A measuring arrangement without a reference electrode i.e. with only a working electrode and counterelectrode is also possible. In this the voltage is merely kept constant externally. The use of three electrodes is also possible, namely a reference electrode, a working electrode and a counterelectrode. Corresponding sensor electrode systems are known from the state of the art, for example from G. Henze and R. Neeb, "Elektrochemische Analytik", Springer-Verlag (1986).
It is important for the electrochemical determination of an analyte that (at least) one electrode, i.e. an electrically conductive surface, contacts an oxidoreductase and a reducible substance which is capable of transferring electrons between the oxidoreductase and the electrically conductive surface. In this connection, it is conceivable that all the required reagents are in a solution together with the sample to be examined or that a portion of the reagents, preferably the oxidoreductase and/or the reducible substance which transfers the electrons, are immobilized on an electrode and the remainder are present in solution, or that all of the reagents necessary for the determined are immobilized on an electrode. In principle is is not decisive for the function of a sensor electrode system whether the working electrode contacts the oxidoreductase and the reducible substance which functions as the electron carrier as dissolved substances or whether these substances are applied to the electrode as solid substances and which, if desired, dissolve on contact with the liquid sample to be determined or even remain immobilized on the electrode after contact with the liquid sample to be determined.
It goes without saying that the previous description applies analogously to the determination of an oxidoreductase. It must then be taken into account that the sensor electrode system contacts an oxidoreductase substrate and a reducible substance according to the present invention. Apart from this the statements made for the determination of an analyte apply correspondingly in this case.
BRIEF DESCRIPTION OF THE DRAWINGS
The attached figures elucidate the invention further. They show
FIG. 1 in part a) A scheme of the function of the reducible substances capable of being used according to the present invention in methods according to the present invention and sensor electrode systems when the concentration of the electron carrier is larger than or the same as the analyte concentration to be determined.
FIG. 1 in part b) A scheme of the function of substances carrying electrons in state-of-the-art methods and state-of-the-art sensor electrode systems.
FIG. 2 in part a) A scheme of the function of the reducible substances capable of being used according to the present invention in methods according to the present invention and sensor electrode systems when the concentration of the substance which transfers electrons is very much smaller than the concentration of the analyte to be determined.
FIG. 2 in part b) A scheme of the function of substances which transfer electrons in state-of-the-art methods and state-of-the-art sensor electrode systems.
FIG. 3: A sensor electrode system for carrying out the method according to the present invention in which the required substances are present in solution.
FIG. 4: A sensor electrode system for carrying out the method according to the present invention which is designed as a disposable sensor.
FIG. 5: A diagram of values obtained from cyclovoltammograms for anodic current density maxima at different glucose concentrations using N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline as the substance transferring electrons in an electrochemical glucose test according to the present invention.
FIG. 6: Diagram showing the relationship between current density and NADH concentration in a NADH test according to the present invention.
FIG. 7: Cyclovoltammograms for N-(2-hydroxyethyl)-N'-p-nitrosophenyl-piperazine and N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline.
FIG. 8: Diagram of the dependence of the current density on the glucose concentration according to the method according to the present invention with N-methyl-N'-(4-nitrosophenyl)-piperazine as the substance transferring electrons in the presence and absence of atmospheric oxygen.
FIG. 9: Diagram of the dependence of the current density on the glucose concentration according to state-of-the-art methods with tetrathiafulvalene as the substance transferring electrons in the presence and absence of atmospheric oxygen.
FIG. 10: Diagram of the dependence of the current density on the LDH concentration according to a method according to the present invention with N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline as the substance transferring electrons at different times after starting the determination reaction with lactate dehydrogenase.
FIG. 11: Current-time curves for the method according to the present invention with a disposable electrode according to FIG. 4 for the detection of glucose.
FIG. 12: Diagram of the dependence of the current on the glucose concentration according to the method according to the present invention with a disposable electrode according to FIG. 4 after 10 seconds reaction time.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 and 2 the differences between the method according to the present invention (a) and the state-of-the-art method (b) are shown when using an excess of the substance which transfers electrons over the analyte to be determined (FIG. 1) and when using a very small amount of the substance which transfers electrons compared to the analyte concentration (FIG. 2). According to the state-of-the-art method according to FIG. 1b) the substance transferring electrons (E ox 1) is converted into the reduced form (E red ) in the presence of the analyte to be determined or of a substance derived from the analyte (S red ) which is enzymatically oxidized to (S ox ). The reduced electron carrier (E red ) is oxidized at an electrode back to the reducible substance used initially (E ox 1) by releasing electrons.
In contrast, according to the method according to the present invention in accordance with FIG. 1a), the reducible substance functioning as the electron carrier (E ox 1) is converted into the reduced form (E red ) in the enzymatic oxidation of the analyte to be determined, or of a substance derived from the analyte (S red ), to (S ox ). In the anodic oxidation at an electrode, an oxidized form of the electron carrier (E ox 2) is then formed which is different from the reducible substance used initially (E ox 1). As a result of the complete absence of E ox 2 at the start of the electrochemical oxidation, E red can be oxidized at a particularly low potential. The reducible substance transferring electrons according to the present invention (E ox 1) can be so chosen that a relatively low potential is sufficient for the anodic oxidation of the reduced form which is formed enzymatically (E red ). Interfering accompanying reactions can be avoided by this means which occur when accompanying substances in the samples to be examined are oxidized when higher potentials are applied to the electrodes and thus lead to a current flow and consequently to a false-positive result. In the state-of-the-art method according to FIG. 1b) a higher potential than that of the reducible substance used initially (E ox 1) is necessary, because of the excess of E ox 1, to reoxidize the reduced form of the electron carrier formed enzymatically (E red ).
If the reducible substance functioning as the electron carrier (E ox 1) is in an amount which is less than the analyte to be determined or a substance derived from the analyte to be determined (S red ), then according to the state-of-the-art method (FIG. 2b) the reducible substance can be recycled between the electrode and enzyme since the reduced form (E red ) is anodically oxidized back into the reducible substance used initially (E ox 1).
According to the method according to the present invention (FIG. 2a), if the oxidized form of the electron carrier formed at the electrode (E ox 2) is reduced by the reduced enzyme as well as the reducible substance used initially (E ox 1), then (E ox 1) can serve for example as a stable storage form for the electron carrier system E ox 2 /E red .
In principle all those sensor electrode systems can be used for the method according to the present invention which are also suitable for carrying out the state-of-the-art methods. Thus, a sensor electrode system according to FIG. 3 can be used such as that which is known from G. Henze and R. Neeb, "Electrochemische Analytik", Springer Verlag (1986).
In this system a working electrode (1), a counterelectrode (2) and a reference electrode (3) are immersed in the liquid sample to be determined (4). The usual materials can be used for the electrodes. The working electrodes and counterelectrodes (1, 2) can for example advantageously consist of noble metals or such metals are used for producing the electrodes. Preferred materials for the working electrode and counterelectrodes (1, 2) are for example gold and platinum. The reference electrode (3) can also be constructed from conventional systems for this. The silver/silver chloride system is for example preferred. The reference electrode (3) is advantageously connected via a salt bridge, for example a potassium chloride solution, with the remaining electrode system (1, 2) in the liquid sample to be determined (4).
The oxidoreductase or the oxidoreductase system (depending on whether an analyte or an oxidoreductase is to be determined) for the method according to the present invention and the reducible substance functioning as the electron carrier can be dissolved in the sample to be determined (4) or they can all, or partially, be located on the working electrode (1). The manner in which the electrodes are electrically connected to one another depends on the electrical signal to be measured and the way they have to be controlled and is obvious for one skilled in the art.
The construction of a disposable electrode which can for example be used for the detection of glucose is shown in FIG. 4. The required electrodes and their accompanying leads are mounted on an insulated carrier material (8), for example a polycarbonate foil. Suitable methods can, for example, be screen printing methods, ink jet methods, evaporation coating methods or thin film techniques. In FIG. 4 (5) denotes the working electrode, (55) denotes the accompanying electrically conductive leads, (6) denotes a reference electrode with lead (66), and (7) denotes counterelectrode with a corresponding lead (77). Well-known electrically conductive materials can be used for the electrodes and leads. Commercial graphite printing pastes can for example be used to produce the electrically conductive leads to the electrodes. The electrodes mostly contain noble metals such as silver, gold or platinum. In the sensor electrode system according to the present invention according to FIG. 4, the working electrode contains the reagents which are necessary for carrying out the electrochemical determination of an analyte or of an oxidoreductase. For the determination of glucose, these are for example glucose oxidase, a reducible substance transferring electrons according to the present invention, a buffer substance which optimizes the pH value of the sample to be examined for the enzymatic reaction, as well as, if desired, a detergent and swelling agent in order to achieve the necessary consistency for the production of an electrode with a material which makes the mixture conductive and in order to make the mixture processable as a paste. Graphite powder can for example be added as the material which makes it conductive. The reference electrode (6) and counterelectrode (7) as well as the corresponding leads (66) and (77) can for example be produced from commercial silver conducting pastes which contain pulverized silver chloride. A sensor electrode system according to FIG. 4 can be produced in a size of about 10×30 mm. The solution to be examined can be applied to the electrode surfaces or the test carrier can be immersed in the liquid to be examined in such a way that the electrode surfaces are covered with liquid. In the amperometric measurement a potential can then be applied to the electrodes and a current measured which is proportional to the analyte to be determined.
For this the current between the counterelectrode (7) and working electrode (5) is measured and regulated in such a way that a pre-determined voltage is maintained between the reference electrode (6) and working electrode (5). The measurement of the voltage between the working electrode (5) and reference electrode (6) is carried out at zero current in order that resistances of the leads do not matter. If the demands on the accuracy of the electrode potentials are very low, then the voltage measurements at zero current can be dispensed with or the reference electrode (6) can be operated simultaneously as a counterelectrode (7).
The invention is elucidated further by examples in the following.
EXAMPLE 1
Glucose Test
A sensor electrode system according to FIG. 3 is used. The working electrode (1) consists of a gold wire with an area of 0.1 cm 2 . The counterelectrode (2) is a platinum wire with an area of 0.1 cm 2 and the reference electrode (3) is a silver/silver chloride system from the Orion Research Inc. Company (Boston, Mass., USA).
A solution of 0.1 mol/l potassium phosphate buffer and 0.1 mol/l potassium chloride, pH 7.0; 10 mmol/l N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline and glucose at a concentration between 0 and 100 mmol/l is in the reaction vessel.
The determination reaction is started by addition of glucose oxidase (EC 1.1.3.4) to the reaction mixture and subsequent mixing. Glucose oxidase is added in such an amount that the concentration in the reaction mixture is 0.5 mg/ml (125 U/ml). One minute after the addition of glucose oxidase a cyclovoltammogram is measured at a scan rate of 100 mV/s with a potentiostate (Mod. 273 EG & G, Princeton Applied Research, Princeton, N.J., USA). The currents of the first oxidation maximum are evaluated at 150 mV. The results obtained are shown in FIG. 5. Corresponding measurements 5 minutes after the addition of glucose oxidase or when oxygen is excluded (under argon) do not result in significant changes.
The result is a linear dependence of the anodic current density maximum on the glucose concentration up to glucose concentrations of about 30 mmol/l as can be seen from the diagram according to FIG. 5. At a higher glucose concentration than 30 mmol/l, the N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline used as the substance which transfers electrons is completely converted to the corresponding phenylenediamine. Higher concentrations than 30 mmol/l glucose therefore do not lead to a further increase in current. Since two glucose molecules are needed to produce one molecule of phenylenediamine and only about two thirds of the total glucose are present in the β-form and are therefore available for conversion by glucose oxidase, the complete conversion which was found of 10 mmol/l electron carrier substance by 30 mmol/l glucose corresponds exactly to the theoretical stoichiometry.
Comparable results are obtained when using glucose-dye-oxidoreductase (EC 1.1.99.17) instead of glucose oxidase (EC 1.1.3.4) in 0.1 mol/l Tris buffer, 0.1 mol/l potassium chloride, pH 7.0 with addition of 1% bovine serum albumin.
EXAMPLE 2
NADH Test
The construction and measuring arrangement are as described in Example 1. The reaction vessel contains 0.1 mol/l potassium phosphate buffer, 0.1 mol/l potassium chloride, pH 7.0, 10 mmol/l N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline and NADH at concentrations between 0 and 10 mmol/l.
The measurement is started by addition and mixing of diaphorase (NADH:dye-oxidoreductase) from microorganisms and mixing the enzyme with the reaction mixture. Enzyme is added in such an amount that the enzyme concentration in the reaction mixture is 0.2 mg/ml (3 U/ml). Measurement of the current density after 1 minute reaction time yields the linear current density-concentration relation shown in FIG. 6.
EXAMPLE 3
Determination of Lactate
Lactate can also be determined using the same experimental construction and the same electron carrier as in Example 1. Lactate oxidase (EC 1.1.3.2) is used as the enzyme and 0.1 mol/l citrate buffer, 0.1 mol/l potassium chloride, pH 5.5 is used as the buffer.
EXAMPLE 4
Determination of Glycerol Phosphate
Glycerol phosphate can be determined analogously when in Example 1 the enzyme glucose oxidase is replaced by glycerophosphate oxidase (EC 1.1.3.21) and the buffer is replaced by 0.1 mol/l Tris buffer, 0.1 mol/l potassium chloride, pH 8.0.
EXAMPLE 5
Determination of Cholesterol
Cholesterol can be determined analogously to Example 1, when in Example 1 glucose oxidase is replaced by cholesterol oxidase from Stretpomyces (EC 1.1.3.6), the electron acceptor is replaced by 10 mmol/l N-methyl-N'-(4-nitrosophenyl)-piperazine and the buffer is replaced by 0.1 mol/l potassium phosphate buffer, 0.1 mol/l potassium chloride, pH 5.5 with 2% Triton×100®.
EXAMPLE 6
Reducible Substances According to the Present Invention Which Transfer Electrons
The compounds mentioned in the following Table 1 are reacted at a concentration of 10 mmol/l in 0.1 mol/l potassium phosphate buffer, 0.1 mol/l potassium chloride, pH 7.0 with 50 mmol/l glucose and 0.5 mg/ml glucose oxidase (125 U/ml). In this case a measuring arrangement as described in Example 1 is used. Corresponding cyclovoltammograms yield the peak potentials in mV against a normal hydrogen electrode of the electron carrier reduced with glucose oxidase and glucose.
In Table 1 the ratio of the oxidation currents at the potential of the highest oxidation peak is listed after one and after ten minutes as a measure for the conversion rate.
TABLE 1______________________________________Electron carrier peak potentials.sup.a conversion rate.sup.b______________________________________N-(2-hydroxyethyl- 340 97N'-p-nitrosophenyl-piperazineN,N-bis-(2-hydroxy- 210 94ethyl)-p-nitroso-anilineo-methoxy-[N,N-bis-(2-hydroxyethyl)]-p-nitrosoaniline 170 35p-nitrosophenol 220 62p-quinone dioxime.sup.c 250 35N,N-dimethyl-4-nitroso-1-naphthyl-amine 175 25N,N,3-trimethyl-4-nitrosoaniline 220 56N-(2-hydroxyethyl)- 80 865-nitrosoindolineN,N-bis-(2-hydroxy- 315 72ethyl)-3-chloro-4-nitrosoaniline2,4-dimethoxy-nitro- 130 95sobenzeneN,N-bis-(2-methoxy- 245 68ethyl)-4-nitroso-aniline3-methoxy-4-nitroso- 140 30phenolN-(2-hydroxyethyl)-6- 95 82nitroso-1,2,3,4-tetra-hydroquinolineN,N-dimethyl-3- 275 27chloro-4-nitroso-anilineN,N-bis-(2-hydroxy- 260 74ethyl)-3-fluoro-4-nitrosoanilineN,N-bis-(2-hydroxy- 195 21ethyl)-3-methylthio-4-nitrosoanilineN-(2-hydroxyethyl-N- 210 592-(2-methoxyethoxy)-ethyl)-4-nitroso-anilineN-(2-hydroxyethyl)- 225 65N-(3-methoxy-2-hydroxy-1-propyl)-4-nitrosoanilineN-(2-hydroxyethyl)- 210 54N-(3-(2-hydroxyethoxy-2-hydroxy-1-propyl)-4-nitrosoaniline______________________________________ .sup.a First peak potential of the electron carrier reduced with glucose oxidase and glucose in mV against Ag/AgCl .sup.b Current of the first maximum in the cyclovoltammogram at 1 minute reaction time when compared with the current at 10 minutes reaction time in %. .sup.c Concentration 5 × 10.sup.-4 mol/l.
The cyclovoltammograms for N-(2)-hydroxyethyl)-N'-p-nitrosophenyl-piperazine and N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline are shown in FIG. 7. The cyclovoltammograms were measured with 10 mmol/l glucose in order to avoid interferences by reactions of residual glucose while recording the cyclovoltammogram.
EXAMPLE 7
Comparison of an Electron Carrier According to the Present Invention with one According to the State of the Art
a) In an experimental construction as described in Example 1, N-methyl-N'-(4-nitrosophenyl)-piperazine is used at a concentration of 10 -4 mol/l in a phosphate buffer pH 7.0. Measurement of cyclovoltammograms at glucose concentrations between 0 and 3 mmol/l yields a dependence of the current density on the glucose concentration as shown in FIG. 8. At low concentrations it is seen that atmospheric oxygen has an influence which can be avoided by measurement under argon. The same result as that using argon as a protective gas is obtained when the electron carrier is used at a higher concentration (10 -2 mol/l). Influence of the measurement by oxygen can also be avoided by use of glucose dehydrogenase instead of glucose oxidase.
b) When tetrathiafulvalene is used as the electron carrier according to the state of the art instead of N-methyl-N'-(4-nitrosophenyl)-piperazine as the electron carrier according to the present invention, the dependence of the current density on the glucose concentration is as shown in FIG. 9. Tetrathiafulvalene shows a substantially higher interference by oxygen than is the case with the electron carrier according to the present invention. In addition, much lower current densities are measured.
Tetrathiafulvcalene is very sparingly soluble. In order to obtain a concentration of 10 -4 mol/l in a phosphate buffer pH 7.0, 2.5% Tween 20® must be used as a detergent. Adjustment to much higher tetrethiafulvalene concentrations, as is possible in the case of the electron carrier according to the present invention, in order to reduce the oxygen interference, is not possible due to the sparing solubility.
EXAMPLE 8
Enzyme Determination
a) Lactate dehydrogenase test
The following solutions are prepared analogous to the test arrangement according to Example 1:
0.1 mol/l sodium phosphate buffer, 0.1 mol/l potassium chloride, pH 9.0,
10 mmol/l N,N-bis-(2-hydroxyethyl)-p-nitrosoaniline
0.1 mol/l D,L-lactate (sodium salt)
1 U/ml diaphorase from microorganisms
10 mmol/l NAD + .
Current is measured at a constant potential of 75 mV against silver/silver chloride while stirring vigorously (magnetic stirrer, 1000 rotations per minute). It is started by addition of lactate dehydrogenase (EC 1.1.1.27). Different amounts of lactate dehydrogenase are added and measurements are made in each case after 100, 200, 300, 400, 500 and 600 seconds. The current/time curves obtained are shown in FIG. 10. The LDH activities plotted on the ordinate were determined according to the usual pyruvate reduction test.
b) Glucose dehydrogenase test
A test for NAD-dependent glucose dehydrogenase can be carried out analogous to the description under a) in 0.1 mol/l potassium phosphate buffer, 0.1 mol/l potassium chloride, pH 7.0 with 10 mmol/l NAD + , 10 mmol/l electron carrier according to the present invention, 1 U/ml diaphorase and 0.1 mol/l glucose.
Oxidases, diaphorase or non-NAD-dependent dehydrogenases can be determined correspondingly.
EXAMPLE 9
Disposable Electrode System for the Detection of Glucose
A sensor electode system according to FIG. 4 is produced by mounting the working electrode (5), reference electrode (6), counterelectrode (7) and leads (55, 66, 77) on a polycarbonate foil (8) by means of screen printing using suitable printing pastes. The leads consist of commercial graphite printing paste (Acheson 421 SS, Deutsche Acheson Colloids, Ulm, German Federal Republic). The reference electrode (6) and the counterelectrode (7) consist of commercial silver conducting paste which is mixed with 20% by weight pulverized silver chloride (Acheson SS 24566, Deutsche Acheson Colloids, Ulm, German Federal Republic).
For the working electrode (5), 3 mmol/l N,N-bis-hydroxyethyl-p-nitrosoaniline, 500 KU glucose oxidase (glucose oxidase, degree of purity II, Boehringer Mannhein GmbH, Mannheim, German Federal Republic) per 100 g mixture, 30% by weight graphite powder (UF 296/97, Graphitwerk Kropfmuhl, German Federal Republic) and 4% by weight ethylene glycol are homogenized in a 25 by weight swelling mixture of hydroxyethyl cellulose (Natrosol 250 G, Hercules BV, Rijswijk, Netherlands) in 0.05 mol/l sodium phosphate buffer (pH 7.0). The areas of the electrodes are:
for the working electrode (5): 4×6 mm 2 =24 mm 2 ,
for the reference electrode (6): 1×1.5 mm 2 =1.5 mm 2 and
for the counterelectrode (7): 1×1.5 mm 2 =1.5 mm 2 .
The sensor electrode system produced by screen printing is immersed in a measuring solution which contains 0.05 mol/l sodium phosphate buffer (pH 7.0), 0.1 mol/l sodium chloride and 0-45 mol/l glucose in such a way that the electrode surfaces are covered by the liquid to be examined. Current/time curves, which are shown in FIG. 11, are recorded at 200 mV potential against the integrated silver/silver chloride reference electrode (6). A plot of the values for current after 10 seconds measurement time yields the calibration curve shown in FIG. 12 which shows the dependence of the current flow on the glucose concentration.
EXAMPLE 10
Production of 2,2'-[(4-nitrosoaryl)imino]bis-ethanols
2 mol N,N-bis-(β-hydroxyethylaniline) (or its aryl-substituted analogues) is added in portions, while stirring vigorously, to a mixture of 200 ml water and 400 ml concentrated hydrochloric acid in a 4 l three-necked flask with stirrer, thermometer and dropping funnel. The resulting solution is cooled to 0° C. with a cold bath and a solution of 148 g (2.1 mol) sodium nitrite in 200 ml water is added dropwise within 20 minutes at 0° to 2° C. while stirring. It is then stirred for a further 30 minutes at 0° C., the mostly crystalline nitroso compound which has a yellow to green colour is aspirated and the filter cake is washed twice with 200 ml ice-cold, half-concentrated hydrochloride acid. For purification, the crude product is dissolved in 900 ml water, 400 ml concentrated hydrochloric acid is added while stirring vigorously, it is stirred for 30 minutes at room temperature, then for 30 minutes while cooling on ice. The crystallizate obtained is subsequently dissolved in 580 ml water to which 265 ml concentrated hydrochloric acid is added, and stirred for 30 minutes at room temperature and 30 minutes while cooling on ice. The crystals which form are aspirated, washed three times with 150 ml ice-cold acetone each time, twice with 200 ml diethylether each time and dried in a vacuum at room temperature. In this way the following are obtained:
a) 2,2'-[(4-nitrosophenyl)imido]bis-ethanolhydrochloride
Yield 32.8% of theory, green crystals; m.p. 160° C. (decomp.).
Using corresponding aryl-substituted analogues the following are obtained analogously:
b) 2,2'-[(3-fluoro-4-nitrosophenyl)imino]bis-ethanolhydrochloride
Yield: 26.5% of theory, yellow crystals; f.p. 140° C. (decomp.). TLC: silica gel 60 (Merck)-mobile phase: ethyl acetate/methanol=5:1, R f =0.59
from 3-fluoro-N,N-bis-[2-hydroxyethyl]aniline (Chem. Abstr. 57, 13922 [1962])
c) 2,2'-[(3-chloro-4-nitrosophenyl)imino]bis-ethanolhydrochloride
Yield: 21% of theory, yellow crystals; m.p. 154° C. (decomp.). TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=5:1, R f =0.72
from 3-chloro-N,N-bis-[2(hydroxyethyl]aniline (M. Freifelder, G. R. Stone, J. Org. Chem. 26, 1499 (1961))
d) 2,2'-[(3-methoxy-4-nitrosophenyl)imino]bis-ethanolhydrochloride
Yield: 32% of theory, ochre-coloured crystals; m.p. 145°-146° C. (decomp.). TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=5:1, R f =0.4
from 3-methoxy-N,N-bis[2-hydroxyethyl]aniline (M. Freifelder et al., J. Org. Chem. 26, 1499 (1961))
e) 2,2'-[(3methylmercapto-4-nitrosophenyl)imino]bisethanol-hydrochloride
Yield: 59.3% of theory, red-brown crystals; m.p. 148° C. (decomp.). TLC: silica gel 60 (Merck)-mobile phase: ethyl acetate/methanol=5:1, R f =0.53
from 3-methylmercapto-N,N-bis-[2-hydroxyethyl]aniline (obtainable from: dissolve 0.1 mol 3-methylmercaptoaniline in 50 ml 4N acetic acid and 0.35 mol ethylene oxide and stir for 12 hours at room temperature. Add excess NaHCO 3 solution, extract with methylene chloride and purify by column chromatography on silica gel 60 (Merck)-mobile phase toluene/acetone=5.2, R f =0.18, yield 25%, colourless oil).
f) 2-[methyl(3-chloro-4-nitrosophenyl)amino]ethanolhydrochloride
Yield: 155 of theory, yellow crystals: m.p. 147° C. (decomp.), TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=19:1, R f =0.34
from 2-[methyl(3-chlorophenyl)amino ethanol (obtained from 2-[(3-chlorophenyl)amino]ethanol by boiling for 3 hours with methyliodide in the presence of 10% NaOH; purified by column chromatography on silica gel 60 (Merck)-mobile phase: toluene/acetone=5.2, R f =0.39, yield 25%, colourless oil).
EXAMPLE 11
2-[(2-hydroxyethoxy)-ethyl-(4-nitrosophenyl) amino]ethanol hydrochloride
A) 2-[(2-hydroxyethoxy)ethyl-(phenyl)amino]ethanol ##STR4##
146 g (0.8 mol) 2-(2-anilinoethoxy)ethanol (obtained by reacting aniline with 2-(2-chloroethoxy)ethanol, yield 54%, colourless oil, b.p. 1 131°-133° C.) is dissolved in 500 ml 4N acetic acid, cooled with a cold bath to 0° C. while stirring and 70.5 g, i.e. ca. 79 ml (1.6 mol), ethylenoxide is added dropwise within five minutes at 0°-10° C. After leaving it to stand for 12 hours at room temperature, 500 water is added, it is neutralised while stirring and carefully adding a total of 200 g NaHCO 3 in small portions. Afterwards the liberated base is extracted with 500 ml methylene chloride, shaken again three times with 250 ml methylene chloride each time, the organic phases are combined, dried over sodium sulphate, aspirated and concentrated in a vacuum. 178.2 g product is obtained. TLC silica gel 60 (Merck)-mobile phase: toluene/acetone=5:2, R f =0.18
B) 2-[2-hydroxyethoxy)-ethyl-(4-nitrosophenyl) amino]ethanol hydrochloride ##STR5##
A mixture of 280 ml concentrated hydrochloric acid and 140 ml water is filled into a 2 l three-necked flask with stirrer, dropping funnel and thermometer, cooled down to -5° C. with a cooling bath of dry ice, 178 g (0.79 mol) of the substance obtained according to A) is added dropwise within 10 minutes at constant temperature and stirred for a further 15 minutes. A solution of 60 g (0.87 mol) sodium nitrite in 120 ml water is added to this at 0° C. whereby the solution becomes a blood-red to brown colour and it is stirred for a further 30 minutes at 0° C. Subsequently it is diluted by adding 500 ml water (pH of the reaction mixture 1.4) and 218 ml concentrated aqueous ammonia solution is added dropwise while cooling on ice at a maximum of 15° C. to pH 9. The liberated nitroso base is extracted five times with 400 ml n-butanol and the solvent is distilled off in a rotary evaporator. 212.8 g dark green oil is obtained. This is mixed with a mixture of 250 ml toluene/acetone=1:1 in order to remove inorganic products, the insoluble portion is aspirated and washed with 50 ml toluene/acetone=1:1. 18.4 g inorganic material remains as a residue. The filtrate is purified chromatographically on a silica gel 60 column (7.5 cm in diameter, filling level 90 cm, separating fluid toluene/acetone=1:1). 155 g nitroso base, dark green oil, is obtained. This is dissolved in 600 ml acetone and reacted dropwise with 250 ml saturated ethereal hydrochloric acid. After stirring for 30 minutes while cooling on ice the crystals which form are aspirated, washed three times with 100 ml acetone and dried in a vacuum at room temperature over diphosphorus pentoxide. 159.9 g (=69.6% of the theoretical yield) of the title compound is obtained; m.p. 118° C., TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone=1:1, R f =0.24.
EXAMPLE 12
The following compounds are produced in an analogous manner to Example 11:
a) 1-[N,N-(2-hydoxyethyl)-(4-nitrosoanilino)]-3-(2-hydroxyethoxy)-2-propanolhydrochloride ##STR6##
Yield: 10.5% of theory, orange coloured crystals, m.p. 104° C. (decomp.); TLC-silica gel 60 (Merck)-mobile phase: toluene/methanol=5:1, R f =0.13 from 1-[N,N-(2-hydroxyethyl)(anilino)]-3-(2-hydroxyethoxy)-2-propanol ##STR7## (this is from 1-[N-(anilino]-3-(2-hydroxyethoxy)-2-propanol ##STR8## which is obtained from aniline with 1-chloro-3-(2-hydroxyethoxy)-2-propanol-yield: 21.5% colourless oil, TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone=5:2, R f =0.6) by reaction with ethylene oxide in the presence of 4N acetic acid. 71% colourless oil, TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone 5:2, R f =0.43
b) 1-[N-(2-hydroxyethyl)-(4-nitrosoanilino)]-3-methoxy-2-propanol hydrochloride ##STR9##
Yield: 44.5% light yellow crystals, m.p. 122° C. (decomp.). TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=49:1, R f =0.55 from (±)-3-[N-(2-hydroxyethyl)anilino]-1-methoxy-2-propanol (Deutsches Reichspatent 603808 (19433)-Friedlander 21, 295), (b.p. 11 212°-214° C.).
c) 2-](2-methoxyethoxy)ethyl-(4-nitrosophenyl) amino]ethanol ##STR10##
Yield: 255 of theory, dark brown resin. TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=19:1, R f =0.49; methylene chloride/methanol=5:1, R f =0.77 (via the amorphous hygroscopic hydrochloride with NH 3 );
from 2-[(2-methoxyethoxy)ethyl-(phenyl)-aminoethanol (A) ##STR11## which was obtained from aniline and 2-methoxyethoxy-chloroethane (heat for one hour to 90° C. and separate by column chromatography on silica gel 60 (Merck) with toluene/ethyl acetate=5:1. The N-(2-methoxyethoxy-ethyl)aniline thus formed (R f =0.69, colourless oil) ##STR12## results in (A) as a colourless oil, TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone=5:1, R f =0.31, with ethylene oxide and 4N acetic acid.
d) 2-[2(2-(2(2-methoxy)ethoxy)ethoxy)ethyl)-4-(nitroso-phenyl)amino]ethanol ##STR13##
Yield 63% of theory, green oil, TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone=1:5, R f =0.64
from 2-[2-(2-(2-(2-methoxy)ethoxy)ethoxy)ethyl-4-(phenyl)amino]ethanol.
The starting compound was produced as follows:
20.5% of the theoretical yield of a yellow oil, R f =0.5 ##STR14## is obtained from aniline and diethylglycol-bis-(2-chloroethylether) (Perry, Hibbert Can. J. Res. 14, 81 (1936) by heating to 140° C. for four hours and subsequent separation by column chromatography on silica gel 60 (Merck) with toluene/ethyl acetate=2:1.
Its reaction with ethylene oxide in a 4N acetic acid yields almost quantitatively ##STR15## as a beige coloured oil, TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=19:1, R f =0.61.
Using NaOCH 3 in methanol (heat for 24 hours under reflux, evaporate, add water, take up in ethyl acetate and subsequently purify the crude product by column chromatography on silica gel 60 (Merck) with toluene/acetone=5:2), 51.3% of the theoretical yield of product is obtained as a colourless oil, R f =0.21.
EXAMPLE 13
N-(4-nitrosophenyl)-N-[(2-diethylamino)-ethyl]-N,N'-diethyl-1,2-ethane-diamine-tris-hydrochloride ##STR16##
m.p. 125° C. (decomp.), TLC: silica gel 60 (Merck)-mobile phase: isopropanol/n-butylacetate/water/concentrated aqueous NH 3 =50:30:15:5, R f =0.566
from N-[di-(2-diethylamino)ethyl]aniline.
EXAMPLE 14
Production of 1-N-substituted 4-(4-nitrosophenyl)-piperazines ##STR17##
a) 1-methyl-4-(4-nitrosophenyl)-piperazinedihydrochloride ##STR18##
17.62 g (0.1 mol) 1-methyl-4-phenyl-piperazine (40.1% of the theoretical yield, b.p. 0 .05 82°-84° C., R f 32 0.31, is obtained as a colourless liquid from 0.3 mol 1-phenylpiperazine by heating to 150° C. for four hours with 0.2 mol tri-methyl phosphate, isolation by adding NaOH and extracting with diethylether and purifying by column chromatography on silica gel 60 (Merck) with methylene chloride/methanol=5:1, (according to Stewart et al., J. Org. Chem. 13, 134 (1948)) is dissolved in a mixture of 20 ml concentrated hydrochloric acid and 10 ml water, then a solution of 8 g (0.12 mol) sodium nitrite in 16 ml water is added dropwise at 0°-2° C. within 15 minutes and it is stirred for a further 30 minutes at 10° C. 60 ml concentrated aqueous ammonia is added at the same temperature while cooling further, it is diluted by addition of 100 ml water and the red-brown solution (pH 9) is extracted three times by shaking with 100 ml methylene chloride each time, the organic phase is dried over Na 2 SO 4 , aspirated and evaporated. The residue (20.6 moss-green crystals) is taken up in 40 ml methanol and reacted with 20 ml saturated ethereal hydrochloric acid while cooling. 15.8 g=5.8% of the theoretical yield of moss-green crystals of the title compound is obtained after aspirating and washing twice with 20 ml ether. m.p. 187°-189° C. (decomp.), TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=5:1, R f =0.72.
The following are prepared analogously:
b) 4-(4-nitrosophenyl()-1-piperazine-ethanoldihydrochloride ##STR19##
from 2-(4-phenyl-piperazine)-ethanol (Kremer, J. Amer. Chem. Soc. 58, 379 (1963)) as light grey crystals; purified by recrystallization from methanol/water=7:1, m.p. 170°-173° C., (decomp.), TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=5:1, R f =0.67
c) 3-[4-(4-nitrosophenyl)-1-piperazinyl[-1,2-propanediol-dihydrochloride ##STR20## from 1-phenyl-4-(2,3-dihydroxypropyl)-piperazine (H. Howell et al., J. Org. Chem. 27, 1711 (1962)) as green crystals, m.p. 163° C. (decomp.)-TLC: silica gel 60 (Merck), mobile phase: ethyl acetate/methanol=2:1, r f =0.41.
d) 4-(4-nitrosophenyl)-α-(methoxymethyl)-piperazine-1-ethanol-dihydrochloride ##STR21##
from 1 phenyl-4-(2-hydroxy-3-methoxypropyl)piperazine (H. Howell et al., J. Org. Chem. 27, 1711 (1962)) as yellow crystals, m.p. 162° C. (decomp.)-TLC: silica gel 60 (Merck), mobile phase: methylene chloride/methanol=19:1, R f =0.51
e) 2-[2-[4(4-nitrosophenyl)-1-piperazinyl]ethoxy]-ethanol-dihydrochloride ##STR22## from 2-[2-[4-(phenyl)-1-piperazinyl]-ethoxy-ethanol (obtained from 2 mol 1-phenylpiperazine and 1-[2-chloroethoxy]-2-methoxyethane (the latter according to U.S. Pat. No. 2,837,574) as green crystals, m.p. 134° C. (decomp.)-TLC: silica gel 60 (Merck)-mobile phase: ethyl acetate/methanol=5:1, R f =0.31. f) 1-(1,4-dioxanylyl)methyl-4-(4-nitrosophenyl)piperazine-dihydrochloride ##STR23## from 1-(1,4-dioxanylyl)methyl-4-(phenyl)-piperazine (obtained by heating 1-chloro-3-(β-hydroxyethoxy)-2-propanol (M. S. Kharash, W. Nudenberg, J. Org. Chem. 8, 189 (1943) for five hours with 1-phenylpiperazine to 130° C., extracting with ethyl acetate and evaporating. Purification by column chromatography on silica gel 60 (Merck)--mobile phase: toluene/acetone=5:2) as green yellow crystals, m.p. 166° C. (decomp.), TLC: silica gel 60 (Merck)--mobile phase: toluene/methanol=5:1, R f =0.69.
EXAMPLE 15
Nitrosoheterocycles
a) 5-nitroso-1-indolinoethanol hydrochloride ##STR24## The nitroso compound is obtained from 1-indolinoethanol (obtained by heating 1 mol indoline with 1 mol 2-chloroethanol in the presence of 1 mol finely powdered K 2 CO 3 under reflux yielding 63.8% of the theoretical yield of a colourless oil, b.p. 0 .1 128°-130° C., TLC: silica gel 60 (Merck)-mobile phase: toluene/acetone=5:2, R f =0.42) and is isolated as a base after addition of ammonia with methylene chloride. It is converted into the hydrochloride with ethereal hydrochloric acid. Light brown crystals are obtained, m.p. 180° C., TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=5:1, R f =0.51
b) 1-methyl-6-nitroso-1,2,3,4-tetrahydroquinoline hydrochloride ##STR25##
The title compound is prepared from 1-methyl-1,2,3,4-tetrahydroquinoline (obtained from 1,2,3,4-tetrahydroquinoline by heating with trimethylphosphate (according to Huisgen et al., Chem. Ber. 92, 203 (1959)). The crude product is produced in the usual manner analogous to Examples 10 and 11 and purified on silica gel 60 (Merck) with isopropanol/n-butylacetate/water=5:3:2. The title compound is obtained by dissolving this in acetone after addition of ethereal hydrochloric acid, m.p. 123°-124° C. (decomp.), TLC: silica gel 60, mobile phase: isopropanol/n-butylacetate/water=5:3:2, R f =0.7.
c) 6-nitroso-3,4-dihydro-1(2H)-quinoline-ethanol hydrochloride ##STR26##
The title compound is obtained from 2-(3,4 dihydro-2H-quinolin-1-yl)ethanol (Zaheer et al., Indian J. Chem. 1, 479 (1963), b.p. 5 140°-144° C.). The crude product is purified by column chromatography on silica gel 60 (Merck), mobile phase: methylene chloride/methanol=19:1. 10.5% of the theoretical yield of ochre-coloured crystals of the title compound are obtained by precipitation of the hydrochloride from isopropanol with ethereal hydrochloric acid and recrystallizing from ethanol, m.p. 193°-195° C. (decomp.), TLC: silica gel 60 (Merck)-mobile phase: methylene chloride/methanol=19:1, R f =0.36. | The subject matter of the invention is a method for the electrochemical determination of an analyte in the presence of an oxidoreductase and a reducible substance which transfers electrons which arise during the course of the determination reaction from the oxidoreductase onto an electrode and thus leads to a signal which is a measure for the analyte to be determined whereby the reducible substance is enzymatically reduced and oxidized at the electrode, which is characterized in that the substance which forms at the electrode by oxidation is different from the reducible substance used initially, as well as a corresponding sensor electrode system and the use of compounds suitable therefor. Finally new nitrosoaniline derivatives and a process for their production are also subject matter of the invention. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method and device for filtering elements of a structured document on the basis of an expression, in particular an expression of XPath type.
2. Related Art
It has a general application in the processing of data streams in markup language and more particularly for files of XML format.
A document, according to the invention, comprises a plurality of elements structuring the data of the document, those elements being termed nodes in XML terminology.
The XPath language (acronym for “XML Path Language”) comes from a specification of the W3C consortium called “XPath Specification 1.0” presented at the address www.w3.org/TR/xpath. The objective of this language is to define a syntax adapted to address parts of a structured document of XML type.
The syntax of this language uses a similar syntax to that used in the expressions relative to LocationPaths in a file system, for example the expression relative to a LocationPath “/bookshop/book”.
The XPath language defines four types of data which are “string”, “Boolean”, “number” and “node-set”, seven types of nodes also termed elements, and expressions making it possible to manipulate the data, in particular the defined operators “equal”, “different”, “less than”, “greater than”, “plus”, “minus”, “multiply”, “divide”, “modulo”, “binary or” and “binary and”. Nodes may represent different types of XML event, for example the start of the document (also termed the root node), an XML element, an attribute, a text, a comment, a processing-instruction, and a namespace. This syntax enables the expression of requests in relation to structured documents, for the purpose, for example, of transforming them (for example the XSLT transformation according to the W3C recommendation defined at the address www.w3.org/TR/xslt), of fast accessing sub-parts (for example according to the W3C recommendation: XPointer: www.w3.org/TR/WD-xptr) or of carrying out processing on parts of the document (for example according to the XQuery 1.0 language, defined at the address www.w3.org/TR/xquery).
The XPath language makes it possible to simplify the development of applications suitable for going through data in structured documents of XML type.
The entity adapted to perform the evaluation of an XPath expression is called an XPath Processor. On the basis of an XPath expression and a reference to XML data stored in a document or received via a network transmission, the XPath Processor evaluates the expression.
The XPath syntax also defines a grammar describing the rules of construction for the different expression and sub-expressions. These expression are in particular expressions returning a Boolean (for example the expressions OrExpr, AndExpr, RelativeExpr, EqualityExpr), the expressions returning a number (for example AdditiveExpr, MultiplicativeExpr), the expressions returning any type of data (for example the expressions FilterExpr and Function Call), and the expressions returning an ordered list of nodes (for example the LocationPath expressions corresponding to the specification of a path to resolve in an XML document).
BRIEF DESCRIPTION
The invention is particularly adapted to the expressions relative to a location path (“LocationPath” according to the XPath language syntax).
An expression relative to a LocationPath may be absolute or relative depending on whether it starts with “/” or not. In the case of an expression relative to an absolute path, the search starts from the beginning of the document, also termed root, whereas in the case of a expression relative to a relative path, the search is contextual, for example starting from the current node.
Any expression relative to a LocationPath is composed of a set of expressions indicating the “Steps” of location in that path, and each location step corresponding to a breakdown level for the evaluation of the expression relative to a LocationPath. More particularly, each location step may be matched with a level of depth in the XML document. For example the expression relative to the path /bookshop/book comprises two location steps which are “bookshop”, searched for at depth 1 , and “book”, searched for at depth 2 .
The evaluation of a location step is in particular carried out on the basis of the expression of the parent location step, i.e. the preceding location step in the expression. The result of the evaluation of a location step provides the evaluation context for the following location step. The context is composed of three elements: a node termed “context node”, a position and a size. The context node is the node in the document which verifies the preceding location step, the position indicates the rank of the solution node of the current location step among its siblings, the size of the context indicates the number of solution nodes of the current location step.
Any location step comprises one to three entities of the following entities:
Firstly, the entity expressing a filiation, also termed axis (“AxisSpecifier” according to the XPath syntax) describes the relationship between a context node and the solution nodes of a location step. This entity is optional. By default, this entity takes the value “child” according to the XPath syntax. For example, the expressions “/a/child::b” and “/a/attribute::b” mean that a search is respectively made for a node “b” child of a node “a”, the node “a” being at the root of the document and a node representing an attribute “b” child of a node “a”, the node “a” also being at the root of the document. The specification defines 13 types of entity expressing a relationship of filiation (“AxisSpecifier”) which are self, child, attribute (or @), namespace, descendant, descendant-or-self, following, following-sibling which are considered as expressions of descending filiation i.e. forward axes, and parent, ancestor, ancestor-or-self, preceding and preceding-sibling which are considered as expressions of ascending filiation i.e. backward or reverse axes.
Next, the entity expressing a test of eligibility of a candidate node (“NodeTest” according to XPath syntax) defines either a constraint of type or a constraint of name that the candidate nodes must comply with to be considered as solution to a location step. This entity is mandatory.
The syntax defines different tests of node type, in particular, the constraint of “node” type (“node( )” according to the XPath syntax), the constraint of “text” type (“text( )” according to XPath syntax), the constraint of “comment” type (“comment( )” according to the XPath syntax) and the constraint of “processing-instruction” type (“processing-instruction( )” according to the XPath syntax).
For example, the expression “/child::b” imposes a constraint of name whereas the expression “/descendant::comment( )” makes it possible to search for all the nodes of comment type.
Lastly, the entity expressing a “Predicate” according to the XPath syntax makes it possible to impose one or more additional conditions for the search for solution nodes for a location step. This entity is optional. An expression termed “predicate”, indicated between square brackets, follows the same rules of construction as any XPath expression. For example the expression “/a/b[2]” makes it possible to select all the second child XML elements of name “b” of each node of XML element type of name “a”, and the expression “/a/b[@id=“3”] makes it possible to select the children of name “b” of the node of XML element type of name “a” having an attribute “id” having a value equal to 3.
The current implementation of the XPath language make it possible to access parts of an XML document after having constructed an intermediate representation of the XML document adapted to facilitate the search, in particular in the form of a tree representing a model of objects of the document (“Document Object Model” or DOM defined at the address www.w3.org/DOM). Thus, the search consists of going through that tree as many times as necessary for the extraction of the requested nodes. Such an approach poses a double problem.
This solution proves to be costly in memory space in particular in the case of XML documents of large size. This is, if an XPath processor is implanted in an apparatus of camera, photocopier or other type, having limited resources, the intermediate representation may be too voluminous to be stored in memory. Furthermore, this solution proves to be costly in execution time on account of the multiple passes through the DOM tree during the search for solution nodes of the XPath expression.
Furthermore, if it is desired to extract at the same time the XML nodes satisfying one (or more) constraint(s) and they do not satisfy it (or them), the syntax of the XPath 1.0 specification imposes the evaluation of several expressions.
The example illustrated in FIG. 1 comprises an example of an XML document (0.1) on which evaluation is made of one or more XPath expressions, such as those illustrated at (0.2). These expressions make it possible to extract from the XML document “book” elements with particular characteristics, represented by the XPath predicates, these predicates being expressions placed between square brackets.
For each of the expressions expressed at (0.2), if it is desired to have, on the one hand, “book” elements satisfying the predicate or predicates, and/or on the other hand, “book” elements not satisfying those predicates or only partially satisfying those predicates in the case of multiple predicates, it is required to write the corresponding XPath expression or expressions, to evaluate them and to combine the results.
Thus, for example, although the conventional XPath expression //book[@price>20] amounts to requesting the XPath processor for the nodes of “book” type having a “price” attribute of which the value is greater than 20, this expression does not however also formulate the following requests: “What are the nodes of type “book” having an attribute “price” of which the value is not greater than 20?” and “What are the nodes of “book” type having an attribute “price” of which the value is greater than 20 and what are those with an attribute “price” of which the value is not greater than 20?”.
A method is known from the document U.S. Pat. No. 6,931,405 entitled <<Flexible subscription-based event notification>> for filtering XML documents based on mechanisms of subscription for reasons of “personalization” of the processing of XML information.
Thus each subscriber only receives the sub-part of an XML document of interest to him. For this, the preferences of the subscribers are translated into XPath requests. This method thus performs the filtering of XML data via the evaluation of a plurality of expressions in relation to the same document.
A method is described according to the document U.S. Pat. No. 6,941,511 entitled “High-performance extensible document transformation” directed to optimizing transformations of XML documents by applying an optimized transformation to the nodes which satisfy an XPath request and a conventional transformation to other nodes. However, this method requires a double evaluation to extract, in a first phase, all the nodes satisfying the request, and in a second phase, the list of the nodes not satisfying the request.
Thus, this document describes a method of filtering XML documents.
Given the above, it would consequently be desirable to be able to provide a means for specifying, in a single expression, the nodes to extract and to yield them at the time of a single evaluation with an associated status, for example satisfying or not satisfying, and overcoming at least some of the drawbacks mentioned above.
The present invention concerns firstly providing a method of filtering elements of a structured document on the basis of an expression, characterized in that, the expression comprising an item of information for identification of the evaluation mode of a part at least of said expression, the method comprises a step of evaluating said expression on the basis of the data of the document, the evaluating step comprising an evaluation of said part of the expression on the basis of the item of information for identification of the evaluation mode.
The method of filtering elements of a structured document on the basis of an expression, in particular an expression of XPath type, according to the invention, makes it possible to carry out an evaluation of the expression using an evaluation mode defined by an item of information for identification of the evaluation mode. Thus, according to the information for identification of the evaluation mode, the expression is evaluated differently.
According to the invention, a part of the expression is evaluated according to the evaluation mode identified.
Thus, writing of advanced expressions is enabled, comprising different modes of evaluation of different parts of the expression and to filter the data of the document according to the expression in a single pass, that is to say without going through the data of the document a plurality of times.
According to a particular feature, the expression comprising at least one sub-expression relative to a LocationPath, at least one sub-expression comprises said part of the expression.
According to this feature, the expression is composed of at least one sub-expression relative to a LocationPath and at least one sub-expression comprises the part of the expression to evaluate according to a particular evaluation mode.
According to another particular feature, each sub-expression relative to a LocationPath comprising at least one location step, at least one location step comprises said part of the expression.
According to one embodiment, each sub-expression is composed of at least one location step and at least one location step comprises the part of the expression to evaluate according to a particular evaluation mode.
Thus, according to this embodiment, it is possible to apply an evaluation mode to a step of locating a LocationPath of the expression being processed.
According to another embodiment, the step of evaluating said expression comprises a step of evaluating at least one location step.
According to a particular embodiment, the step of evaluating at least one location step furthermore depends on the position of said at least one location step in the sub-expression relative to the LocationPath.
According to another particular embodiment, the step of evaluating at least one location step furthermore depends on the nature of the sub-expression relative to the LocationPath.
According to a particular feature, at least one location step comprising at least one predicate, the step of evaluating said at least one location step furthermore depends on the result of the evaluation of said at least one predicate associated with said at least one location step.
According to this feature, the evaluation of a location step depends on the result of the evaluation of a predicate of the location step.
According to another particular feature, said at least one predicate comprises said part of the expression.
Thus, according to this feature, it is possible to associate an evaluation mode with a predicate of the expression being processed.
According to still another particular feature, said information for identification of the evaluation mode of said at least one predicate identifying a mode of extraction of the elements satisfying said at least one predicate and of the elements not satisfying said at least one predicate, the step of evaluating the location step extracts elements satisfying said at least one predicate and elements not satisfying said at least one predicate.
Thus, in a single pass through the whole of the document, it is possible to obtain a set of nodes satisfying the expression including said at least one predetermined predicate and a set of nodes satisfying the expression with the exception of said at least one predetermined predicate.
According to this feature, if a predicate is evaluated so as to identify the elements satisfying and not satisfying the part of the expression, then the location step is evaluated with that same evaluation mode.
According to a particular feature, said information for identification of the evaluation mode identifies an extraction mode of the elements not satisfying said part of the expression.
Thus, the invention makes it possible to avoid the re-writing of one or more expressions for the purpose of extracting such elements, which process may prove to be relatively complex.
According to another particular feature, said information for identification of the evaluation mode identifies an extraction mode of the elements satisfying said part of the expression and of the elements not satisfying said part of the expression.
The invention makes it possible to filter the elements satisfying and not satisfying a part of the expression without complex re-writing and without necessitating several processing operations on the document to filter.
According to one embodiment, the method comprises a step of associating an item of information with the extracted elements, indicating the satisfaction or non-satisfaction of the elements extracted from said part of the expression.
According to this embodiment, the evaluation mode of the filtered elements is associated with those filtered elements, thus with the extracted elements. The application for which these elements is destined is thus informed of the fact that an element received satisfies the expression or not, which facilitates the processing of such an element.
According to a particular feature, a pertinence measurement is furthermore associated with the extracted elements.
Thus, it is also possible to retrieve from the document to filter, elements only partially satisfying the expression to process.
According to this feature, a pertinence measurement is associated with the extracted elements in this way making it possible, for example to classify the nodes according to their pertinence measurement.
According to a particular embodiment, the pertinence measurement is a function of the percentage of predicates satisfied with respect to the total number of predicates in the expression.
According to a particular embodiment, the method comprises a step of determining the data extracted from the document verifying the set of the sub-expressions.
In a complementary manner, the invention also concerns a device for filtering elements of a structured document on the basis of an expression, characterized in that, the expression comprising an item of information for identification of the evaluation mode of a part at least of said expression, the device comprises means for evaluating said expression on the basis of the data of the document, the evaluating means being adapted to evaluate said part of the expression on the basis of the item of information for identification of the evaluation mode.
This device has the same advantages as the method of filtering elements of a structured document on the basis of an expression, briefly described above, and they will therefore not be reviewed here.
According to other aspects, the invention also concerns computer programs for an implementation of the method of the invention described briefly above.
BRIEF DESCRIPTION OF THE DRAWINGS
Other aspects and advantages of the present invention will appear more clearly on reading the following description given solely by way of non-limiting example and made with reference to the accompanying drawings in which:
FIG. 1 represents an example of an XML document on which an expression is evaluated;
FIG. 2 illustrates the application context of the invention;
FIG. 3 is a diagrammatic representation of an apparatus in which the invention is implemented;
FIG. 4 illustrates an algorithm for compiling an XPath expression in accordance with the invention;
FIG. 5 illustrates an algorithm for analyzing filiation expressions in accordance with the invention;
FIG. 6 represents an algorithm for evaluating an XPath expression according to the invention;
FIG. 7 illustrates an algorithm for verifying possible predicates contained in the location step comprising the different operations of the step S 614 of FIG. 6 according to the invention;
FIG. 8 illustrates an algorithm for calculating evaluation status of a location step in accordance with the invention;
FIG. 9 illustrates the status for each evaluation mode, depending on the predicates and the position of the location step and on the type of expression in accordance with the invention;
DETAILED DESCRIPTION
The invention consists of filtering nodes of a document, for example an electronic document written in a markup language, in particular the XML language, the filtering being specified by means of an expression, in particular an XPath expression.
Filtering on the fly makes it possible to limit the quantity of XML data stored in a memory, in particular in a random access memory and to provide to the application a means for obtaining results progressively with their obtainment.
For this, an XPath processor interprets special characters inserted in XPath expressions. Depending on the presence or absence of these special characters, the XPath processor is configured in an evaluation mode.
The three permitted extraction modes in accordance with the invention, also termed filtering operations, are the following: the extraction of the nodes satisfying the expression, termed “mode match”, the extraction of the nodes not satisfying the expression, termed “mode non-match”, and the extraction of the nodes satisfying and the nodes not satisfying the expression, termed “mode match/non-match”.
FIG. 2 illustrates the application context of the invention in which an application 1 processes XML data extracted by an XPath processor 2 by means of one or more XML analyzers 3 from an XML data stream 4 , it being possible for an XML analyzer to be an XML browser.
According to one embodiment, the XPath processor 2 comprises three entities.
Firstly, it comprises a compiler 21 the role of which is to analyze the expressions and to translate them into an internal representation. The operation of this compiler is described below with reference to FIG. 4 .
Next, the XPath processor comprises an execution control unit 22 adapted to manage the interactions between the different modules of an XPath processor as well as to manage the communication of the XPath processor with the application 1 . Furthermore, it deals with the evaluation of the nodes.
Furthermore, the XPath processor comprises one or more XPath navigators 23 which enable the execution control unit 22 to generically drive one or more XML analyzers 3 . The XPath navigators 23 are also adapted to represent the XML events received from the XML analyzers in the form of XPath nodes. The XPath navigators 23 have a buffer memory intended if need be to store the XPath nodes. The XML analyzers are responsible for the extraction of XML information from the stream or from a document 4 and for the sending thereof to the XPath processor 2 .
The evaluation of an XPath expression is in particular described below with reference to FIGS. 4 and 5 , and comprises a phase of analysis for the purpose of the compilation implemented for example by the compiler 21 and a phase of evaluation for the purpose of the extraction of the nodes according to the chosen evaluation mode implemented for example by the execution control unit 22 .
Thus, the invention is implemented in particular in the XPath processor or processors.
With reference to FIG. 3 , a device adapted to operate as a device for filtering elements of a structured document on the basis of an expression, in particular an XPath expression will now be described in terms of its hardware configuration.
The device of FIG. 3 has all the means necessary for the implementation of the method of filtering elements of a structured document on the basis of an expression, in particular an XPath expression according to the invention.
According to the embodiment that is chosen, the device is for example a microcomputer 300 connected to different peripherals, for example a digital camera 301 (or a scanner, or any other image acquisition or storage means) connected to a graphics card.
The micro-computer 300 preferably comprises a communication interface 302 connected to a network 303 adapted to transmit digital information. The micro-computer 300 also comprises a storage means 304 , such as a hard disk, as well as a diskette drive 305 .
The diskette 306 as well as the disk 304 can contain XML data according to the invention as well as the code of the invention which, once read by the micro-computer 300 , will be stored on the hard disk 304 .
According to a variant, the program or programs enabling device 300 to implement the invention are stored in a read only memory ROM 307 .
According to another variant, the program or programs are partly or wholly received via the communication network 303 in order to be stored as stated.
The micro-computer 300 may also be connected to a microphone 308 through an input/output card 314 . The micro-computer 300 also comprises a screen 309 in particular to enable the user to view the results of the evaluations. Using the keyboard 310 or any other appropriate means, the user may specify an XPath expression.
The central processing unit CPU 311 executes the instructions relating to the implementation of the invention, which are stored in the read only memory ROM 307 or in the other storage means described.
On powering up, the programs and methods for filtering elements of a structured document on the basis of an expression, in particular an XPath expression, stored in one of the non-volatile memories, for example the ROM 307 , are transferred into the random access memory RAM 312 , which will then contain the executable code of the invention as well as the variables necessary for implementing the invention.
As a variant, the methods may be stored in different storage locations of the device 300 . Generally, an information storage means, which can be read by a computer or microprocessor, integrated or not into the device, and which may possibly be removable, stores a program of which the execution implements the method of filtering elements of a structured document on the basis of an expression. It is also possible to upgrade the embodiment of the invention, for example, by adding filtering methods brought up to date or improved that are transmitted by the communication network 303 or loaded via one or more diskettes 306 . Naturally, the diskettes 306 may be replaced by any form of information carrier such as CD-ROM, or memory card.
A communication bus 313 enables communication between the different elements of the micro-computer 300 and the elements connected thereto. It will be noted that the representation of the bus 313 is non-limiting. Thus the central processing unit CPU 311 may, for example, communicate instructions to any element of the micro-computer 300 , directly or via another element of the micro-computer 300 .
FIG. 4 illustrates an algorithm for compiling an XPath expression implemented in the compiler of an XPath processor in accordance with the invention.
The XPath expression to evaluate may be specified by a user or else stored for example in a file and read by the application 1 .
According to another embodiment, the XPath expression results from the execution by the application of a program generating XPath expressions.
The expression is received by the XPath processor 2 at step E 41 .
Step S 42 , which follows step S 41 consists of commencing the lexical analysis of the expression. For this and according to one embodiment, the characters of the XPath expression are analyzed one by one in order, next, to group together the characters and form symbols, also known as “tokens”.
The grouping together of the characters makes it possible in particular to determine the reserved symbols defined in the XPath specification, for example the character “/” or classes of characters representing for example numbers or simple characters.
Furthermore, the grouping together makes it possible to determine the specific signaling characters of the evaluation mode.
According to one embodiment, the specific character “?” defines the “non-match” evaluation mode and the specific character “??” the “match/non-match” evaluation mode.
However, it is to be noted that any particular character not reserved for the XPath normative syntax may be used to carry out that signaling.
Step S 42 is followed by step S 43 during which symbols generated by the lexical analyzer during step S 42 are tested, the generated symbols comprising in particular the specific characters.
Thus, in accordance with the invention, at step S 43 , the lexical analyzer identifies the predefined symbols making it possible to signal the evaluation mode, i.e. the specific characters “?” and “??”.
If during this step, one of the symbols is analyzed as being not permitted or unknown, the step S 43 is followed by step S 44 during which the compiler terminates its execution and informs the XPath processor 2 of the non-conformity of the expression. It will thus not be possible for the expression to be evaluated.
According to a variant embodiment, the unrecognized symbol is not considered and the compilation continues.
If at step S 43 , no invalid, unauthorized or unknown symbol is detected, step S 43 is followed by step S 45 during which the step of grammatical analysis is executed.
This steps consists, for the compiler 21 , of going through the list of symbols determined at step S 42 and of identifying the types of expression defined by the XPath 1.0 syntax in the expression to compile, the modified grammar of XPath 1.0 being described in Appendix A.
For example, if the first symbol found corresponds to “/”, the expression is relative to an absolute LocationPath (“AbsoluteLocationPath” according to the XPath syntax) within the meaning of the XPath grammar. In this case, the compiler 21 continues the analysis of the symbols for identifying the components of that path, that is to say the location steps, which may be composed of entities expressing a filiation relationship (“AxisSpecifier” in the XPath syntax), a test of eligibility (“NodeTest” in the XPath syntax) and possibly one or more predicates. During this same step S 45 , as soon as the compiler identifies a location expression, it initializes an XPath navigator 23 which will take on the task of searching for candidate notes at the resolution of that expression. This processing is described below with reference to FIGS. 6 and 7 .
Step S 45 is followed by step S 46 during which it is verified that the expression, that is to say the series of symbols, is valid according to the XPath grammar.
In the negative, the compilation of the expression is made to terminate and a signal: “expression invalid” is sent during step S 44 .
On the contrary, if the expression is valid, the algorithm continues at the step S 47 during which the compiler 21 allocates in memory a structure for representing each component of the expression, in particular a structure by type of XPath sub-expression.
This step is followed by the step S 48 which, for each location step extracted by the compiler 21 , consists of configuring the associated evaluation mode. This step will be described in more detail below with reference to FIG. 5 .
During this step, for each of each location step of each expression relative to a LocationPath, determination is made of the evaluation mode which must be implemented by the execution control unit 22 on evaluation of that location step.
At the end of this analysis, the compiler 21 informs the execution control unit 22 of the end of the analysis, the latter will then commence the evaluation of the expression (step S 49 ).
The step S 48 of FIG. 4 determines, for each location step of each expression relative to a LocationPath of an XPath expression, the evaluation mode of the XPath processor 2 . Each location step is represented by a structure which contains at least one link to the LocationPath from which it comes (positioned during step S 45 ), a link to the preceding location step of that LocationPath (positioned during step S 45 ), a link to the next location step of that LocationPath (positioned during step S 45 ) and a link to a list of predicates to verify (positioned during step S 45 ), an evaluation status (positioned during the evaluation S 49 ), an evaluation mode (which is the subject of step S 48 ), and, possibly, a pertinence coefficient.
The analysis of the location steps will now be described with reference to FIG. 5 .
This analysis thus applies to all the LocationPaths identified at step S 45 as composing the XPath expression to evaluate.
According to one embodiment, this analysis is integrated into compilation step S 45 . In this embodiment, step S 45 also comprises the steps S 46 to S 48 at the time of grammatical analyses.
According to another embodiment, step S 48 appears as one of the steps consecutive to the step S 45 .
The analysis of the location steps coming from the compilation commences with the step S 500 consisting of obtaining the structure constructed by the compiler at step S 47 of FIG. 4 representing the expression relative to a LocationPath of which the location steps will be analyzed.
This structure comprises a list of the location steps which compose the expression relative to a LocationPath.
If the XPath expression does not comprise the LocationPath, step S 500 and by incidence step S 48 are terminated and the evaluation mode is, by default, the “match” mode.
If a LocationPath is present in the XPath expression, the algorithm continues at the step S 501 during which it is verified whether the expression relative to the LocationPath commences with a signaling symbol or not.
If a signaling symbol is present, step S 501 is followed by step S 502 during which the value of the symbol is kept in the structure representing the LocationPath constructed at step S 46 .
In the opposite case, that is to say if the path does not commence with a signaling symbol, the algorithm continues at the step S 503 during which the default value of the evaluation mode (“match”) is kept in the structure for representing the LocationPath.
The steps S 502 and S 503 are followed by the step S 504 consisting or retrieving the first location step from the expression relative to the current LocationPath.
The algorithm continues at the step S 505 consisting of verifying whether that location step contains at least one predicate.
If the location step comprises no predicate, step S 506 follows step S 505 during which the value of the evaluation mode of that expression is initialized to the value “match”. The following step is the step S 509 during which it is tested whether there remains a location step to process.
If during the test of step S 505 , it proves to be the case that the current location step contains at least one predicate, the following step (step S 510 ) consists of verifying whether at least one of the predicates contains a signaling symbol.
If no predicate is marked, the algorithm continues at the step S 508 during which the value of the evaluation mode of the current location step is initialized with the value saved at the step S 502 or S 503 . Next, the algorithm continues at the step S 500 during which it is tested whether there remains an expression relative to a LocationPath to process.
Table 1, illustrated below, shows the calculation of the evaluation mode of a location step with unmarked predicates, while considering the processing of the last location step “b”.
TABLE 1
Evaluation mode of the
expression relative to a
Evaluation mode of a
Expression
LocationPath.
location step.
/a[c]/b[d]
“match”
“match”
/a[?c]/b[d]
“match”
“match”
?/a[c]/b[d]
“non-match”
“non-match”
/a[??c]/b[d]
“match”
“match”
??/a[c]/b[d]
“match/non-match”
“match/non-match”
During the step S 510 , if the current location step contains at least one marked predicate, the algorithm continues at the step S 511 making it possible to determine the value of the evaluation mode to perform.
If at least one of the predicates contains a signaling symbol with the value of the evaluation mode “match/non-match”, that value is kept as the value of the evaluation mode of the current location step.
In the opposite case, the “non-match” mode is activated.
Step S 511 is followed by step S 509 consisting of testing whether there remains at least one location step to process.
Table 2, illustrated below, shows the calculation of the evaluation mode of a location step with marked predicates, while considering the processing of the last location step “b”.
TABLE 2
Evaluation mode of the
Evaluation mode of the
Expression
LocationPath
Step b
/a[c]/b[??d]
“match”
“match/non-match”
/a[c]/b[?d]
“match”
“non-match”
?/a[c]/b[?d]
“match”
“non-match”
/a[c]/b[d][?e]
“match”
“non-match”
/a[??c]/b[?d]
“match”
“non-match”
??/a[c]/b[??d]
“match/non-match”
“match/non-match”
This algorithm is reiterated until the last LocationPath of the expression, that is to say until the test of step 500 is negative.
Thus, the algorithm of FIG. 5 terminates as well as the step S 48 of FIG. 4 .
The following step S 49 of FIG. 4 corresponds to the evaluation of the expression and is described below, with reference to FIG. 6 .
The evaluation of an XPath expression in accordance with the invention is therefore now described with reference to FIG. 6 .
The evaluation of an XPath expression is carried out on the basis of the structure generated by the compiler in particular as described with reference to FIG. 5 .
With each type of expression of the XPath syntax there is associated a representation structure with references to the sub-expression or sub-expressions which compose it.
Furthermore, with each structure there is associated a list of instructions to execute for its evaluation. This list in particular comprises a call for the execution of the sub-expression or sub-expressions and of the instructions for managing the errors and/or the results. For example, for an expression of addition type (“AdditiveExpr” according to the XPath syntax), the list of instructions would be: evaluate the left operand, evaluate the right operand then apply the operator “+” to these 2 operands.
The algorithm for evaluation of an XPath expression commences with the step S 600 , consisting of initializing an execution control unit 22 .
This step consists of resetting to zero all the information linked to the earlier evaluations as well as the results, the XML events still in memory in the XPath navigator 23 , the intermediate states of evaluations of the expressions relative to LocationPaths or location steps.
Step S 601 , following on from step S 600 , consists of initializing the different expressions relative to an absolute LocationPath (“AbsoluteLocationPath” in the XPath syntax) which compose the XPath expression to evaluate.
For this, for each expression relative to an AbsoluteLocationPath, a buffer memory is reserved intended to receive intermediate evaluation results.
If this memory has already been reserved, in particular during a prior evaluation of that same expression, the data contained in that memory are reset to zero during that same step.
Step S 601 is followed by step S 602 consisting of preparing, on the basis of each expression relative to an AbsoluteLocationPath contained in the XPath expression, a list of location steps to evaluate, the evaluation and the going through of the XML document being based in particular on the break down into location steps.
Thus, during this step S 602 , the location steps are classified according to the values of the entities expressing a filiation relationship (“AxisSpecifier” according to the XPath syntax) of those steps.
According to one embodiment, during that step S 602 , the location steps are classified on the basis of the depth at which to search for a candidate node.
For example, an attribute (“attribute” according to the XPath specification) and a “context node” (“self” according to the XPath specification) take priority with respect to a child (“child” according to the XPath specification) and with respect to a following one (“following” according to the XPath specification).
More particularly, the former ones designate a candidate XML node located at the current depth whereas the latter ones respectively necessitate exploring possible elements having a depth incremented by 1 with respect to the current node and to consider the nodes located beyond the end of the current element.
Furthermore, the location steps may be provisionally stored in the memory of the execution control unit 22 .
Step S 602 is followed by step S 603 consisting of going through the XML document 4 by means of the XML analyzer 3 in search of the next XML node.
Next, the extracted node is returned to the XPath navigator 23 , to be stored in its list of nodes.
The following step (step S 604 ) verifies whether the node received may be considered as a candidate for the resolution of one or more of the location steps present in the list constructed at step S 602 .
If the node corresponds to an attribute, an XML element, a text node or a comment node, that node is considered as a candidate node. The algorithm then continues at the step S 608 described below.
If that is not the case, the algorithm continues at the step S 605 consisting of testing whether the node obtained corresponds to an XML element end.
In the positive case, step S 605 is followed by step S 606 during which the algorithm returns to the previous list of the location steps.
Step S 606 is followed by step S 607 consisting of testing whether the list is empty or not. In this way, it is tested whether a return has been made beyond the first step of the expressions relative to the path considered.
If the list is empty, the end of the evaluation is detected. In the opposite case, the algorithm continues at step S 602 described earlier.
If, at step S 605 , the node retrieved does not corresponds to an XML element end, the node is ignored and the algorithm continues at the step S 603 consisting of going through the XML document.
Returning to step S 604 , if the extracted node is a candidate node, the algorithm continues at the step S 608 consisting of obtaining an entity expressing an eligibility test of a candidate node (“NodeTest” according to the XPath syntax).
Next, the algorithm continues at the step S 609 consisting of testing that node with respect to the eligibility test of the current location step.
The application of each eligibility test at step S 609 consists of verifying either the name, or the type of candidate node with respect to the values imposed by the eligibility test of the location step.
Thus if the eligibility test is satisfied at step S 609 , the algorithm continues at the step S 610 during which the current location step has its evaluation status set to the value “potentially resolved”.
In the opposite case, the algorithm continues at the step S 611 during which the current location step is marked as “not resolved”.
Next, step S 611 is followed by the step S 612 consisting of testing whether a location step remains to process.
If that is the case, the following location step is proceeded to and the algorithm continues at the step S 608 already described until the end of the list, that is to say until the test of step S 612 is negative.
Returning to step S 610 , this step is followed by the step S 613 consisting of verifying whether the location step contains at least one predicate.
If that is the case, step S 613 is followed by step S 614 consisting of verifying one or more predicates contained in the location step.
This step is described with reference to FIG. 7 .
At the end of step S 614 , the evaluation status of the current step may have the following values:
Firstly, the status may be “Resolved with intermediate solution” in the case of an intermediate location step for which a solution node has been found.
Next, the status may be “Resolved with final result” in the case of a last location step of an expression relative to a LocationPath composing the principal expression. This may, for example, be the expression /bookstore/book/title. More particularly, if the principal expression contains an expression of LocationPath type, the expected result is a list of nodes. The result given by any expression of LocationPath type situated in the predicates, in particular on each side of a comparison operator or in function calls, is either a Boolean, or a list of nodes intended to be converted into another type, in particular that produced by the function. Thus, the invention applies to the principal expressions yielding a list of nodes.
Furthermore, the status may be “Resolved with partial result” in the case of a last location step arising from an expression relative to a LocationPath composing a sub-expression of the principal expression. This may be, for example, the expression /bookstore/book/title=“Learning XML”, the principal expression here being an expression of equality (“EqualityExpr” in XPath syntax). According to the example considered, the nodes resulting from the expression are intermediate results on which the equality operator is applied. More particularly, the expected result for the evaluation of the expression of the example is a Boolean and not one or more nodes.
Furthermore, the status may be “Resolved without solution”, whatever the type of location step for which no node satisfies the constraints.
The step S 614 is followed by step S 612 making it possible to pass on to the following location step in the list calculated at step S 602 .
If a following location step exists, the algorithm continues starting from the step S 608 already described.
Otherwise, the algorithm continues at the step S 615 consisting of preparing the following list.
Step S 615 is followed by step S 616 during which it is tested whether the following list is empty or not.
If the list is empty, the algorithm continues at step S 617 .
This means that the last steps of locating expressions relative to current LocationPaths, prepared during step S 601 , have been attained.
During this step, the algorithm yields results. The execution control unit 22 retrieves the node or nodes, from memory of the XPath navigator 23 , that satisfied the last location step or steps of each expression relative to a LocationPath, transmits them to the application if the expected result is of node list type or else applies to them a function or a test according to the type of expression to evaluate.
During this sending and in the case of a “match/non-match” evaluation mode, the status of the node, stored in memory in the structure representing an XPath node, is also provided to the application.
Step S 617 is followed by step S 606 in order to climb the list of previous location steps, as already described, in order to search for new candidate nodes for the resolution of the expressions relative to LocationPaths if that list is not empty (test of step S 607 ).
If the test of step S 616 indicates that a list of location steps is not empty, the algorithm continues at the step S 602 already described in order to evaluate those location steps.
Returning to step S 613 , if the test is negative, that is to say if the location step does not contain any predicate, the algorithm continues at the step S 618 consisting of updating the evaluation status of the current location step.
If it is an intermediate location step, its evaluation status takes the value: “resolved with intermediate solution”.
If it is the last location step of an expression relative to a LocationPath corresponding to the principal expression, it is marked as “resolved with final result”.
If it is a location step arising from an expression relative to a LocationPath corresponding to a sub-expression of the expression to evaluate, its evaluation status takes the value: “Resolved with partial result”.
The step S 618 is followed by the step S 612 already described, consisting of testing whether a location step remains to process.
FIG. 7 illustrates an algorithm for verifying predicates that may be contained in the location step, this algorithm illustrating the different operations carried out at the step S 614 .
This predicate verification algorithm commences at step 710 by saving the evaluation context of the execution control unit 22 . For this, the following information is stored in a memory of the execution control unit 22 : the list of the current location steps, the location step on which the predicate or predicates are verified, termed context location step, and the context node situated in memory of the XPath navigator 23 .
After having stored in memory the evaluation context, step S 710 is followed by step S 711 during which the evaluation of the first predicate commences. For this, the first predicate of the list is obtained.
According to one embodiment, a link on the list of predicates contained in the location step makes it possible to obtain the first predicate.
This first predicate becomes the current predicate.
The following step (step S 712 ) consists of evaluating the XPath sub-expression representing the current predicate.
The evaluation of the predicate corresponds to the evaluation of an expression in accordance with the algorithm of FIG. 6 already described.
However, a specificity is the fact that the nodes resulting from an expression representing a predicate are not transmitted to the application but translated into a “true” or “false” Boolean result according to the test to be carried out in the predicate, for example a test of value, a test of position, a test of name or test of mere existence.
Thus, step S 712 produces a Boolean result. This step is followed by the step S 713 consisting testing the value of the result.
If the result has the value false, the following step (step S 714 ) consists of calculating the evaluation status of the location step.
This step is described later on with reference to FIG. 8 .
Step S 714 is followed by step S 715 during which the evaluation context corresponding to the context location step is restored. This context is reestablished from information stored in the memory of the execution control unit 22 .
If, during the test of step S 713 , the result takes the value true, the algorithm continues at the step S 716 during which the next predicate to verify is obtained from the list of predicates of the current location step.
Step S 716 is followed by step S 717 during which it is tested whether a new predicate has been found.
If that is the case, the algorithm continues at previously described step S 712 in order to evaluate the associated expression. Next, the steps S 713 to 717 are reiterated.
This iteration takes place as long as the current predicate has the value “true” (step S 713 ) and the test of step S 717 is positive.
If the test of step S 717 is negative, that is to say if there is no longer any predicate, the algorithm continues at the step S 714 already described consisting of calculating the evaluation status of the current location step, and then of restoring the evaluation context at step S 715 .
FIG. 8 illustrates an algorithm for calculating the evaluation status of a location step in accordance with the invention.
The evaluation status of a location step is calculated according to the steps of FIG. 8 .
For this, the data considered are, the position of the location step in the expression relative to a LocationPath from which it comes, the nature of that LocationPath, for example principal expression or sub-expression, the evaluation mode of the location step, the initial evaluation status of the location step and the result of the evaluation of the predicate or predicates associated with the location step.
The algorithm commences at step S 800 consisting of obtaining the initial value of the evaluation status of the current location step.
Step S 800 is followed by step S 801 during which the value obtained is tested relative to the value “potentially resolved”.
If the value obtained is different from the value “potentially resolved”, the algorithm continues at the step S 802 during which the evaluation status of the location step takes the value “resolved without solution”.
In the opposite case, that is to say if the value obtained is “potentially resolved”, the evaluation status depends both on the evaluation mode of the location step and on the result of evaluating its predicate or predicates.
Thus, the algorithm continues at the step S 803 during which the value of the evaluation status of the current location step is obtained, i.e. the value “match”, or the value “non-match” or the value “match/non-match”.
The step S 804 following the step S 803 consists of obtaining the result of the verification of the predicate or predicates associated with the location step, that is to say the value true or the value false.
Next, the following step (step S 805 ) makes it possible to obtain the position of the location step in the expression relative to the LocationPath. The information obtained is a Boolean indicating that it is an intermediate location step or the last location step.
Lastly, the step S 805 is followed by the step S 806 during which the type of the expression relative to the LocationPath is obtained and it is determined whether it is a principal expression or a sub-expression.
During the following step (step S 807 ), these data are used as input data in the look-up table illustrated in FIG. 9 in order to extract the evaluation status.
FIG. 9 illustrates the status for each evaluation mode, depending on the predicates and the position of the location step and on the type of expression.
According to one embodiment, the implementation of the invention also makes it possible to classify the nodes of an XML document according to a degree of pertinence relative to a given XPath expression.
According to this embodiment, a marker indicating the “match” or “non match” character is no longer joined to the detected nodes having the “match/non-match” mode, but a pertinence measurement is associated with the result nodes that is determined as a function of the percentage of satisfied predicates with respect to the total number of predicates of the expression.
For example, if the following expression is considered applied to the XML document illustrated in FIG. 1 and presented earlier ??//book[@price<20][title/@lang=“French”], then the elements “book” below may be yielded, after application of the data of Table 3 for the calculation of the degree of pertinence of a result.
TABLE 3
Pertinence
Predicate 1
Predicate 2
Total
(%)
0
0
0
0
0
1
1
33
1
0
2
66
1
1
3
100
A first result having a pertinence measurement of 66% is the following element:
<book price=“17.99”> <title lang=“English”>Harry Potter and the Half Blood Prince</title> <author>JK Rowling</author> </book>
A second result having a pertinence measurement of 100% is the following element:
<book price=“16.47”> <title lang=“French”>Les Misérables</title> <author>V Hugo</author> </book>
A third result having a pertinence measurement of 0% is the following element:
<book price=“26.37”> <title lang=“English”>Learning XML</title> <author>E T Ray</author> </book>
A fourth result having a pertinence measurement of 66% is the following element:
<book price=“13.57”>
<title lang=“German”>Selected Poems</title>
<author>Goethe</author>
</book>
On sending the result, the degree of pertinence may be either requested from the XPath processor by the application on reception of the result node, or integrated as first attribute or first element of each XML node.
In order to enable this kind of application, each expression relative to a LocationPath composing a principal expression must keep a word of n bits, n being the number of predicates composing the expression relative to a LocationPath.
During the resolution of each location step, when the evaluation mode has the value “match/non-match”, the word is updated as described above.
For a given location step, the latter possesses a predicate index going from 0 to n. If it is considered that the predicate having the symbol “i” is in course of verification at step S 614 of FIG. 6 , the i-th binary element of the word of n binary elements is then updated with the value resulting from the evaluation of that predicate i.
However, according to this embodiment, it is necessary to process all the predicates of a location step even if one of them is evaluated as false. This may be carried out at a step S 713 ′ inserted between the steps S 713 and S 714 in FIG. 7 .
Thus, as illustrated in Table 4 below for calculating the degree of pertinence, the pertinence value is available at the same time as the result node.
TABLE 4
Predicate 1
. . .
Predicate n
Total
Pertinence (%)
0
0
0
0
0
0
0
1
1
100/(2 n -1)
. . .
. . .
. . .
. . .
. . .
1
1
0
2 n -2
100(2 n -2)/(2 n -1)
1
1
1
2 n -1
100
APPENDIX A
[14]
Expr
::=
OrExpr
[21]
OrExpr
::=
AndExpr |
OrExpr ‘or’ AndExpr
[22]
AndExpr
::=
EqualityExpr |
AndExpr ‘and’ EqualityExpr
RelationalExpr |
[23]
EqualityExpr
::=
EqualityExpr ‘=’ RelationalExpr |
EqualityExpr ‘!=’ RelationalExpr
AdditiveExpr |
[24]
RelationalExpr
::=
RelationalExpr ‘<’ AdditiveExpr |
RelationalExpr ‘>’ AdditiveExpr |
RelationalExpr ‘<=’ AdditiveExpr |
RelationalExpr ‘>=’ AdditiveExpr
[25]
AdditiveExpr
::=
MultiplicativeExpr |
AdditiveExpr ‘+’ MultiplicativeExpr |
AdditiveExpr ‘−’ MultiplicativeExpr
UnaryExpr |
[26]
MultiplicativeExpr
::=
MultiplicativeExpr MultiplyOperator
UnaryExpr |
MultiplicativeExpr ‘div’ UnaryExpr |
MultiplicativeExpr ‘mod’ UnaryExpr
[27]
UnaryExpr
::=
UnionExpr | ‘−’ UnaryExpr
[18]
UnionExpr
::=
PathExpr |
UnionExpr ‘|’ PathExpr
LocationPath |
[19]
PathExpr
::=
FilterExpr |
FilterExpr ‘/’ RelativeLocationPath |
FilterExpr ‘//’ RelativeLocationPath
[20]
FilterExpr
::=
PrimaryExpr | FilterExpr Predicate
VariableReference |
‘(‘ Expr ’)’ |
[15]
PrimaryExpr
::=
Literal |
Number |
FunctionCall
RelativeLocationPath |
‘?’RelativeLocationPath |
[1]
LocationPath
::=
‘??’RelativeLocationPath |
AbsoluteLocationPath |
‘?’AbsoluteLocationPath |
‘??’AbsoluteLocationPath
[2]
AbsoluteLocationPath
::=
‘/’ RelativeLocationPath? |
AbbreviatedAbsoluteLocationPath
Step |
[3]
RelativeLocationPath
::=
RelativeLocationPath ‘/’ Step |
AbbreviatedRelativeLocationPath
[10]
AbbreviatedAbsoluteLocationPath
::=
‘//’RelativeLocationPath
[11]
AbbreviatedRelativeLocationPath
::=
RelativeLocationPath ‘//’ Step
[4]
Step
::=
AxisSpecifier Node Test Predicate* |
AbbreviatedStep
[12]
AbbreviatedStep
::=
‘.’ | ‘..’
[5]
AxisSpecifier
::=
AxisName ‘::’ |
[13]
AbbreviatedAxisSpecifier
::=
AbbreviatedAxisSpecifier
‘@’?
NameTest |
[7]
NodeTest
::=
NodeType ‘(‘ ’)’ |
‘processing-instruction’ ‘(‘ Literal ’)’
[37]
NameTest
::=
‘*’ | NCName ‘:’ ‘*’ | QName
[38]
NodeTest
::=
‘comment’ | ‘text’ | ‘processing-
instruction’ | ‘node’
‘[‘ PredicateExpr ’]’ |
[8]
Predicate
::=
‘[’ ?PredicateExpr ’]’ |
‘[’ ??PredicateExpr ’]’
[9]
PredicateExpr
::=
Expr
[16]
FunctionCall
::=
FunctionName ‘(‘ (Argument ( ’,’
Argument)* )? ‘)’
[17]
Argument
::=
Expr | Method, device and computer-readable medium are provided for filtering elements of a structured document on the basis of an expression including an item of information for identification of an evaluation mode of a part of the expression. A step of evaluating the expression on the basis of the data of the structured document is performed by evaluating the part of the expression on the basis of the item of information for identification of the evaluation mode, the evaluation mode corresponding to (i) an extraction of elements not satisfying the part of the expression, (ii) an extraction of elements satisfying the part of the expression, or (iii) an extraction of elements satisfying the part of the expression and an extraction of elements not satisfying the part of the expression. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is concerned with improvements in the manufacture of sheet materials having a relief effect wherein the relief is formed by selective decomposition of a blowing agent incorporated in the sheet.
2. Description of the Prior Art
In British Pat. No. 1,458,297 there is described and claimed a process for the preparation of a differentially expanded sheet material which comprises (a) applying an organic solvent to the surface of an expandable thermoplastic sheet containing a blowing agent and allowing the treated sheet to at least partially dry, (b) applying a composition comprising an ink and a kicker for the blowing agent to selected areas of the treated surface and (c) heating the sheet to a temperature at which the blowing agent in contact with kicker decomposes and retaining the sheet at this temperature for a suitable time so that those areas of the sheet in contact with the kicker are expanded to a greater extent than those areas not in contact with the kicker.
Kickers are well known in the art and their effect is to lower the decomposition temperature of certain blowing agents. If a kicker is in association with the blowing agent in certain areas only of the sheet, depression of the decomposition temperature of the blowing agent is obtained in only those areas. Hence a greater degree of expansion of those areas of the sheet containing kicker will be obtained than those areas not containing kicker when the sheet is heated to the depressed decomposition temperature for a given period of time.
Differential expansion of an expandable thermoplastic sheet material containing a blowing agent may be obtained by applying a kicker to certain areas only of the surface of the sheet before heating the sheet to achieve expansion. Application of a kicker to the surface of the sheet possesses attractive advantages however it was found that, when the kicker is applied together with an ink to the surface of an expandable thermoplastic sheet the adhesion of the ink to the thermoplastic sheet is inadequate during subsequent treatment of the sheet. In particular, when multi-colour printing is employed, ink from one printing station has a tendency to pick-off at a subsequent printing station or onto a path roller.
A significant improvement in the adhesion of the ink is obtained when, as described in British Pat. No. 1,458,297, an organic solvent possessing an affinity for the thermoplastic material is applied to the surface of the sheet before applying the kicker. The organic solvent is preferably applied in combination with a resinous binder as a lacquer in which case it will form at least part of the solvent phase. The advantage of applying a lacquer is that, with one coating, the thermoplastic sheet may be treated with the organic solvent and with one or more additional agents present in the lacquer such as a silica or silicate matting agent.
SUMMARY OF THE INVENTION
We have now found that the quantity of kicker required to give the desired degree of expansion to the thermoplastic sheet may be reduced in certain circumstances. The printing of metallic inks onto a sheet material intended for decorative purposes can yield a visually pleasing appearance and the application of such inks to expandable thermoplastic sheets has been investigated. Surprisingly however, we have discovered that when such inks are applied to those areas of the sheet that receive an application of kicker the sheet can be expanded in those areas to an extent greater than would have been expected.
According to one feature of the present invention therefore there is provided a process for the preparation of a differentially expanded sheet material which comprises (a) applying an organic solvent to the surface of an expandable thermoplastic sheet containing a blowing agent and allowing the treated sheet to at least partially dry, (b) applying a composition containing a metallic powder and a kicker for the blowing agent to selected areas of the treated surface and then (c) uniformly heating the sheet to a temperature at which the blowing agent in contact with the kicker decomposes but below that at which it decomposes in the absence of the kicker; and retaining the sheet at this temperature for a suitable time so that those areas of the sheet in contact with the kicker are expanded to a greater extent than those areas not in contact with the kicker.
The desired degree of expansion of the sheet is achieved with a reduced amount of kicker in those areas that are printed with a metallic ink. The effect is particularly unexpected in view of the fact that we have not observed that a metallic ink causes any significant reduction in the decomposition temperature of the blowing agent. We have seen the effect when using only those amounts of metallic ink required to confer the desired decorative appearance. Thus one achieves the significant economic advantage of being able to obtain expansion with a reduced amount of kicker when the metallic ink is merely being used in those amounts normally chosen to impart upon the sheet material the desired visual effect.
We have tended to concentrate on using inks containing those grades of metallic powder hitherto employed in the production of metallic effects. Although metallic powders are available in varying degrees of coarse and fine particle sizes, the former materials are commonly used to achieve the traditional metallic finish with sheet materials. One may use inks containing fine particle size metallic powders although the results may not be so good.
Satisfactory expansion through the full depth of the sheet is dependent upon migration of the kicker through the depth of the sheet. Hence, it has particularly surprised us that a component which tends not to migrate into the full depth of the sheet should, nevertheless, enhance to an unexpected degree the extent of expansion of the full depth of the thermoplastic layer.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 illustrates one method of producing a sheet material according to the invention on-line.
FIG. 2 is an enlarged partial longitudinal section of an expandable thermoplastic sheet.
FIG. 3 is a section of the sheet shown in FIG. 2 carrying a coating of a lacquer.
FIG. 4 is a section of the sheet shown in FIG. 3 after application of an ink to the treated surface.
FIG. 5 is a section of the sheet shown in FIG. 4 after expansion.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
It should be understood that FIGS. 1-5 are purely diagrammatic and no attempt is made therein to show the relative thicknesses of the various layers that compose the sheet material.
By reason of their availability we particularly prefer to use, as the metallic powder, aluminum powders and a range of finishes may be obtained by selection of an appropriate powder. The advantages that we have achieved are however not confined to aluminium powders and copper, tin and bronze powders may also be used to obtain the enhanced extent of expansion referred to above.
Since the advantage of a saving in the amount of necessary kicker is obtained only in those areas that receive an application of metallic ink it is, in general, convenient to apply the kicker and metallic powder together. One may thus formulate a composition in which the metallic powder is dispersed and then suspend or solubilise kicker therein. Such a composition will, typically, include kicker, metallic powder, a binder and an organic solvent. Alternatively the metallic ink may be applied to the solvent treated thermoplastic sheet either before or after application of the kicker and while these techniques may result in a further improvement in the extent of expansion obtained with a given amount of kicker this does not generally offset the convenience of applying kicker and metallic powder in one step.
The improvement in extent of expansion is particularly apparent in the process according to the invention if the heating that is required to effect expansion is carried out shortly after the application of kicker and metallic powder. This is a further advantage of the process according to the invention since a reduction in overall time of production of the finished sheet is possible with consequent savings in storage costs and space. The steps of treating the sheet with a solvent, applying metallic powder and kicker and expanding the sheet may thus be effected in line.
A further enhancement of the extent of expansion may be achieved by subjecting the sheet to accelerated ageing after printing. Thus, for example, the sheet may be heated for a short period of time although, of course, heating must not be effected to a temperature at which decomposition of the blowing agent in the presence of the kicker occurs. Heating to about 100° C for about 30 minutes has, in general, achieved adequate accelerated ageing.
The metallic ink may be formulated for application in the usual way by, for example, stirring the metal powder into a lacquer. In general such a composition will contain from 2-10% preferably 3-7% by weight of metallic powder. Correspondingly the kicker will be ordinarily present in the composition from which it is applied (which may also contain the metallic powder) in amounts of up to 25% by weight, preferably 5 to 20% by weight. In general more kicker, by weight, is applied than metallic powder and we have found that satisfactory results are achieved with about 2 parts by weight of kicker to 1 part by weight of metallic powder.
The process according to the invention is of particular value in the production of wall coverings since the thermoplastic sheet material may be formed as an unsupported sheet or as a coating on paper, a non-woven synthetic fibre web, a spunbonded web or other suitable base. Differential expansion of the thermoplastic material results in the formation of a sheet having a visually attractive appearance which is well suited to decoration of a wall or ceiling. The process according to the invention is however not limited to the production of wall coverings and the sheet materials may also find utility as floor coverings, decorative laminates, display stickers and decalcomania. In the production of floor coverings the thermoplastic sheet will ordinarily be formed on a relatively substantial base which may be a suitable plastics material, a felted sheet, or a woven or knitted fabric formed, for example from natural or synthetic fibres.
In general, in the production of wallcoverings (rather than floor-coverings and the like), one seeks a relatively large degree of expansion of the raised areas of the sheet material with respect to the remainder of the sheet. It is thus necessary to employ relatively large amounts of kicker and such kicker applications are preferably achieved by increasing the ratio of kicker to resin (present in the kicker-containing composition). Thus we prefer a weight ratio of kicker to resin of at least 0.75:1, desirably at least 0.9:1, and, in general, not more than 3:1, advantageously not more than 1.5:1.
It is at these higher kicker to resin ratios (particularly in the range of from 0.9:1 to 3:1) that the problem of ink adhesion discussed above in relation to British Pat. No. 1,458,297 becomes more evident. As a practical measure we therefore consider it essential to employ the step of applying an organic solvent to the surface of the expandable thermoplastic sheet since this step does significantly enhance the adhesion of inks to the expandable sheet.
As stated above, the problem of poor ink adhesion manifests itself at higher kicker to resin ratios. It is the presence of kicker which appears to effect the ink adhesion and it follows that the step of applying an organic solvent to the surface of the expandable thermoplastic sheet to enhance ink adhesion need only be performed on those areas of the sheet that, eventually, receive an application of kicker-containing metallic ink. In general however, from the point of view of efficiency and ease of operation, it will usually be better to apply the solvent to the whole of the surface of the expandable thermoplastic sheet.
The thermoplastic sheet may be formed of any convenient expandable synthetic resinous material. Preferred materials include polymers of vinyl chloride or copolymers of vinyl chloride and anoterh copolymerisable monomer such as vinyl acetate or an acrylic or methacrylic monomer such as an ester of acrylic or methacrylic acid or acrylic or methacrylic acids themselves. The expandable sheet may be formed from a plastisol in which case the thermoplastic polymer or copolymer will be mixed with a blowing agent, a stabiliser, a plasticiser which may be any of the the usual phthalate compounds and pigments or extenders. The stabiliser should be so selected as to have a much lower catalytic action with the blowing agent under the chosen processing conditions than the kicker. The plastisol is formed into a sheet in any convenient manner and may, for example, be applied to a base web of paper or like substance as discussed above, the weight of plastisol being for example, from 40 to 800 g/m 2 .
While a variety of techniques may be used to apply a plastisol to a base such as paper some techniques are of especial advantage in large scale manufacture. Thus we prefer to apply the plastisol to the base sheet using reverse roll coating. In reverse roll coating a pair of rolls are operated in reverse directions and the plastisol is applied to the base as the latter passes through the nip between the pair of rolls. The plastisol is subjected to very high shear in this application technique and the surface of the plastisol layer produced has a distinctive character.
After the plastisol has been applied we prefer to gel and consolidate the resulting surface. Consolidation is effected by passing the gelled plastisol through the nip of a pair of sand blasted rolls. Sand blasted rolls have a uniform, slightly rough surface and the consolidation process produces a distinctive character on the surface of the gelled plastisol layer.
The precise choice of blowing agent will depend upon the particular thermoplastic material employed and, its decomposition temperature in the presence of the kicker should be appropriate to the thermoplastic material. Blowing agents are well known and have been described in the literature. Suitable blowing agents include azobis-formamide and azobis-isobutyronitrile. The blowing agent may conveniently be present in the thermoplastic sheet in amounts of up to 15%, e.g. 1 to 15%, preferably from 3 to 9%, by weight based on the weight of the expandable, synthetic resinous material.
An alternative technique for use in the production of the expandable thermoplastic sheet is hot melt coating. This technique may be applied to a wide range of materials such as polyethylene, polyvinyl chloride, polyester and acrylic polymers.
Application of the solvent may be made in any convenient manner as described fully in British Pat. No. 1,458,297. Since the function of the solvent appears to be, in part at least, to etch the surface of the sheet the solvent should be chosen according to the character of the thermoplastic material. Thus, in the case of expandable thermoplastic sheets based upon polymers of vinyl chloride or copolymers of vinyl chloride and another copolymerisable monomer, we prefer that the organic solvent should be polar since such solvents usually possess a greater affinity for the thermoplastic material than do non-polar solvents.
Suitable solvents for application to the thermoplastic sheet include hydroxylic compounds for example mono- and polyhydric alcohols; aliphatic and alicyclic ethers such as tetrahydrofuran; esters such as ethylacetate or isopropyl acetate; glycol ethers; glycol esters such as 2-ethoxyethyl acetate; aliphatic and alicyclic ketones such as methyl ethyl ketone, methyl isobutylketone or cyclohexanone; halogenated hydrocarbons in particular chlorinated aliphatic hydrocarbons; nitro compounds such as nitro propane or nitrobenzene; and Lewis bases such as substituted amides for example dimethylformamide and dimethylacetamide and di(loweralkyl)sulphoxides for example dimethylsulphoxides.
There may be advantages associated with the use of strongly polar solvents in certain cases and, in such cases it may be desirable to use the chosen solvent in conjunction with a less polar or non-polar solvent. The latter material serves as a diluent for the polar solvent and may conveniently be a hydrocarbon such as toluene, xylene or methylated spirits.
In the particular case of thermoplastic sheets formed of vinyl chloride homopolymers and copolymers we have found aliphatic ketones such as methyl ethyl ketone and aromatic hydrocarbons such as toluene or xylene to be advantageous solvents to use.
The rate application of the chosen solvent to the expandable thermoplastic sheet will depend upon the method of application used. In general a rate of application of from 10 to 700 g/sq.m, preferably 30 to 500 g/sq.m, will yield satisfactory results. In the particular case of application of the solvent by gravure printing the rate of application may be from 25 to 300 g/sq.m, preferably from 50 to 150 g/sq.m.
As stated above the chosen solvent may be applied as the solvent phase of a lacquer. The use of a lacquer is a convenient way of treating the surface of the thermoplastic material with an additional component such as a matting agent or pigment. The heat treatment in the expansion step may produce a glossy surface on the resulting sheet and it may be desirable to introduce a matting agent to reduce this effect. The lacquer may contain, as binder, any suitable resin such as a polymer or copolymer of ethylenically unsaturated monomers for example vinyl and/or acrylic or methacrylic monomers. Other suitable binders for the lacquer include polyurethanes, polyesters and epoxy resins. The lacquer may be applied by any of the well-known techniques such as gravure, roller coating, screen printing or flexo-graphic printing and since these methods may also be used to apply compositions containing a kicker and a metallic powder the whole technique readily lends itself to an in-line industrial operation.
We particularly prefer to employ gravure rollers in the application of a lacquer to the surface of the thermoplastic sheet. The gravure rollers will preferably be engraved with 80 to 200 lines per linear inch.
The kicker will ordinarily be a compound of zinc, cadmium or lead and conveniently the kicker will be a salt of zinc, cadmium or lead although other compounds of the chosen metals may be employed such as, for example, zinc oxide. Zinc, cadmium or lead salts may be formed of inorganic or organic acids. Inorganic acids which may be used in salt formation include hydrochloric and nitric acids whilst suitable organic acids include carbonic, oxalic, acetic, lactic, citric, formic, sebacic, octanoic, stearic, phthalic and benzoic acids. The preferred kickers are the salts of octanoic acid and a particularly convenient kicker to employ is zinc octoate.
The solvent for the metallic ink may be any of the usual solvents for such inks employed in the production of printed wall coverings. Thus, for example, ketones such as methyl ethyl ketone; esters such as 2-ethoxyethyl acetate; nitro compounds such as nitropropane and hydrocarbons such as toluene may all be used with advantage.
Formulation of the kicker and metallic powder composition(s) will depend upon the precise manner of printing onto the treated sheet material chosen. The composition(s) may however be applied with equal advantage in printing using any of the conventional techniques such as those listed above for application of the lacquer.
As mentioned above the expandable thermoplastic sheet is preferably formed from a plastisol and in the case of such sheet materials the degree of gelation of the expandable sheet materials at the time of application of the organic solvent and the kicker is important. Thus, if the degree of gelation is too low the surface character of the sheet will be destroyed during the application of the solvent, especially if such application involves passage of the sheet through the nip of printing rollers. Conversely, if the degree of gelation is too great it will be difficult to obtain satisfactory expansion of the sheet. Satisfactory gelation of the sheet may be achieved by heating it to 110°-140° C for a relatively short period of time. A few minutes heating at low temperatures is generally sufficient while heating for less than a minute may be adequate at higher temperatures.
Expansion of the printed thermoplastic sheet may take place as an in-line operation after the printing steps. Alternatively the printed sheets may be stacked as sheets or wound on to a reel and expanded subsequently. In this latter case there may be a tendency for kicker from one sheet to migrate into adjacent stacked or wound sheets causing undesired expansion in areas of those adjacent sheets.
The thermoplastic sheet may be provided with a coating which is impervious to the kicker after the printing step in order to avoid this problem and the impervious layer may be applied either to the back or to the front of the sheet before it is stacked or reeled. The layer is preferably applied as a transparent lacquer to the top face of the printed sheet after the final printing step. Application of the impervious layer to the top face is preferred because, in addition to providing the barrier to migration of the kicker, such a coating may serve as a wear layer to protect the sheet in use.
If desired the sheet material obtained by the process according to the invention may be presented with a coating of adhesive on the side for application to the substrate. For example, in the particular case of wall coverings the side of the sheet material to be applied to the wall or ceiling may be provided with a coating of a water-activatable adhesive. The adhesive coating may be provided at any convenient point in the manufacture of the sheet material.
In the case of water-activatable adhesives the coating may be applied as an aqueous solution, dispersion or emulsion to the surface of the sheet and dried. Adhesive may be applied at the rate of 2 to 30 grams/square meter of surface area and the adhesive may be a natural or synthetic resinous material, a vegetable gum, a soluble starch or starch ether or other suitable material.
It may be preferably to incorporate into the adhesive coating other ingredients such as for example surface active agents to improve the water-absorption properties of the adhesive coating and fungicides to inhibit mould growth.
The process according to the invention may be used in the preparation of sheet materials having the most variegated effects. Thus, for example, two or more applications of a kicker composition may be made to different areas of the surface of the sheet after the treatment with a solvent. Conventional pigments may be employed in addition to the metallic ink in the different kicker compositions which, moreover, may contain differing concentrations of kicker. After expansion of such a sheet, a product is formed in which a variety of degrees of expansion have been obtained giving a product having a pleasing decorative effect.
In order that the invention may be well understood the production of a sheet material according to one preferred mode of operation according to the invention will be described by way of illustration only with reference to the accompanying drawings.
An expandable thermoplastic layer 1 is applied as a plastisol to a sheet of suitable paper 2 and partially gelled by the oven 12 to produce a sheet material as shown in FIG. 2. The sheet material so formed is presented to the nip between a pair of rolls 6 as shown in FIG. 1 and receives a coating of a lacquer 3 from a bath 7 whereafter it is partially dried by oven 11 to produce a lacquered sheet as shown in FIG. 3. The lacquer contains a dispersion of matting agent in a solution of a vinyl chloride homo- or copolymer in an organic solvent possessing an affinity for the thermoplastic sheet. A suitable lacquer is described more fully in Example 1 below.
The lacquered sheet then proceeds to the nip between a pair of conventional printing rolls 8 and ink from bath 9 is applied to certain areas only of the lacquered surface of the sheet. The ink contains aluminium powder and a kicker appropriate to the blowing agent present in the thermoplastic layer 1 and formulations for such inks are described more fully in Example 1 below. The sheet material is then of an appearance as shown in FIG. 4 and has a number of discreet areas 4 coated with kicker-containing ink.
The printed sheet shown in FIG. 4 then passes on to an oven 10 wherein the sheet attains a temperature intermediate between the decomposition temperature of the blowing agent and a mixture of the blowing agent and the kicker. Differential expansion is thereby obtained to form a product, as shown in FIG. 5, in which those portions of the sheet that received an application of kicker-containing ink are expanded to a greater extent than those portions of the sheet which received no such coating. The resulting sheet material is visually attractive and may be used as a wall covering.
In order that the invention may be further understood the following examples are given by way of illustration only. In the examples parts referred to are parts by weight.
EXAMPLE 1
(a) Preparation of expandable thermoplastic sheet
______________________________________Polyvinyl chloride 100 partsDicapryl phthalate (plasticizer) 65 partsOrgano-tin stabiliser 1 partEpoxidised oil stabiliser 6 partsAzobis-formamide 6 partsTitanium dioxide 40 partsWhite spirit 5 parts______________________________________
was applied by means of a doctor blade at a thickness of 0.2 mm and a dried weight of 190 gm/M 2 on to 90 gm/m 2 Paper. The coating was gelled at a temperature of 120-130° C for 60 seconds to yield an expandable thermoplastic sheet
(b) Treatment of expandable sheet with solvent
A lacquer was prepared by dispersing the following formulation:
______________________________________Vinyl chloride/vinylacetate copolymer 18 partsSilica matting agent 8 partsMethyl ethyl ketone 40 partsXylene 10 partsToluene 24 parts______________________________________
The viscosity of the lacquer was adjusted by addition of methyl ethyl ketone to 30 seconds (as measured on Ford No. 4 cup) and the lacquer was then applied to the surface of the gelled polyvinyl chloride sheet prepared in (a) using a gravure roller engraved with 140 lines per linear inch.
(c) Printing
After partial drying the following ink composition was applied to the treated sheet:
______________________________________Vinyl chloride polymer in methylethyl ketone 25 parts2-Ethoxyethylacetate 5 partsMethylethylketone 28 partsToluene 12 partsZinc Octoate 20 partsAluminum powder (superfine grade) 6 parts______________________________________
If necessary the viscosity of the ink was adjusted to 30 seconds (as measured on Ford No. 4 Cup) by addition of methyl ethyl ketone. The ink was applied in a chosen pattern using a gravure roller engraved with 120 lines per linear inch and blown at 200° C for one minute after accelerated ageing at 100° C for 30 minutes.
The product obtained has an expansion in the inked areas of more than 0.014 inches relative to the unprinted areas and a visually attractive appearance enhanced by the sheen of the areas printed with the metallic ink.
As a comparison, a sheet treated with solvent as described above in (b) was partially dried and then the following ink composition was applied thereto:
______________________________________Vinyl chloride polymer in methylethyl ketone 25 parts2-Ethoxyethylacetate 5 partsMethyl ethyl ketone 28 partsToluene 12 partsZinc octoate 20 partsPigment 6 parts______________________________________
The ink was applied after any necessary adjustment of viscosity in the manner described above and the sheet was blown after the same accelerated ageing schedule. The product obtained had an expansion in the inked areas of 0.012 inches more than in the unprinted areas. An enhancement of at least 0.002 inches in expansion was thus achieved with the use of an ink containing aluminium powder.
EXAMPLE 2
(a) Preparation of expandable thermoplastic sheet
______________________________________Polyvinyl chloride 100 partsDicapryl phthalate (plasticizer) 60 partsOrgano-tin stabiliser 0.75 partEpoxidised oil stabiliser 4.5 partAzobis-formamide 4 partsTitanium dioxide 20 partsWhite spirit 5 partsFiller 14 partsViscosity depressant 1 part______________________________________
was applied by means of a doctor blade at a thickness of 0.2 mm and a dried weight of 190 gm/m 2 on to 90 gm/m 2 Paper. The coating was gelled at a temperature of 120°-130° C for 60 seconds to yield an expandable thermoplastic sheet
(b) Treatment of expandable sheet with solvent
A lacquer was prepared by dispersing the following formulation:
______________________________________Acrylic resin 8.5 partsSilica matting agent 22 partsMethyl ethyl ketone 42 partsOxitol acetate 27.5 parts______________________________________
The viscosity of the lacquer was adjusted by addition of methyl ethyl ketone to 30 seconds (as measured on Ford No. 4 cup) and the lacquer was then applied to the surface of the gelled polyvinyl chloride sheet prepared in (a) using a gravure roller engraved with 140 lines per linear inch.
(c) Printing
After partial drying the following ink composition was applied to the treated sheet:
______________________________________Acrylic resin 11 partsEthyl acetate 9 partsMethylethylketone 38.5 partsSilica matting agent 14 partsZinc Octoate 11 partsAluminum powder (gravure grade) 6 partsOxitol acetate 16.5 parts______________________________________
If necessary the viscosity of the ink was adjusted to 30 seconds (as measured on Ford No. 4 cup) by addition of methyl ethyl ketone. The ink was applied in a chosen pattern using a gravure roller engraved with 120 lines per linear inch and blown at 200° C for one minute after accelerated ageing at 100° C for 30 minutes.
The product obtained has an expansion in the inked areas of more than 0.016 inches relative to the unprinted areas and a visually attractive appearance enhanced by the sheen of the areas printed with the metallic ink.
EXAMPLES 3 and 4
Using the treated sheet prepared as described in Example 2(b) ink composition were applied using a gravure roller. In the ink compositions employed ink formulations were employed analogous to that described in Example 2(c) except that 6 parts of copper powder (Example 3) and 6 parts of bronze powder (Example 4) were substituted for the 6 parts of aluminium powder.
In each case visually attractive products were obtained and in the products the inked areas had expanded 0.014 inches more than the unprinted areas. | A process for the manufacture of a differentially expanded sheet material comprises applying an organic solvent to the surface of an expandable thermoplastic sheet containing a blowing agent and allowing the treated sheet to at least partially dry before a composition containing a metallic powder and a kicker for the blowing agent is applied to selected areas of the treated surface. The sheet is then uniformly heated to a temperature at which the blowing agent in contact with the kicker decomposes but below that at which it decomposes in the absence of the kicker, so that the areas of the sheet in contact with the kicker expand to a greater extent than the uncontacted areas. | 3 |
BACKGROUND OF THE INVENTION
The present invention relates to medical pin holder devices and more particularly to medical pin holder devices utilized in orthopedic external fixation apparatus wherein the repositioning and immobilization of a fractured bone is facilitated by means external of the soft tissue surrounding the fractured bone.
Various external fixation devices are currently available in the marketplace, all of which in one form or another utilize plural transfixing and/or half pins positioned on opposite sides of a bone fracture which extend through the fractured bone and outward beyond the soft tissue surrounding the bone. The exposed ends of the plural pins are rigidly attached to one or more pin holders which are interconnected by multiple adjustment rods to form an external frame about the soft tissue of a patient. By adjusting the relative orientation of the pin holders on opposite sides of the fracture and securely maintaining a desired orientation during rehabilitation, the bone fracture may be accurately realigned to permit proper healing of the fracture. Thus, the pin holders form an integral component of the entire orthopedic external fixation device which must be capable of rigidly clamping the pins in a desired position to provide complete immobilization of the bone fracture.
Heretofore, the prior art pin holder devices utilized in orthopedic external fixation apparatus have been formed in various design configurations, all of which have provided for the selective clamping of either singular or multiple pins within the pin holder. Although such prior art pin holder devices have proven useful in general applications, there are inherent deficiences associated in their use.
These inherent deficiencies have focused primarily upon the prior art pin holder's inability to provide sufficient clamping forces to positively prevent movement of the pins within the pin holder as well as a failure to provide any means for the independent removal or adjustment of individual pins upon the pin holder. As such, the prior art devices have often permitted to undesirable movement of the fractured bone during rehabilitation or limited operative and post-operative adjustment and modification of the pins upon the patient.
Thus, there exists a substantial need for an improved external fixation pin holder device which rigidly clamps the pin in a desired position, and additionally provides for the independent adjustment of multiple pins within the pin holder.
SUMMARY OF THE PRESENT INVENTION
The present invention comprises an improved external fixation pin holder device which significantly eliminates the deficiencies associated in the prior art. Specifically, the present invention comprises a pin holder device which positively clamps individual pins within the pin holder and facilitates the independent adjustment of a desired pin without disturbing the remaining pins within the pin holder.
The improved clamping and adjustment features of the present invention are made possible by a novel pin holder body and reciprocal pin lock member arrangement wherein individual pins extend through a pair of aligned apertures formed in the body member and pin lock member. Both of the apertures are provided with a V-shaped clamping section on opposed portions of their cylindrical walls, which are adapted to tangentially contact the diameter of the pin along discrete clamping lines. By manually reciprocating the pin lock member in a direction perpendicular to the axis of the aligned apertures, the V-shaped sections center the pin within the apertures, and apply a concentrated shearing force to the pin which positively clamps the pin within the pin holder.
Additionally, in the preferred embodiment, the present invention provides multiple pin lock members in the body portion of the device, each of which may be independently reciprocated within the body portion to permit selective adjustment of individual pins without disturbing the remaining pins within the pin holder.
DESCRIPTION OF THE DRAWINGS
These as well as other features of the present invention will become more apparent upon reference to the drawings wherein:
FIG. 1 is a partially exploded perspective view of the pin holder of the present invention, illustrating its detailed construction and depicting a manner in which it may be mounted to a support frame of the external fixation device;
FIG. 2 is a cross-sectional view of a portion of the pin holder of FIG. 1 taken about lines 2--2 of FIG. 1 showing the shape and orientation of a pocket formed therein which receives the pin lock member of FIG. 1; and
FIG. 3 is an enlarged partial side view of the pin holder of FIG. 1, illustrating the manner in which an individual pin is rigidly locked in place within the pin holder.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown the improved pin holder device 10 of the present invention which is specifically adapted for use upon a particular orthopedic external fixation device developed by Dr. David Fischer, and assigned to Ace Orthopedic Manufacturing (the assignee of the subject application). A complete description of such an external fixation device is contained in the recently filed United States patent application by Dr. David Fischer, entitled IMPROVED EXTERNAL FIXATION DEVICE (Serial Number unknown), the disclosure of which is expressly incorporated herein by reference.
As shown in FIG. 1, the pin holder 10 of the present invention is formed having an elongate body section 12 including a flange 14 at its distal end. The flange 14 is provided with a mounting boss 16 and threaded stud 18 which are adapted to mount the pin holder 10 to an I-beam frame segment 20 of the external fixation device (not shown). The length of the mounting boss 16 is formed slightly less than the distance between the outboard edges 22 and web portion 24 of the frame segment 20, such that the lower surface 26 of the flange 14 may abut the outboard edges 22 of the frame segment 20. With the threaded stud 18 inserted through a mounting aperture 28 formed in the frame segment 20, an acorn fastener 30 may be threaded onto the stud 18, from the opposite side of the frame segment 12, thereby rigidly mounting the pin holder 10 to the frame segment.
By such an arrangement, the pin holder 10 may be selectively rotated about the axis of the threaded stud 18 and subsequently locked in a desired orientation by the manual tightening of the acorn fastener 30 against the web portion 24 of the frame segment 12. Further, it will be recognized that the mounting boss 16 and threaded stud 18 may be modified with other conventional mounting means to permit the pin holder 10 of the present invention to be utilized on other particular types of external fixation devices (not shown).
The body section 12 of the pin holder 10 includes a plurality of apertures 32 extending through its width, each sized to loosely receive the exposed end of a transfixing or half pin 34 which extends through the body's soft tissue (not shown) and into the fractured bone (not shown). As best shown in FIG. 3, the lower portion of each of the apertures 32 is formed with a V-shaped wall portion 36 having an included angle of approximately 120 degrees.
A plurality of rectangular pockets 40 are formed in the body section 12 of the pin holder 14 being disposed perpendicular to the apertures 32. The pockets 40 initiate at the upper surface 11 of the body section 12 terminating at a distance below the apertures 32 but above the lower surface 13 of the body section 12 (shown in FIG. 2). Pockets of any other non-circular shape may, of course, be used.
Each of the pockets 40 are sized to slidingly receive a pin lock member 50 having a rectangular shaped body 52 and a threaded stud 54. The body 52 of the pin lock member 50 includes a central aperture 56 which extends through the pin lock member 50 and is provided with a V-shaped wall portion 58 adjacent its upper end, which is formed in the manner previously described in relation to the V-shaped wall 36 of the apertures 32. The threaded stud 54 of the pin lock member 50 extends through an aperture 60 (see FIG. 2) formed centrally between the lower surface 41 of the pocket 40 and the bottom surface 13 of the body section 12, and receives an acorn fastener 62.
The operation of the pin holder 10 of the present invention may be described with specific reference to FIGS. 1 and 3. In operation, the pin lock member 50 is loosely positioned within one of the pockets 40 formed in the body section 12, and the exposed end of the transfixing or half pin 34 inserted through both of the apertures 32 and 56 formed in the body section 12 and pin lock member 50, respectively. Subsequently, the acorn fastener 62 may be mounted onto the threaded stud 54 causing the pin lock member 50 to be pulled tightly downward toward the lower surface 41 of the pocket 40.
During this downward movement of the pin lock member 50, the horizontal center line of the aperture 56 formed in the pin lock member 50 passes beneath the horizontal center line of the aperture 32 formed in the body section 12, whereby the opposed V-shaped wall portions 36 and 58 contact the outside diameter of the pin 34. Due to the V-shaped configuration of the wall portions 36 and 58, upon contact therewith, the pin 34 is self-centered along the aligned vertical center lines of the apertures 32 and 56.
Continued manual tightening of the acorn fastener 62 causes the pin 18 to be tightly clamped between the opposing V-shaped wall portions 36 and 58 with the clamping forces being concentrated along four discrete clamping lines 70a, 70b, 70c, and 70d corresponding to the tangential contact between the outer diameter of the pin 34 with the V-shaped wall portions 36 and 58. The application of the concentrated clamping forces along the four discrete clamping lines 70a through 70d generates a shearing force upon the pin 34 which has been found to positively clamp the pin 34 within the pin holder 14.
Additionally, as shown in FIG. 1, each of the pockets 40 formed in the body section 12 of the pin holder 14 is provided with a respective pin lock member 50 which facilitates multiple pins 34 to be positively clamped within the pin holder 10. Due to each of the pins 34 being mounted to the pin holder 10 by use of a separate pin lock member 50, individual pins may be selectively adjusted within the pin holder 10 by merely loosening the appropriate acorn fastener 62 from the respective pin lock member 50 without disturbing or affecting the other pins 34 in the holder 10. As such, the present invention permits an orthopedic surgeon to independently adjust and modify pin fixation upon the patient to meet necessary operative and post-operative procedures.
Thus, in summary, the pin holder 10 of the present invention, by use of the noval V-shaped wall portions 36 and 58 and individual pin lock members 50 yields independent positive clamping of multiple pins 34 upon an external fixation device. Although in the preferred embodiment the pin holder 14 is formed to clamp three individual pins 34, those skilled in the art will recognize the teachings of the present invention are equally applicable to single as well as multiple pin clamping operations. Also, while the description refers to certain orientation as upper and lower, it will be evident that this is only for convenience and description and does not limit the orientation of the present invention. | An improved orthopedic fixation pin holder device is disclosed composed generally of a body member having a pin receiving aperture formed therethrough and a locking member slidingly mounted within the body member including a mating pin receiving aperture formed therethrough. Both apertures are provided with opposingly disposed V-shaped wall portions which apply a concentrated shearing force at discrete locations along the pin diameter to positively clamp the pin within the pin holder. | 0 |
BRIEF SUMMARY OF THE INVENTION
A conventional concrete structure having interior steel reinforcement may take the form of walls, slabs, cylindrical pipe, etc., but all have in common the use of steel rods, preferably in mesh form, as the reinforcing medium. In the manufacture of, say, cylindrical pipe, the method involves the use of a cylindrical form within which a cylindrical mesh cage is disposed concentrically. Normally, wire or like spacers are attached at intervals to the cage and have radial projections engageable with the form wall or walls for maintaining the spacing between the form and the cage. The best known patented forms of such spacers are those shown in the U.S. Pat. Nos. to Schmidgall 3,440,792 and 3,722,164 and Swenson 3,471,986. Schmidgall '792 shows a spacer intended primarily for use with dual-cage reinforcement and serves not only to space the cages from the form wall but from each other. Schmidgall '164 depicts a spacer having somewhat serpentine hooks for hooking into crossed wires of the same cage and is suited for single-cage reinforcement but is too light for heavy-duty application and braces in only one direction. Swenson's spacer is directed to use in single-cage reinforcement and is made of flat relatively thin steel having opposite hooked ends intended to snap over parallel wires of the cage and to remain in place by the resilient reactions forces between the wires and hooks. Another spacer is known as CMC (last known to have been available from Engineered Wire Products, a Division of Price Bros. Co., P.O. Box 825, Dayton, Ohio 45401) and comprises a rod-like member bent to hairpin shape having hooks at its terminal ends and somewhat less than a hook at its closed or bight end.
All of these prior art spacers suffer from several defects. As said above, the spacer of Schmidgall '792 is intended primarily for dual-cage structures. Schmidgall '164 has been discussed above. The Swenson spacer does not possess the necessary strength for heavy-duty application and cannot withstand side loading. Also, the Swenson spacer, being flat, presents too great an area to the flow of concrete and often results in voids in the finished product. Being thin and flat, it presents sharp edges to the jacket seam during rotation of the cages in the jacket, especially when the packer-head method of forming is used, which method radially compacts the concrete, in a semi-moist no-slump state, by rollers within a jacket and wherein the spacers quite often become partially or totally dislodged, resulting in further defects in the finished product. Being flat, the only way the Swenson spacer can be made stronger is to increase its cross-sectional area, but this still further impedes the free flow of concrete. Also, an increase in size and strength of the Swenson spacer renders it still more difficult to apply the spacer to the cage. The CMC spacer, although of rod-like steel, is of mild steel and is easily distorted. Since its one end at the bight is not a positive hook, it is easily dislodged from the cage. Because it has no resilience, it cannot be applied to cages having mis-spaced and/or heavy gauge wires.
According to the present invention, an improved spacer is provided. Among its desirable features are that it is made of relatively heavy-gauge spring steel and thus is positive in its grip on the cage and can adapt itself to wires of varied tolerance and/or gauge. It has positive hooks at both ends and at one end is provided with an integral lengthwise prolongation serving as a lever for receiving a force-applying tool whereby the spacer may be forcibly applied to the cage in even the most stubborn of cases. The spacer may be easily and economically mass-produced and thus may be provided to the user at relatively low cost. Most heavy-duty spacers must be welded to the mesh, which the present spacer eliminates.
Further features will appear as a preferred embodiment of the spacer is disclosed in detail in the ensuing description and accompanying drawings. The present spacer is also improved in the area of the hump or projection by means of which the cage is spaced from the form wall. The legs or struts of the hump are so designed and related to the hook portions of the spacer so that as radially inward load is applied to the spacer, its grip on the cage increases.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a part section, part elevation of the inventive spacer in relation to a form wall and a pair of mesh wires.
FIG. 2 is a perspective showing the spacer in place on a portion of mesh.
FIG. 3 shows the initial stage of applying the spacer to a pair of mesh wires.
FIG. 4 shows a succeeding stage of application.
FIG. 5 shows the final installation.
FIG. 6 illustrates the spacer as subjected to loading during the compacting process.
DETAILED DESCRIPTION
Reference will be had first to FIG. 2, wherein is best shown a representative form of reinforcing mesh 10 made up of a plurality of relatively uniformly spaced horizontal wires 12 and a plurality of cross or vertical wires 14, the wires being typically welded at their intersections to provide a unitary product. A preferred embodiment of the spacer according to the present invention is designated in its entirety by the numeral 16. FIG. 1 shows the relationship of the mesh and spacer to a form wall 18, usually a steel jacket, which in the case of concrete pipe will be cylindrical and will have a longitudinal seam (not shown) where the ends of the jacket meet. This, as indicated, is conventional and details need not be elaborated on. In the illustration here, the form, mesh and spacer are shown as they would be related in the manufacture of concrete pipe by the process of radially compacting semi-dry, semi-moist concrete with roller compaction as in the so-called packer-head method. That is, an interior core is not needed. The present spacer will, of course, function in either system and is not limited in any way to the manufacture of pipe but can be used in the manufacture of other concrete structures.
In any case, it is important that the spacer attach itself firmly to the mesh so as not to become dislodged as a result of forces occurring during the compacting process. It is also important that the spacer maintain a predetermined spacing between the mesh and the form wall, which is accomplished here by hump means 20 included as part of the spacer. The interior of the form wall represents a surface spaced from the mesh and the point of contact between the hump means and this surface represents a point located by the spacer. A typical spacer includes first hook means 22 for hooking over one wire 12 and second hook means 24 for hooking over another wire 12. In the present case, the spacer is shown hooked over neighboring wires but cases are known in which the spacer is long enough to hook over, say, the first and third wires of a group. The present description will continue on the basis of hooking over adjacent wires, but this is not a limitation.
The present spacer is a one-piece rod-like spring steel member formed generally as a hairpin, having a bight 26 and a pair of parallel, elongated, coplanar legs 28. The terminal end portions of the legs provide duplicate hooks 30 which constitute the first hook means 22, and these are so shaped as to obtain a positive hooking action over its wire; that is to say, each hook embraces a substantial portion of the circumference of the wire and thus cannot be accidentally dislodged. The bight end of the spacer is shaped to provide a second pair of duplicate hooks 32, each of S shape. The initial portion of each S-shaped hook that is an extension of the respective leg forms a first hook portion 34 that faces toward the opposite hooks 30 and this portion of each hook is continued in the reverse direction as at 36 to continue the S shape. Where the portions 34 and 36 merge a ramp or cam 38 results, and the portions 36 are continued as prolongations 40 of the length of the spacer and then are cross-connected by the transverse portion 42 of the bight. These prolongations and the portion of the bight establish a lever arm 44 by means of which application of the spacer to the mesh by a tool is facilitated.
FIG. 4 illustrates the use of a tool, such as a lever 46, received in the lever arm 42 and fulcrumming against the adjacent wire 12 and subject to downward manual pressure (arrow 48) to cam the dual S-shaped hooks over the wire which creates a positive lock of the spacer on to the mesh. As will be further seen from FIG. 4, the spacer is so dimensioned relatively to the wire spacing that, as the spacer is levered into place, the wires are drawn somewhat together (arrows 50) because of their inherent resilience, but the wires and spacer ultimately spring back and coact with the hooks to retain the spacer on the mesh. In some sizes of mesh and spacers, manual application without the tool 46 may be achieved because of the generous length of lever arm 40-42.
A further feature of the inventive spacer is the construction of the hump means 20, which is in this case of dual nature because of the spacer legs 28. Each hump has an apex 52 which serves as the contact with the form wall 18. From each apex, a pair of struts 54 diverge to blend into the spacer legs at junctions 56, each of which lies inwardly of the spacer portion that engages the wire. As best shown in FIG. 6, this enables the spacer to better embrace the wires as the spacer is deflected under radial inward load (arrow 58). The spacer will deflect (full lines as compared with dotted lines) and the wires will deflect as shown by the arrows 60. These forces all contribute to the further tenacity of the spacer to remain in place on the mesh.
As previously indicated, the form wall or jacket 18 is customarily formed in such manner as to include a longitudinal seam or splice. These never result in smooth connections, and consequently, a slight obstruction will be encountered by the spacers as the cage or mesh and spacers rotate within the form during the manufacturing process. In the present case, the dual humps minimize spacer displacement. As the first hump meets the splice it raises and lifts the trailing hump over the splice. By the time the trailing hump encounters the splice, the leading hump is past the splice and it rides the smooth surface, thus keeping the spacer stable and minimizes spacer displacement. The construction of the spacer from heavy duty spring steel is an important contributor to the strength and tenacity of the spacer and to its ability to stay in place despite substantial forces encountered during the manufacturing process.
The spacer shown is but one of the sizes in which it may be manufactured. That shown here is formed of 3/16" diameter mechanical spring wire, hard drawn. It is adapted for use on mesh having a wire spacing of 2". All inside radii are 3/16". The angle of the lever arm 40, as measured from a line tangent to the curve at 32 and perpendicular to a radius of that curve is on the order of 15°, which means that the lever arm is not only a prolongation of the length of the spacer itself but is also directed back toward the common plane of the legs 28. As best seen in FIG. 4, this improves the lever action of the tool 46. As indicated, these dimensions, etc., are representative and may be varied according to variations in the size, strength, etc., of any selected spacer. | A spacer element is provided for attachment to a pair of parallel wires of a mesh spaced from a surface of a concrete form or wall and having a projection adapted to maintain the spacing between the wall and the plane of the mesh, the element being of generally hairpin shape and providing a duplicate pair of hooks for hooking over one wire, a duplicate pair of second, S-shaped hooks for hooking over a parallel wire, a duplicate pair of V-shaped projections, and a bight joining the S-shaped hooks and providing a looped lever arm for receiving a tool for forcibly applying the element to the mesh. | 4 |
BACKGROUND OF THE INVENTION
A control arrangement for hydraulically operated implements, especially for lifting and lowering an implement arranged on an agricultural vehicle are known in the art and such a control arrangement is for instance disclosed in the German Offenlegungsschrift No. 27 35 559, and which comprises a reversing valve, a stop block in the fluid pressure stream leading to a cylinder and piston unit connected over a linkage to the implement for lifting and lowering the latter, as well as control valves for precontrolling the reversing valve and the stop block. The stop block comprises a stop valve and a releasing piston cooperating therewith, which during lifting of the implement controls a connection from the reversing valve over the releasing piston to the stop valve and which during lowering of the implement controls a connection from the stop valve over the releasing piston to a return conduit. If this known control arrangement is suddenly reversed by actuation of the magnet valves in the precontrol stage from lowering to lifting of the implement connected thereto, then it may happen that the reversing slide of the reversing valve throttles the connection from the pump to the return conduit, whereas the releasing piston has not yet opened the working conduit leading from the reversing valve over the releasing piston and the stop valve to the cylinder and piston unit connected to the implement. If this happens undesirable short pressure peaks will occur which can be relieved only over a pressure limiting valve, whereby the thereby occuring energy losses are likewise of disadvantage.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a control arrangement of the aforementioned kind in which undesirable pressure peaks and the therewith connected energy losses are avoided during operation of the control arrangement.
With these and other objects in view, which will become apparent as the description proceeds, the control arrangement according to the present invention for lifting and lowering an implement mainly comprises a cylinder and a piston movable in the cylinder and defining in said cylinder to one side of said piston therein a compartment; linkage means between said piston and said implement for lifting the latter upon feeding of pressure fluid into said compartment and for lowering the implement upon discharge of pressure fluid from the compartment, a source of pressure fluid, a tank, conduit means connecting the source of pressure fluid with the compartment, first valve means in the conduit means operable between a first position passing the pressure fluid from the source through the conduit means and a second position discharging the pressure fluid to the tank, second valve means in the conduit means downstream of the first valve means operable between a first position feeding pressure fluid passed by the first valve means into the compartment to lift the implement and a second position discharging pressure fluid from the compartment to the tank to lower the implement, and means coordinated with the second valve means to prevent during sudden shifting of the latter from the second to the first position pressure peaks and energy losses in the arrangement.
The aforementioned conduit means may comprise an inlet conduit leading from the source of pressure fluid to the first valve means, a working conduit leading from the first valve means to the second valve means and a consumer conduit leading from the second valve means to the compartment. The arrangement includes further a discharge conduit leading from the first valve means to the tank and a return conduit leading from the second valve means likewise to the tank. The first valve means may comprise a reversing valve having a reversing slide movable between a first position connecting the inlet conduit to the working conduit and a second position connecting the inlet conduit to the discharge conduit, whereas the second valve means preferably comprise a releasing valve and stop valve downstream of the releasing valve and coordinated therewith, the releasing valve has a damping chamber at one end and a control chamber at the other end thereof and further includes a releasing piston movable between a first position permitting flow of pressure fluid over a section of the working conduit downstream of the releasing valve to the stop valve and from the latter through the consumer conduit to the compartment and a second position connecting the consumer conduit to the return conduit. The arrangement includes further first and second control valve means respectively connected to the reversing and the releasing valves for controlling movement of the same between the positions thereof.
The aforementioned pressure peak preventing means preferably comprise passage means connecting a portion of the working conduit upstream of the releasing valve with the damping chamber of the latter and a pressure valve in this passage means controlled in dependence on the pressure prevailing in the working conduit upstream of the releasing valve.
The releasing valve has adjacent the damping chamber an outlet chamber and the releasing piston has a first piston section arranged to connect in the first position of the releasing piston, in which the stop valve is separated from the return conduit and connected to the upstream section of the working conduit, the damping chamber with the outlet chamber and to interrupt in a position adjacent the second position of the releasing piston the connection between the chambers and in which an additional throttle connection is provided between the chambers and in which the aforementioned passage means in the first position is separated from the upstream section of the working conduit. This arrangement permits a dampened movement of the releasing piston in one of its end positions as well as avoidance of pressure peaks during sudden reversing of the movement of the implement from lowering to lifting. This arrangement has the further advantage that in the neutral position of the control arrangement and during idling of the pump constituting the source of pressure fluid no pressure fluid can pass over the pressure valve into the return conduit so that at the start of the lowering procedure sufficient pressure for movement of the various pistons will be available.
An especially advantageous arrangement is obtained when according to the present invention the aforementioned passage means and the pressure valve are arranged in the releasing piston.
The novel features which are considered as characteristic of the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 schematically illustrates the control arrangement according to the present invention with the various elements of the arrangements shown shortly after reversing of the movement of the implement from a lowering to a lifting movement; and
FIG. 2 illustrates a part of the control arrangement according to FIG. 1 at a stopping position of the releasing piston.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 schematically illustrates a control arrangement 10 which is used as an electromagnetically controlled regulating valve for controlling a pressure fluid operated lifter 11 which may be mounted on a tractor. The control arrangement 10 mainly comprises first valve means constituted by a reversing valve 12 having a reversing slide 13 and a control slide 14 arranged in a bore of the reversing slide 13, a stop valve 15 having the function of a one-way valve and of a lowering valve and a releasing valve having a releasing piston 16 coordinated with the stop valve which has an additional control function, and a first precontrol valve 17 coordinated with the reversing valve 12 and a second precontrol valve 18 coordinated with the releasing piston 16. The releasing valve with the releasing piston 16 and the stop valve 15 form together second valve means or a stop block 19, whereas the two precontrol valves 17 and 18 form together a precontrol stage 21.
The reversing slide 13 is arranged in a bore 22 of the reversing valve 12 and the bore 22 has at opposite ends radially enlarged portions forming a first control chamber 23 and a second control chamber 24. Between these two chambers are, subsequent to the first control chamber 23, a third control chamber 25, an outlet chamber 26, an inlet chamber 27, a consumer chamber 28 and a relief chamber 29. The inlet chamber 27 is connected by an inlet conduit 31 with a pump 32 forming a source of pressure fluid and sucking pressure fluid, for instance oil, from a tank 33. A first control conduit 35 leads from the inlet conduit 31 over a throttle 36 to the first control chamber 23. The first control conduit 35 is further connected through a control channel 37, in which a one-way valve 38 is arranged with the third control chamber 25, so that the throttle 36 and the one-way valve 38 are connected in parallel with each other. The inlet conduit 31 is further connected through a conduit in which a pressure limiting valve 39 is arranged with the relief chamber 29. The reversing slide 13 has three sections 41, 42 and 43 of which the second, that is the intermediate section, has a fine control chamfer 44. The first section 41 of the reversing slide has a coaxial longitudinal bore 45 in which the control slide 14 is guided. The first section 41 has a transverse bore 46 communicating with the longitudinal bore 45 to thus connect the first control chamber 23 with the third control chamber 25, whereby this connection may be closed by the control slide 14. The control slide 14 is held by a spring 47 in the shown rest position. A second spring 47' arranged in the second control chamber 24 engages the reversing slide 13 and biases the latter in the direction towards the first control chamber 23. The transverse bore 46 in the reversing slide 13 forms together with the control channel 37 and the one-way valve 38 therein part of a second control conduit 48 which connects the first control chamber 23 with the inlet conduit 31 in parallel to the first control conduit 35. A discharge conduit 49 leads from the outlet chamber 26 to the tank 33.
The release piston 16 is guided in a bore 53 in which a damping chamber 54, an outlet chamber 55, a forwarding chamber 56, a inlet chamber 57, as well as a control space 58 are arranged adjacent to each other. A consumer channel 59 leads from the inlet chamber 57 to the consumer chamber 28 of the reversing valve 12, whereas the relief chamber 29 of the latter is connected through a relief channel 61 with the outlet chamber 55 at the release piston 16. The outlet chamber 55 is further connected through a return conduit 62 with the tank 33. The releasing piston 16 is biased by compression coil spring 63 arranged in the damping chamber 54 in the direction toward the control space 58. The release piston 16 has a first piston section 64 facing the damping chamber 54 and a second piston section 65 limiting the control space 58. The first piston section 64 closes in its left end position as shown in FIG. 1, the connection between the damping chamber 54 and the outlet chamber 55. In the same position of the release piston 16 are the two chambers 54 and 55 connected to each other over a throttle connection 66 arranged in the first piston section 64. If the releasing piston 16 is in its starting position, as illustrated in FIG. 2, the first piston section 64 is arranged to provide in addition to the throttle connection 66 also a connection between the damping chamber 54 and the outlet chamber 55. A push rod 67 coaxially projects from the first piston section 64 to the stop valve 15 with a pin section 68 of reduced diameter at the free end of the push rod. A first bore 69 in the interior of the release piston 16 passes over an annular chamber 71 under formation of a valve seat 72 into a second coaxial bore 73. A piston shaped closure member 74 is closely guided in the first bore 69 and the closure member 74 has a conical end portion which is biased by a spring 75 against the valve seat 72. The spring receiving portion of the first bore 69 is connected by a transverse bore 76 with a first annular groove 77 formed at the outer periphery of the release piston 16. This annular groove 77 is located between the first piston section 64 and the second piston section 65. A transverse bore 78 leads from the second bore 73 to a second annular groove 79 arranged in the outer periphery of the second piston section 65. An axial bore 81 leads from the annular chamber 71 through the first piston section 64 to the end face of the releasing piston 16 in the damping chamber 54. The closure member 74 is part of a pressure valve 82 located in a connection 83 leading from the second annular groove 79 to the damping chamber 54. The pressure valve 82 and the spring coordinated therewith are constructed to open the connection 83 already at relative low pressure. The releasing piston blocks in its left end position, as shown in FIG. 1 the connection between the inlet chamber 57 to the forwarding chamber 56 whereas the latter is connected to the outlet chamber 55. In this position is the second annular groove 79 connected to the inlet chamber 57. If, however, the releasing piston 16 is in its starting position, as illustrated in FIG. 2, then the forwarding chamber 56 is connected with the inlet chamber 57, whereas the connection between the forwarding chamber 56 to the outlet chamber 55 is interrupted. At the same time the second piston section 65 interrupts in the position of the releasing piston 16 as shown in FIG. 2 the connection between the inlet chamber 57 and the second annular groove 79.
The stop valve 15 has a stepped main valve body 85 which controls the connection between a first chamber 87 communicating with the consumer conduit 86 and a second chamber 89 which over a channel 88 is connected with the forwarding chamber 56 at the releasing piston 16. The stop valve 15 with its ball shaped precontrol member which is arranged between two valve seats and which is actuatable by the pin 68, is known per se. The consumer conduit 86 is connected over a pressure limiting valve 91 to the return conduit 62.
The two precontrol valves 17 and 18 of the precontrol stage 21 are of the same construction and constructed as 3port-2position valves. The spring loaded control slides 92 and 93 thereof are respectively actuatable by electromagnets 94, respectively 95. Each of the precontrol valves 17 and 18 has an inlet port 96 respectively 97, a consumer port 98, respectively 99 as well as a common return port 101. The inlet ports 96 and 97 are connected by a common conduit 102 to the inlet chamber 27 of the reversing valve 12. A conduit 103 leads from the return port 101 to the return conduit 62 to a point of the latter which is downstream of a throttle 104 arranged in the return conduit 62. The consumer port 98 is connected over a conduit 105 to the second control chamber 24 of the reversing valve 12 and the consumer port 99 is connected over a conduit 106 with the control space 58 at the releasing piston 16.
The consumer channel 59, the channel 88 and the consumer conduit 86 form parts of a working conduit leading from the reversing valve 12 over the stop block 19 to the lifter 11. The pressure fluid operated lifter 11 comprises a cylinder 11a, a piston 11b reciprocatable therein and forming to one side of the piston a compartment 11c with which the consumer conduit 86 communicates. The piston 11b actuates by means of a piston rod a lifting arm 108 mounted on the non-illustrated tractor and the lifting arm 108 actuates over a known 3-point linkage 109 a plow 110.
The operation of the control arrangement of the present invention will now be explained, whereby the known function of the control arrangement 10 in the neutral, the lifting and lowering position will be discussed only insofar as is necessary for the proper understanding of the invention.
In the neutral position, which is not illustrated, of the various elements of the control arrangement 10 the two precontrol valves 17 and 18 are not actuated, the second control chamber 24 of the reversing valve 12 and the control space 58 at the releasing piston 16 are relieved over the two precontrol valves 17 and 18 to the tank 33. The oil pumped by the pump 32 is directed by the reversing slide 13 into the discharge conduit 49, whereby due to the force of the spring 47' a smaller neutral circulating pressure is maintained in the inlet chamber 27. The releasing piston 16 which is in its starting position, as shown in FIG. 2 blocks the connection between the consumer channel 59 to the return conduit 62. The lifter 11 is hydraulically blocked by the stop valve 15.
In order to start the lowering procedure (not illustrated) at the lifter 11, the second precontrol valve 18 is actuated. Thereby the control space 58 is connected over the conduit 106, the ports 99 and 97 at the second precontrol valve 18 and the conduit 102 with the inlet chamber 27 of the reversing valve 12. Thereby the neutral circulation pressure can be built up in the control space 58 which moves the releasing piston 16 from its starting position towards the left in its end position. This movement may proceed very fast in the beginning, as long as the first piston section 64 does not close the connection of the damping chamber 54 to the outlet chamber 55. When the first piston section 64 closes this connection, oil must flow from the damping chamber 54 over the throttle connection 66, thereby damping the movement of the releasing piston 16. During its movement towards the left, the releasing piston 16 opens the connection from the forwarding chamber 56 to the outlet chamber 55. At the same time the releasing piston opens with its pin 68 the stop valve 15 in the manner of a follow-up control. Thereby pressure fluid may flow from the compartment 11c over the opened stop valve 15, the channel 88, the releasing piston 16 and the return conduit 62 to the tank 33 and during this lowering of the plow 110 the reversing slide 12 reduces the neutral circulation pressure to a pressure which is sufficient for the actuation of the releasing piston 16. During this lowering of the plow 110 the throttle 104 together with the releasing piston 16 will act as a pressure limiting valve whereby a uniform lowering of the lifter 11 independent from the load acting thereon is obtained. The neutral circulation pressure throttled by the reversing slide 13 during the lowering process acts thereby over the consumer channel 59, the inlet chamber 57, the transverse bore 78 and the second bore 73 in the releasing piston onto the closure member 74. Since the pressure valve 82 is adjusted to a pressure which is slightly above the neutral circulation pressure, the closure member 74 will close the connection through 83.
FIG. 1 illustrates now the situation which occurs shortly after the lifter 11 is suddenly reversed from lowering to lifting of the plow 110. The first precontrol valve 17 actuated by the magnet 94 connects the second control chamber 24 of the reversing valve 12 over the conduit 105, the consumer port 98, the inlet port 96 and the conduit 102 with the inlet chamber 27 of the reversing valve 12. Thereby the neutral circulation pressure will build up in the second control chamber 24 resulting in a pressure equalization between the control chambers 23 and 24. The second spring 47' presses the reversing slide 13 towards the left, as viewed in FIG. 1, whereby pressure fluid may escape unthrottled from the first control chamber 23 over the control slide 14, the transverse bore 46, the third control chamber 25 and the one-way valve 38. The reversing slide 13 is thereby moved relatively fast toward the left by the spring 47', whereby the fine control chamfer 44 throttles the flow of pressure fluid from the pump 32 into the discharge conduit 49. Whereas the reversing valve 12 acts relatively fast, the releasing piston 16 has moved shortly after reversing not far from its left end position. The spring 63 in the damping chamber 54 tries to move the releasing piston towards the right in its starting position as shown in FIG. 2. Thereby pressure fluid can flow from the control space 58 over the conduit 106, the non-actuated second precontrol valve 18 and the conduit 103 into the return conduit 62. During this movement of the releasing piston towards the right, pressure fluid will be sucked from the outlet chamber 55 over the throttle connection 66 into the damping chamber 54, as long as the first piston section 64 closes the connection between these two chambers. At the same time, the second piston section 65 of the releasing piston 16 interrupts in the position shown in FIG. 1 the working conduit 107. If now the fluid pressure is increased by the fine control chamfer 44 to a pressure which surpasses the usually low neutral circulation pressure, this increased pressure will act over the consumer channel 59 also in the inlet chamber 57 and over the cross bore 78 onto the closure member 74 of the pressure valve 82. The pressure valve 82 opens at relatively low pressure which is slightly greater than the neutral circulation pressure, and lets the pressure fluid flow over the axial bore 81 into the damping chamber 54. Thereby the movement of the releasing piston 16 from its left end position towards the right is accelerated. In this way the pressure in the system can practically not increase beyond a predetermined value determined by the pressure valve 82. If this would not occur, this would lead only to a still faster movement of the releasing piston towards its starting position. Thereby, in any case the connection of the forwarding chamber 56 to the outlet chamber 55 will be closed and the connection between the forwarding chamber 56 and the inlet chamber 57 will be opened. If now the releasing piston 16 reaches its starting position, as illustrated in FIG. 2, then the lifter 11 will perform its lifting operation due to the flow of the pressure fluid from the pump 32 over the releasing valve 12 and the working conduit 107 and the stop valve 15 to the lifter 11. In the starting position of the releasing piston 16 pressure fluid can flow from the damping chamber 54 as well as from the control space 58 over the return conduit 62 to the tank 33. In this position the second piston section 65 of the releasing piston 16 closes further the connection from the inlet chamber 57 to the second annular groove 79 and therewith to the pressure valve 82. The pressure building up in the working conduit 107 can therefore not pass over the pressure valve 82 to the return conduit 62. The pressure prevailing in the forwarding chamber 56 further acts over the cross bore 76 onto the rear face of the closure member 74 and presses the latter tightly against the valve seat. The closure member 74 which is tightly guided in the first bore 69 prevents escape of pressure medium over the first bore 69 to the return conduit 62. Therefore no pressure fluid will be lost during the lifting process. The specific construction of the connection 83 and of the pressure valve 82 will assure that also in the neutral position of the control arrangement 10 and during idling of the pump 32 a sufficient pressure will be built up for the proper precontrol.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of control arrangement differing from the types described above.
While the invention has been illustrated and described as embodied in a control arrangement for lifting and lowering of an implement, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Of course, various modifications are possible without deviating from the basic principle of the invention. Even though the arrangement of the pressure valve 82 in the connection 83 in the interior of the releasing piston 16 is especially advantageous, the elements may also be arranged in the housing of the control arrangement. Of course, the control arrangement 10 may be used not only for lifting or lowering of a plow, but other implements may also be controlled thereby. It is also possible to provide the precontrol stage 21 with valves which are not actuated by magnets as disclosed but which are actuated by other means known in the art.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | A control arrangement for lifting and lowering a hydraulically operated implement comprises a precontrolled reversing valve and a precontrolled stop block arranged in the fluid pressure stream leading from a source of fluid pressure over the reversing valve to the compartment of a cylinder and piston unit connected to the implement for lifting the latter during feeding of pressure fluid into the compartment and for lowering the implement during discharge of pressure fluid from the compartment. The stop block comprises a releasing piston cooperating with a stop valve of the stop block to alternatingly connect the compartment to a return conduit leading to a tank to discharge pressure fluid from the compartment or to the reversing valve to feed pressure fluid into the compartment. A pressure valve arranged in the releasing piston controls a connection leading from the reversing valve to a damping chamber at one end of the releasing piston which is additionally influenced by the movement of the latter. During sudden reversing of the movement of the implement from lowering to lifting fluid flows from the reversing valve over the pressure valve into the damping chamber and accelerates reversing movement of the releasing piston whereby pressure peaks in the system are avoided. | 5 |
RELATED PATENT APPLICATIONS
This patent application is a continuation of my application Ser. No. 297,916, filed Aug. 31, 1981, which is a division of my application Ser. No. 144,579, filed Apr. 28, 1980, both now abandoned. This patent application is also related to my U.S. Pat. No. 4,321,317, filed Apr. 28, 1980.
FIELD OF THE INVENTION
This invention relates to photomasks used in the manufacture of integrated circuits. It more particularly relates to an improved photomask and photomask manufacturing process which provides increased dimensional accuracy and lower cost over photomasks conventionally made.
BACKGROUND OF THE INVENTION
Integrated circuit semiconductor devices are typically made using photoetching techniques in which a photoresist is exposed to a light source through a working photomask. The working photomask conventionally is a glass plate having a pattern of opaque areas photographically developed thereon. The working photomask is photographically formed by irradiating a photodarkenable emulsion through a master mask that has been made by photoetching techniques. The master photomask usually is made by photoetching a chromium layer on a glass substrate. In this latter instance, the photoresist does not need to contain grains of a material which will darken upon irradiation and development. Accordingly, where extremely high dimensional accuracy is desired, one may choose to use a chromium photomask as the actual working mask. However, since working masks tend to deteriorate with use, use of the chromium masks as working masks is quite expensive.
A recent report discloses using a normally transparent photoetching photoresist, such as Shipley's AZ-1350 and Tokyo Oka Kogyo's OMR-83 or OSR, as an opaque emulsion for a working mask. The report indicated that the photoresist was hardened by ion implantation and optically darkened enough to block out ultraviolet light above wave lengths of 300 nanometers. The hardening made the photoresist more scratch resistant. This type of film material does not require grains of photodarkening material to produce opacity. Film pattern resolution is therefore not limited by grain size, and dimensional accuracy is improved. In addition, the cost of making the photomask is reduced, due to process simplicity.
The aforementioned photoresist films have base polymers that are respectively cresol novolac resin, cyclized polyisoprene, and poly (-vinyloxethyl cinnamate). Such photoresists are sensitive to visible light and to near ultraviolet light. Upon exposure to such light, through a mask, a pattern is activated in the transparent resist. The exposed portions of the film are selectively washed away when the film is rinsed in an appropriate solvent. Patterned photoresist coatings of up to about 4000 angstroms were darkened and hardened by ion implantation at energies of about 20-180 keV at a rate of about 0.16-1.25 microamperes per square centimeter, in dosages of about 10 14 -10 16 ions per square centimeter.
I have now found that an electron sensitive resist on a quartz substrate can also be satisfactorily darkened to ultraviolet radiation and made scratch resistant by ion implantation. However, a thicker coating and a different ion implantation procedure is required. In this patent application I propose a two-stage ion implantation process that initially darkens and hardens the electron resist, and then makes it extremely adherent to its quartz substrate. Since the resist pattern is delineated by electron irradiation, an extremely high degree of dimensional accuracy is inherently available. My two-step ion implantation process does not significantly degrade it. Consequently, extremely narrow line widths, i.e. of the order of 0.5 micrometer and less, can be readily obtained. Master photomasks of high dimensional accuracy can be obtained, in a simple process. This at least provides master photomasks of lower cost, and may even provide master masks of higher quality. Such master photomasks can also be used as working photomasks, if desired. However, it is quite costly to generate the pattern in the resist by electron beam irradiation. Hence, use of an electron beam generated photomask as a working mask is not practical at this time.
On the other hand, it has recently been reported that the electron resists such as polymethyl methacrylate (PMMA) and polymethyl isopropenyl ketone (PMIK) can be satisfactorily activated by deep ultraviolet light sources, 220 nanometers and 253.3 nanometers in wave length, respectively. My two-stage ion implantation can be used on such resists, regardless as to whether they have been patterned by electron beam or ultraviolet radiation. Pattern definition by ultraviolet radiation cannot provide as fine a resolution as obtained by electron beam irradiation. However, it is a considerably quicker and less expensive process, and the resolutions attainable are more than adequate for most present integrated circuit designs. The deep ultraviolet radiation to which PMMA and PMIK are sensitive inherently provides almost twice the resolving power resolution as the near ultraviolet radiation now typically used for photoresists such as the aforementioned AZ-1350, OMR-83 or OSR. Hence, I intend to use my invention to also make working photomasks of PMMA, PMIK or the like. However, the patterns of the working masks would be generated by ultraviolet radiation, not by an electron beam. I have also found that if the resist is implanted as described herein, it will satisfactorily block ultraviolet light down to about 200 nanometers. Hence, an extremely fine resolution master photomask made in accordance with this invention can be used to make a very fine resolution working photomask made in accordance with this invention. Use of this invention in providing such an improved masking system is described more fully and claimed in the aforementioned U.S. Pat. No. 4,321,317.
OBJECTS AND SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide unique high dimensional accuracy master and working photomasks.
Another object of the invention is to provide an improved method for making extremely high resolution master photomasks and very high resolution working photomasks.
The invention comprehends applying a layer about 0.5-1.0 micrometers thick of a transparent electron sensitive resist onto a transparent plate. The resist is then progressively exposed to an electron beam and developed in a conventional manner, to delineate a pattern of transparent resist on the plate. The resist is then given a two-stage ion implantation. In one example, the transparent resist is given a first implantation at an energy of 200 keV and a rate of 3 microamperes per square centimeter, to harden it and reduce its transmittency of ultraviolet light. It is then given a second ion implantation at an energy of about 100-150 keV at a rate of 3 microamperes per square centimeter to make the resist sufficiently scratch resistant. Both implantations are in dosages of 10 15 -10 16 ions per square centimeter.
Other objects, features and advantages of this invention will become more apparent from the following description of preferred examples thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In making a photomask in accordance with this invention a transparent resist pattern is delineated on a quartz plate in the usual manner. For example, a film of electron resist is spun onto a flat, smooth glass substrate, and then baked to drive off excess solvent. The electron resist film is then selectively irradiated by a very small diameter electron beam that progressively scans the resist, under a computerized control. The resist coated plate is then immersed in an appropriate solvent that selectively dissolves the resist. In a positive electron resist, the resist portions which are irradiated by the electron beam are dissolved away. In a negative electron resist, the resist portions which are not irradiated by the electron beam are dissolved away. If the resist is one such as PMMA or PMIK, the pattern can be delineated by blanket exposure to deep ultraviolet light through a mask instead of by the computerized electron beam. In any event, a pattern of transparent resist is delineated on the quartz plate. The manner is not critical to this invention, and can be similar to that which one might use to delineate the resist for etching of a chromium film on a glass plate. However, in this invention no chromium film is needed and no etching of a chromium film is therefore required. Consequently, higher dimensional accuracies, simpler processing and higher mask quality are inherently obtainable.
After the electron resist has been delineated on the quartz plate, the entire surface of the plate on which the patterned resist resides is given a two-stage ion implantation. The first stage ion implantation makes the electron resist significantly less transparent to ultraviolet light, and hardens it. On the other hand, the bare quartz regions exposed to the ion implantation remain transparent and hard.
The same coated surface of the quartz plate is then given a second stage ion implantation, apparently to increase adhesion of the already hardened resist to its underlying quartz surface. In any event, scratch resistance is significantly improved. Optical density does not appear to change much. Scratch resistance is at least comparable to chrome photomasks, and approaches that of the underlying quartz itself.
The resultant resist is sufficiently optically dense for use in defining patterns in the aforementioned photoresists AZ-1350, OMR-83 and OSR, that are sensitive using near ultraviolet light. However, it is also dense enough for use in defining patterns in other electron resist coatings using deep ultraviolet light. Resolutions of the order of 0.1 micrometer are readily obtainable in my implanted resist, using presently available electron beam equipment for mask pattern generation. It is expected that improvements in electron beam equipment will permit even smaller resolutions to be obtainable. Since both electron beam lithography and ion implantation are now conventional manufacturing techniques in the semiconductor industry, my photomasks are relatively easy to fabricate.
In a specific example of this invention a 0.8 micrometer thick coating of polymethyl methacrylate (PMMA) positive-type electron resist was applied to a 15 mm thick, flat, clear and colorless quartz plate in the usual manner. The liquid resist was applied to the plate and the plate spun to get a uniform thin coating. The coated plate was then baked in air at 80° C. for 30 minutes. Selected regions of the resist were then progressively exposed by selective irradiation with a 10 keV electron beam in a dosage of about 10 -6 C per square centimeter. The beam source was such as used in a scanning electron microscope and had an electron beam mean diameter of about 0.1 μm. The exposed resist was then developed by immersion of the irradiated coated plate in methyl-isobutyl-ketone for about 2 minutes at room temperature. The methyl-isobutyl-ketone was manually agitated during this immersion. The portions of the electron resist exposed to the electron beam were dissolved away, leaving a pattern of transparent electron resist on the quartz plate.
The quartz plate having the thus formed resist pattern on it was then given a uniform ion implantation across its entire surface, using 28 Si + at an energy of approximately 200 keV and a flux of 3 microamperes per square centimeter in a dosage of 5×10 15 silicon ions per square centimeter. It darkened somewhat and exhibited a transmittancy of about 1.5% and 1% with respect to near and deep ultraviolet light of a wavelength of 400 nm and 220 nm, respectively. This implantation caused the electron resist to shrink in thickness from the original 0.8 micrometer to about 0.16 micrometer. However, only a thickness shrinkage was observed. No significant lateral shrinkage was noticed. Accordingly, the high dimensional accuracy attributable to the electron beam pattern generation was preserved. However, the resist was not scratch resistant.
The entire aforementioned surface of the quartz plate, including the resist, was then given a second uniform implantation with 28 Si + . However, this time the implantation energy was 100 keV at a flux of 3 micrometeres per square centimeter in a dosage of 5×10 15 silicon ions per square centimeter. The resist shrank in thickness only slightly, if at all. Thus, dimensional accuracy was still preserved. However, the resist became highly scratch resistant. It appears to be at least comparable to that of chromium and approaches the scratch resistance of the underlying quartz itself. Transmittancy, however, remained about the same as after the first implantation.
Electron sensitive resists such as PMMA and PMIK do not lose as much transmittancy due to ion implantation as do other photoresists. Accordingly, it seems necessary to start with thicker coatings of about 0.5-1.0 micrometers. Lesser thicknesses do not provide sufficient optical density. However, once sufficient density is acquired, it is effective on wave lengths as low as about 200 nanometers. Higher thicknesses apparently require implantation energies beyond the capability of ion implantation equipment ordinarily available. I believe that if the entire thickness of the resist is not exposed to the implanted ions, the entire thickness will not harden. It not hardened throughout, an initial requirement for scratch resistance is not realized.
Implantation energies of at least about 180 keV are apparently necessary to provide complete penetration of the photoresist. 200 keV is the maximum energy available on the equipment I used. However, I believe that higher implantation energies would be useful in this invention. On the other hand, high implantation energies alone are not sufficient to darken the electron resist. The implantation must also be conducted at a rate, i.e. flux, of at least about 2 microamperes per square centimeter and preferably higher. I prefer, and have mostly used, 3 microamperes per square centimeter. While 3 microamperes per square centimeter is the highest rate my equipment will provide, I expect that higher implantation rates will be at least equally satisfactory.
Implantation must not only be at high energies and fluxes but also at dosages of at least about 1×10 15 ions per square centimeter. Otherwise, sufficient optical density for effective masking does not obtain. Dosages in excess of about 5×10 16 ions per square centimeter are to be avoided because they are time consuming and costly and do not provide further benefits. Optical density may even decrease.
I expect that this invention is not dependent on any particular ion species to produce its effect. The prior one-step ion implantation process for darkening and hardening the resist disclosed that each ion species of 31 P + , 40 Ar + , 11 B + and 49 BF 2 + would work. As noted above, I prefer to use 28 Si + . There is obviously a change that occurs in the electron resist by the first implantation of this invention. Presumably, graphitization occurs through decomposition of the resist by energy imparted by the ion bombardment. As previously indicated, the electron resist shrinks in thickness to about 1/4 or less of its original thickness. I believe that this change in thickness permits the implanted ions to penetrate too deeply through the resist into the underlying quartz substrate. I further believe that this deep penetration of the ion species does not permit the densified resist to adequately adhere to the quartz surface.
In any event, I have found that if the original densifying and hardening implant is followed with a lower energy implant of about 100-150 keV, a considerably higher degree of scratch resistance is obtained. Above and below the range of 100-150 keV, the resultant resist has a lesser scratch resistance. I do not believe the second implant produces significant hardening of the resist coating itself. I believe that the resist is hardened by the first implant but the hardened resist does not adhere well to the quartz. The added scratch resistance is thus attained because the second implant lodges ions at or near the resist-quartz interface. This activates the interface, and bonds the densified film to the underlying quartz substrate.
Implant energies of about 100-150 keV alone are not enough to achieve the additional scratch resistance. The implantation must be at a rate of at least 2 microamperes per square centimeter and preferably 3 microamperes per square centimeter. As mentioned in connection with the first implantation, it may be desirable to use implantation rates above 3 microamperes per square centimeter, but this is the limit of the equipment which I used. Analogous to the first implantation, dosages should be about 10 15 -10 16 ions per square centimeter. Dosages of less than 1×10 15 ions per square centimeter are unsatisfactory because the required adhesion is not obtained. Dosages more than about 5×10 16 ions per square centimeter are unsatisfactory because optical density decreases above 5×10 16 ions per square centimeter.
While I have described this invention only in connection with the electron resist polymethyl methacrylate, I believe that it is equally applicable to other electron resists such as polymethyl isopropenyl ketone. I further believe that this invention is applicable to any other electron or photoresist which does not exhibit adequate darkening at a low enough wave length, or adequate scratch resistance, from the previously known one-step stage implantation process. In such instance, an initial implant would be given at a higher energy to obtain optimum optical density and a second implant be given at a lower energy to obtain optimum scratch resistance.
Accordingly, this invention can be used to form masks of any sort, with any resist. However, in its preferred form, it appears to be most advantageously used to form an electron beam delineated master working mask which in turn is used to form an ultraviolet light delineated working photomask. Both the master photomask and the working photomask can thus be made of polymethyl methacrylate patterned resist on a quartz substrate hardened in accordance with this invention. Such masks can even be used to delineate a pattern of electron resist on a silicon slice for high resolution etching purposes, as is more fully described and claimed in my aforementioned U.S. Pat. No. 4,321,317.
In the foregoing description of this invention I describe using a quartz plate as a transplant substrate for the resist, instead of a glass plate. The glass in plates ordinarily used for current integrated circuit masks will transmit near ultraviolet light adequately but not deep ultraviolet light. Quartz is sufficiently transparent to deep ultraviolet light to provide a practical substrate. Accordingly, I prefer to use quartz substrates. On the other hand, if deep ultraviolet light is not to be used, or if a glass is available that is sufficiently transparent to deep ultraviolet light, it may be desirable to use glass as a substrate instead of quartz. Glass may even be preferred as a substrate, because of its lower cost, when one wants to use my process to merely impart enhanced darkening and/or scratch resistance over the known single stage ion implantation process, for resist masks used with near ultraviolet light. | A hard and adherent coating is formed from a sulfur-free organic resin coating by ion bombardment at an initial range, to at least partially carbonize the coating, and then at a lesser range, to enhance scratch resistance through improved adhesion. | 8 |
FIELD OF THE INVENTION
[0001] The invention relates to the field of moisture-curing hotmelt adhesives.
PRIOR ART
[0002] Hotmelt adhesives (hotmelts) are adhesives which are based on thermoplastic polymers. These polymers are solid at room temperature, soften on heating to give viscous liquids and can therefore be applied as a melt. In contrast to the so-called warmmelt adhesives (warmmelts), which have a pasty consistency and are applied at slightly elevated temperatures, typically in the range from 40 to 80° C., the application of the hotmelt adhesives is effected at temperatures from 85° C. On cooling to room temperature, they solidify with simultaneous buildup of the adhesive strength. Classical hotmelt adhesives are unreactive adhesives. On heating, they soften or melt again, with the result that they are not suitable for use at elevated temperature. In addition, classical hotmelt adhesives often also tend to creep even at temperatures well below the softening point (cold flow).
[0003] These disadvantages were substantially eliminated in the case of the so-called reactive hotmelt adhesives by introducing into the polymer structure reactive groups leading to crosslinking. In particular, reactive polyurethane compositions are suitable as hotmelt adhesives. They are also referred to as PU-RHM for short. They generally consist of polyurethane polymers which have isocyanate groups and are obtained by reacting suitable polyols with an excess of diisocyanates. After their application, they rapidly build up a high adhesive strength by cooling and acquire their final properties, in particular their heat distortion resistance and resistance to environmental influences, by the postcrosslinking of the polyurethane polymer as a result of reaction of the isocyanate groups with moisture. Owing to the molar mass distribution resulting during the preparation of the polyurethane polymers having isocyanate groups, however, such PU-RHM generally contain significant amounts of unreacted monomeric diisocyanates which are partly expelled in gaseous form at the application temperatures of 85° C. to 200° C., typically 120° C. to 160° C., which are usual in the case of hotmelt adhesives and, in the form of irritant, sensitizing or toxic substances, they constitute a health hazard for the processor. For this reason, various efforts have been made to reduce the content of monomeric diisocyanates in reactive polyurethane compositions in general and in PU-RHM in particular.
[0004] An obvious approach is the physical removal of the monomeric diisocyanate by distillation or extraction. These methods require complicated apparatus and are therefore expensive; in addition, they cannot be readily used for all diisocyanates.
[0005] Another approach consists in the use of special diisocyanates having isocyanate groups of different reactivity. For example WO 03/033562 A1 describes the use of an asymmetrical MDI isomer, 2,4′-diphenylmethane diisocyanate, with which polyurethane polymers having a low content of monomeric diisocyanates at low viscosity can be obtained in a simple manner. A disadvantage of this process is the insufficient availability of suitable diisocyanates on an industrial scale, associated with a high price. In addition, it is necessary to make sacrifices in the crosslinking rate since mainly only the isocyanate groups having the lower reactivity are available for the crosslinking reaction.
[0006] Finally, one approach consists in using, instead of the monomeric diisocyanates, adducts or oligomers thereof in the reaction with polyols in order to reduce the volatility, described, for example, in DE 44 29 679 A1. Here, there are disadvantages in the case of the viscosity and the reactivity of the products thus prepared.
SUMMARY OF THE INVENTION
[0007] It is therefore an object of the present invention to provide reactive polyurethane compositions (PU-RHM) which can be used as hotmelt adhesive, have isocyanate groups and are obtainable in a simple process starting from polyols and industrially available monomeric diisocyanates, and which have a low content of monomeric diisocyanates and a long shelf-life and are readily processable and which undergo rapid crosslinking.
[0008] Surprisingly, it was found that the object can be achieved by compositions as claimed in claim 1 . These contain polyurethane polymers which are solid at room temperature, have aldimino groups and can be prepared by reaction of corresponding polyurethane polymers having isocyanate groups with special compounds which contain one or more aldimino groups and an active hydrogen.
[0009] A further aspect of the invention relates to a cured composition as claimed in claim 14 , and the use of the composition as a hotmelt adhesive and a method for adhesive bonding and articles resulting from such a method.
[0010] Finally, in a further aspect, the invention relates to a method for reducing the content of monomeric diisocyanates in polyurethane polymers having isocyanate groups or in compositions which contain polyurethane polymers having isocyanate groups, by reacting the polyurethane polymers having isocyanate groups with special compounds which contain one or more aldimino groups and an active hydrogen.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] The invention relates to compositions comprising
[0000] a) at least one polyurethane polymer of the formula (I) which is solid at room temperature and has aldimino groups
[0000]
[0000] where, in formula (I)
p is an integer 1 or 2, preferably 1,
q is an integer 0 or 1, preferably 1,
with the proviso that p+q=2;
either R 1 is a monovalent hydrocarbon radical having 6 to 30 C atoms which optionally has at least one heteroatom, in particular in the form of ether oxygen;
or R 1 is a substituent of the formula (II)
[0000]
[0000] in which R 6 is a divalent hydrocarbon radical having 2 to 20 C atoms which optionally has at least one heteroatom, in particular in the form of ether oxygen, and R 7 is a monovalent hydrocarbon radical having 1 to C atoms;
R 2 and R 3 are either two substituents independent of one another which in each case are a monovalent hydrocarbon radical having 1 to 12 C atoms, or R 2 and R 3 together form a single substituent which is a divalent hydrocarbon radical having 4 to 20 C atoms, which is part of a carbocyclic ring having 5 to 8, preferably 6, C atoms, it being possible for this carbocyclic ring to be substituted;
R 4 is a divalent hydrocarbon radical having 2 to 12 C atoms which optionally has at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen;
R 5 is the radical of a polyurethane polymer which is solid at room temperature and has isocyanate groups, after removal of (p+q) isocyanate groups; and
X is O, S or N—R 8 , in which either R 8 is a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, sulfone or sulfonic acid ester group or R 8 is a substituent of the formula (III) having the abovementioned meanings for R 1 , R 2 , R 3 and R 4
[0000]
[0000] b) at least one polyurethane polymer P having isocyanate groups, if q in formula (I) is zero, or if X in formula (I) is N—R 8 with R 8 as a substituent of the formula (III).
[0012] The dashed lines in the formulae in this document are in each case the bond between a substituent and the associated molecular radical.
[0013] In a particularly preferred embodiment, R 2 =R 3 =methyl, and R 1 is a hydrocarbon radical having 11 to 30 C atoms.
[0014] These compositions are suitable as reactive hotmelt adhesive compositions, also referred to as “PU-RHM” for short.
[0015] In the present document, the term “polymer” comprises firstly a group of macromolecules which are chemically uniform but differ with respect to degree of polymerization, molar mass and chain length, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation). Secondly, the term also comprises derivatives of such a group of macromolecules from polyreactions, i.e. compounds which were obtained by reactions such as, for example, additions or substitutions, of functional groups on specified macromolecules and which may be chemically uniform or chemically nonuniform. However, the term also comprises so-called prepolymers, i.e. reactive oligomeric preadducts whose functional groups are involved in the synthesis of macromolecules.
[0016] The term “polyurethane polymer” comprises all polymers which are prepared by the so-called diisocyanate polyaddition process. This also includes those polymers which are virtually or completely free of urethane groups. Examples of polyurethane polymers are polyether-polyurethanes, polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.
[0017] A temperature of 25° C. is designated as “room temperature”.
[0018] The polyurethane polymer of the formula (I) which is solid at room temperature and has aldimino groups can be prepared by the reaction of at least one aldimine of the formula (XI) containing an active hydrogen with at least one polyurethane polymer D having isocyanate groups. That reactive group of the aldimine of the formula (XI) which carries the active hydrogen undergoes an addition reaction with an isocyanate group of the polyurethane polymer D. In the present document, the term “active hydrogen” designates a deprotonatable hydrogen atom bonded to a nitrogen, oxygen or sulfur atom. The term “reactive group containing an active hydrogen” designates a functional group having an active hydrogen, in particular a primary or secondary amino group, a hydroxyl group, a mercapto group or a urea group.
[0000]
[0019] In the formula (XI), R 1 , R 2 , R 3 , R 4 and X have the same meaning as described for formula (I).
[0020] The aldimine of the formula (XI) can be prepared from at least one sterically hindered aliphatic aldehyde A and at least one aliphatic amine B corresponding to the formula H 2 N—R 4 —XH, which, in addition to one or more primary amino groups, also has a further reactive group containing a reactive hydrogen.
[0021] The reaction between the aldehyde A and the amine B takes place in a condensation reaction with elimination of water. Such condensation reactions are very well known and are described, for example, in Houben-Weyl, “Methoden der organischen Chemie [Methods of Organic Chemistry]”, vol. XI/2, page 73 et seq. Here, the aldehyde A is used stoichiometrically or in a stoichiometric excess relative to the primary amino groups of the amine B.
[0022] For the preparation of the aldimine of the formula (XI), at least one sterically hindered aliphatic aldehyde A of the formula (IV) is used
[0000]
[0023] In the formula (IV), R 1 , R 2 and R 3 have the same meaning as described for formula (I).
[0024] The aldehyde A is odorless. An “odorless” substance is understood as meaning a substance which has such little odor that it cannot be smelled by most human individuals, i.e. is not perceptible with the nose.
[0025] The aldehyde A is prepared, for example, from a carboxylic acid R 1 —COOH and a β-hydroxyaldehyde of the formula (V) in an esterification reaction. This esterification can be effected by known methods, described, for example, in Houben-Weyl, “Methoden der organischen Chemie [Methods of Organic Chemistry]”, vol. VIII, pages 516-528. The β-hydroxyaldehyde of the formula (V) is obtained, for example, in a crossed aldol addition from formaldehyde—or oligomeric forms of formaldehyde, such as paraformaldehyde or 1,3,5-trioxane—and an aldehyde of the formula (VI).
[0000]
[0026] In the formulae (V) and (VI), R 2 and R 3 have the same meaning as described for formula (I).
[0027] For example the following may be mentioned as suitable carboxylic acids R 1 —COOH for the esterification with the β-hydroxyaldehydes of the formula (V): saturated aliphatic carboxylic acids, such as enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid; monounsaturated aliphatic carboxylic acids, such as palmitoleic acid, oleic acid, erucic acid; polyunsaturated aliphatic carboxylic acids, such as linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid; cycloaliphatic carboxylic acids, such as cyclohexanecarboxylic acid; arylaliphatic carboxylic acids, such as phenylacetic acid; aromatic carboxylic acids, such as benzoic acid, naphthoic acid, toluic acid, anisic acid; isomers of these acids; fatty acid mixtures from the industrial saponification of natural oils and fats, such as, for example, rapeseed oil, sunflower oil, linseed oil, olive oil, coconut oil, oil palm kernel oil and oil palm oil; and monoalkyl and monoaryl esters of dicarboxylic acids, as obtained from the monoesterification of dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, maleic acid, fumaric acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 3,6,9-trioxaundecanedioic acid and similar derivatives of polyethylene glycol, with alcohols such as methanol, ethanol, propanol, butanol, higher homologues and isomers of these alcohols.
[0028] Caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, the isomers of these acids and industrial mixtures of fatty acids which contain these acids are preferred. Lauric acid is particularly preferred.
[0029] Suitable aldehydes of the formula (VI) for reaction with formaldehyde to give β-hydroxyaldehydes of the formula (V) are, for example, isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenylacetaldehyde. Isobutyraldehyde is preferred.
[0030] Suitable β-hydroxyaldehydes of the formula (V) are, for example, the products from the reaction of formaldehyde with the aldehydes of the formula (VI) which are mentioned above as being suitable. 3-Hydroxypivalaldehyde is preferred.
[0031] The amine B is an aliphatic amine which, in addition to one or more primary amino groups, also has a further reactive group which contains an active hydrogen. In the present document, the term “primary amino group” designates an NH 2 group which is bonded to an organic radical, while the term “secondary amino group” designates an NH group which is bonded to two organic radicals. The term “aliphatic amine” designates compounds which contain at least one amino group which is bonded to an aliphatic, cycloaliphatic or arylaliphatic radical. They thus differ from the aromatic amines in which the amino group is bonded directly to an aromatic radical, such as, for example, in aniline or 2-aminopyridine.
[0032] For example, the compounds mentioned below are suitable as amines B:
aliphatic hydroxyamines, such as 2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4-(2-aminoethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol; derivatives of glycols, such as diethylene glycol, dipropylene glycol, dibutylene glycol and higher oligomers and polymers of these glycols, which carry a primary amino group, for example 2-(2-aminoethoxy)ethanol, triethylene glycol monoamine, α-(2-hydroxymethylethyl)-ω-(2-aminomethylethoxy)poly(oxy(methyl-1,2-ethanediyl)); derivatives of polyalkoxylated trihydric or higher-hydric alcohols or of polyalkoxylated diamines which carry a hydroxyl group and an amino group; products from the monocyanoethylation and subsequent hydrogenation of glycols, for example 3-(2-hydroxyethoxy)propylamine, 3-(2-(2-hydroxyethoxy)ethoxy)propylamine, 3-(6-hydroxyhexyloxy)propylamine; aliphatic mercaptoamines, such as 2-aminoethanethiol (cysteamine), 3-aminopropanethiol, 4-amino-1-butanethiol, 6-amino-1-hexanethiol, 8-amino-1-octanethiol, 10-amino-1-decanethiol, 12-amino-1-dodecanethiol; aminothio sugars, such as 2-amino-2-deoxy-6-thioglucose; di- or polyfunctional aliphatic amines which, in addition to one or more primary amino groups, carry a secondary amino group, such as N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N-(2-ethylhexyl)-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethylpiperidine, 3-(4-aminobutyl)piperidine, N-aminoethylpiperazine, diethylenetriamine (DETA), bishexamethylenetriamine (BHMT); di- and triamines from the cyanoethylation or cyanobutylation of primary mono- and diamines, for example N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-hexyl-1,3-propanediamine, N-(2-ethylhexyl)-1,3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine, 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3-(2-ethylhexyl)amino-1-pentylamine, 3-dodecylamino-1-pentylamine, 3-cyclohexylamino-1-pentylamine, dipropylenetriamine (DPTA), N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, and fatty diamines, such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine, N-tallowalkyl-1,3-propanediamine or N—(C 16-22 -alkyl)-1,3-propanediamine, as are obtainable, for example, under the trade name Duomeen® from Akzo Nobel; the products from the Michael-like addition of aliphatic primary di- or polyamines with acrylonitrile, maleic or fumaric acid diesters, citraconic acid diesters, acrylic and methacrylic acid esters and itaconic acid diesters, reacted in the molar ratio 1:1; trisubstituted ureas which carry one or more primary amino groups, such as N-(2-aminoethyl)ethyleneurea, N-(2-aminoethyl)propyleneurea or N-(2-aminoethyl)-N′-methylurea.
[0037] Particularly suitable aliphatic hydroxy- and mercaptoamines are those in which the primary amino group are separated from the hydroxyl or the mercapto group by a chain of at least 5 atoms, or by a ring, such as, for example, in 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino-1-dodecanol, 4-(2-aminoethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2-(2-aminoethoxy)ethanol, triethylene glycol monoamine, α-(2-hydroxymethylethyl)-ω-(2-aminomethylethoxy)poly(oxy(methyl-1,2-ethanediyl)), 3-(2-hydroxyethoxy)propylamine, 3-(2-(2-hydrooxyethoxy)ethoxy)propylamine, 3-(6-hydroxyhexyloxy)propylamine, 6-amino-1-hexanethiol, 8-amino-1-octanethiol, 10-amino-1-decanethiol and 12-amino-1-docanethiol.
[0038] Preferred amines B are di- or polyfunctional aliphatic amines which, in addition to one or more primary amino groups, carry a secondary amino group, in particular N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethylpiperidine, 3-(4-aminobutyl)piperidine, DETA, DPTA, BHMT and fatty diamines, such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine and N-tallowalkyl-1,3-propanediamine. Aliphatic hydroxy- and mercaptoamines in which the primary amino group are separated from the hydroxyl or the mercapto group by a chain of at least 5 atoms, or by a ring, are also preferred, in particular 5-amino-1-pentanol, 6-amino-1-hexanol and higher homologues thereof, 4-(2-aminoethyl)-2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2-(2-aminoethoxy)ethanol, triethylene glycol monoamine and higher oligomers and polymers thereof, 3-(2-hydroxyethoxy)propylamine, 3-(2-(2-hydroxyethoxy)ethoxy)propylamine and 3-(6-hydroxyhexyloxy)propylamine.
[0039] The reaction between an aldehyde A and an amine B leads to hydroxyaldimines if a hydroxyamine is used as amine B; to mercaptoaldimines if a mercaptoamine is used as amine B; to aminoaldimines if a di- or polyfunctional amine which, in addition to one or more primary amino groups, carries a secondary amino group is used as amine B; or to ureaaldimines if a trisubstituted urea which carries one or more primary amino groups is used as amine B.
[0040] Hydroxyamines and amines having one or two primary amino groups and a secondary amino group are preferred as amine B.
[0041] In one embodiment, the aldimines of the formula (XI) have a substituent N—R 8 as substituent X. Such aldimines of the formula (XI) can be prepared by reacting at least one sterically hindered aliphatic aldehyde A of the formula (IV) with a difunctional aliphatic primary amine C of the formula H 2 N—R 4 —NH 2 in a first step to give an intermediate of the formula (VII) which, in addition to an aldimino group, also contains a primary amino group, and then reacting this intermediate in a second step in an addition reaction with a Michael acceptor of the formula (VIII) in a ratio of the number of double bonds:number of NH 2 groups=1:1. An aminoaldimine which, in addition to an aldimino group, also contains a secondary amino group forms.
[0000]
[0042] In the formula (VII), R 1 , R 2 , R 3 and R 4 have the same meaning as described for formula (I).
[0000]
[0043] Thus, aldimines of the formula (XI) in which X is the radical N—R 8 and R 8 is a monvalent hydrocarbon radical of the formula (IX) or (IX′) form. Here, in the formulae (VIII), (IX) and (IX′), R 9 is a radical which is selected from the group consisting of —COOR 13 , —CN, —NO 2 , —PO(OR 13 ) 2 , —SO 2 R 13 and —SO 2 OR 13 and R 10 is a hydrogen atom or a radical from the group consisting of —R 13 , —COOR 13 and —CH 2 COOR 13 and R 11 and R 12 , independently of one another, are a hydrogen atom or a radical from the group consisting of —R 13 , —COOR 13 and —CN, R 13 being in each case a monovalent hydrocarbon radical having 1 to 20 C atoms.
[0044] The amine C is an aliphatic amine having two primary amino groups.
[0045] Examples of suitable amines C are aliphatic diamines, such as ethylenediamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3- and 1,4-butanediamine, 1,3- and 1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexamethylenediamine (HMDA), 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof (TMD), 1,7-heptanediamine, 1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 4-aminomethyl-1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,9-nonanediamine, 5-methyl-1,9-nonanediamine, 1,10-decanediamine, iso-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, methylbis(3-aminopropyl)amine, 1,5-diamino-2-methylpentane (MPMD), 1,3-diaminopentane (DAMP), 2,5-dimethyl-1,6-hexamethylenediamine; cycloaliphatic diamines, such as 1,2-, 1,3- and 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane (H 12 MDA), bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, bis(4-amino-3-ethyl-5-methylcyclohexyl)methane (M-MECA), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (=isophoronediamine or IPDA), 2- and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3- and 1,4-bis(aminomethyl)cyclohexane, 1-cyclohexylamino-3-aminopropane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA, produced by Mitsui Chemicals), 3(4),8(9)-bis(aminomethyl)tricyclo-[5.2.1.0 2,6 ]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane; arylaliphatic diamines, such as 1,3-xylylenediamine (MXDA), 1,4-xylylenediamine (PXDA), aliphatic diamines containing ether groups, such as bis(2-aminoethyl)ether, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine and higher oligomers thereof; polyoxyalkylenediamines, obtainable, for example, under the name Jeffamine® (produced by Huntsman Chemicals). Preferred diamines are those in which the primary amino groups are separated by a chain of at least 5 atoms, or by a ring, in particular 1,5-diamino-2-methylpentane, 1,6-hexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,10-decanediamine, 1,12-dodecanediamine, 1,3- and 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane, 1,3- and 1,4-xylylenediamine, and polyoxyalkylenediamines, obtainable, for example, under the name Jeffamine® (produced by Huntsman Chemicals).
[0046] Examples of suitable Michael acceptors of the formula (VIII) are maleic or fumaric acid diesters, such as dimethyl maleate, diethyl maleate, dibutyl maleate, diethyl fumarate; citraconic acid diesters, such as dimethyl citraconate; acrylic or methacrylic acid esters, such as methyl(meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, tetrahydrofuryl (meth)acrylate, isobornyl(meth)acrylate; itaconic acid diesters, such as dimethyl itaconate; cinnamic acid esters, such as methyl cinnamate; vinylphosphonic acid diesters, such as dimethyl vinylphosphonate; vinylsulfonic acid esters, in particular aryl vinylsulfonates; vinyl sulfones; vinyl nitriles, such as acrylonitrile, 2-pentenenitrile or fumaronitrile; 1-nitroethylenes, such as β-nitrostyrene; and Knoevenagel condensates, such as, for example those obtained from malonic acid diesters and aldehydes, such as formaldehyde, acetaldehyde or benzaldehyde. Maleic acid diesters, acrylic acid esters, phosphonic acid diesters and vinylnitriles are preferred.
[0047] The reaction of the aldehyde A with the amine C to give the intermediate of formula (VII) is effected in a condensation reaction with elimination of water, as described further above for the reaction of the aldehyde A with the amine B. The stoichiometry between the aldehyde A and the amine C is chosen so that 1 mol of aldehyde A is used for 1 mol of amine C. A solvent-free preparation process is preferred, the water formed in the condensation being removed from the reaction mixture by application of a vacuum.
[0048] The reaction of the intermediate of the formula (VII) with the Michael acceptor of the formula (VIII) is effected, for example, by mixing the intermediate with a stoichiometric or slightly superstoichiometric amount of the Michael acceptor of the formula (VIII) and heating the mixture at temperatures of from 20 to 110° C. until complete conversion of the intermediate into the aldimine of the formula (XI). The reaction is preferably effected without use of solvents.
[0049] The aldimines of the formula (XI) can, if appropriate, be in equilibrium with cyclic forms, as shown by way of example in formula (X). These cyclic forms are cyclic animals, for example imidazolidines or tetrahydropyrimidines, in the case of aminoaldimines; cyclic aminoacetals, for example oxazolidines or tetrahydrooxazines, in the case of hydroxyaldimines; cyclic thioaminals, for example thiazolidines or tetrahydrothiazines, in the case of mercaptoaldimines.
[0000]
[0050] In the formula (X), R 1 , R 2 , R 3 , R 4 and X have the same meaning as described for formula (I).
[0051] Surprisingly, most aldimines of the formula (XI) do not tend to undergo cyclization. Particularly for aminoaldimines it is possible to show by means of IR and NMR spectroscopic methods that these compounds are present predominantly in the open-chain form, i.e. the aldimine form, whereas the cyclic form, i.e. the animal form, does not occur or occurs only in traces. This is in contrast to the behavior of the aminoaldimines according to the prior art, as described, for example, in U.S. Pat. No. 4,404,379 and U.S. Pat. No. 6,136,942: those are in fact present mainly in the cycloaminal form. Hydroxy- and mercaptoamines in which the primary amino group are separated from the hydroxyl or the mercapto group by a chain of at least 5 atoms, or by a ring, also show scarcely any cyclization. The substantial absence of cyclic structures in the aldimines of the formula (XI) is to be regarded as advantageous, in particular with respect to the use thereof in isocyanate-containing compositions, since the aldimines are thereby substantially free of the basic nitrogen atoms which occur in animals, oxazolidines and thioaminals and which could reduce the shelf-life of the isocyanate-containing composition.
[0052] The aldimines of the formula (XI) are odorless. They have a long shelf-life under suitable conditions, in particular in the absence of moisture. On admission of moisture, the aldimine groups of the aldimines can hydrolyze via intermediates formally to amino groups, the corresponding aldehyde A used for the preparation of the aldimine being liberated. Since this hydrolysis reaction is reversible and the chemical equilibrium is substantially on the aldimine side, it is to be assumed that only some of the aldimine groups undergo partial or complete hydrolysis in the absence of groups reactive toward amines.
[0053] A polyurethane polymer D of the formula (XII) which is solid at room temperature and has isocyanate groups is suitable as polyurethane polymer D for the preparation of a polyurethane polymer of the formula (I) which is solid at room temperature and has aldimine groups.
[0000]
[0054] In the formula (XII), p, q and R 5 have the same meaning as described for formula (I).
[0055] Polyetherdiols, polyesterdiols and polycarbonatediols, and mixtures of these diols, are particularly suitable as diols for the preparation of a polyurethane polymer D.
[0056] Particularly suitable polyetherdiols, also referred to as polyoxyalkylenediols, are those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of an initiator having two active hydrogen atoms per molecule, such as, for example, water, ammonia or compounds having two OH or NH groups, such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, aniline and mixtures of the abovementioned compounds. Both polyoxyalkylenediols which have a low degree of unsaturation (measured according to ASTM D-2849-69 and stated in milliequivalents of unsaturation per gram of diol (mEq/g)), prepared, for example, with the aid of so-called double metal cyanide complex catalysts (DMC catalysts), and polyoxyalkylenediols having a higher degree of unsaturation, prepared, for example, with the aid of anionic catalysts, such as NaOH, KOH or alkali metal alcoholates, can be used.
[0057] Particularly suitable are polyetherdiols or polyoxyalkylenediols, in particular polyoxyethylenediols.
[0058] Polyoxyalkylenediols having a degree of unsaturation of less than 0.02 mEq/g and having a molecular weight in the range from 1000 to 30 000 g/mol, and polyoxypropylenediols having a molecular weight of from 400 to 8000 g/mol are especially suitable.
[0059] So-called “EO-endcapped” (ethylene oxide-endcapped) polyoxypropylenediols are also particularly suitable. The latter are special polyoxypropylenepolyoxy-ethylenediols which are obtained, for example, if pure polyoxypropylenediols are alkoxylated with ethylene oxide after the end of the polypropoxylation and thereby have primary hydroxyl groups. In the present document, “molecular weight” is always understood as meaning the weight average molecular weight M n .
[0060] The most suitable polyetherdiols are those having a degree of unsaturation of less than 0.02 mEq/g and having a molecular weight in the range from 7000 to 30 000, in particular from 10 000 to 25 000 g/mol. For example, such polyethers are sold under the trade name Acclaim®® by Bayer.
[0061] Particularly suitable polyesterdiols are those which are prepared from dihydric alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, or mixtures of the abovementioned alcohols, with organic dicarboxylic acids or the anhydrides or esters thereof, such as, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the abovementioned acids, and polyesterdiols obtained from lactones, such as, for example, from ε-caprolactone.
[0062] Particularly suitable polyesterdiols are polyesterdiols obtained from adipic acid, azelaic acid, sebacic acid or dodecanedicarboxylic acid as dicarboxylic acid and from hexanediol or neopentyl glycol as a dihydric alcohol. The polyesterdiols preferably have a molecular weight of from 1000 to 15 000 g/mol, in particular from 1500 to 8000 g/mol, preferably from 1700 to 5500 g/mol.
[0063] Semicrystalline, crystalline and amorphous polyesterdiols which are liquid at room temperature and are in the form of adipic acid/hexanediol polyesters, azelaic acid/hexanediol polyesters and dodecanedicarboxylic acid/hexanediol polyesters are particularly suitable. Suitable polyesterdiols which are liquid at room temperature are solid not far below room temperature, for example at temperatures of from 0° C. to 25° C.
[0064] Suitable polycarbonatediols are those which are obtainable by reacting, for example, the above-mentioned dihydric alcohols—used for the synthesis of the polyesterdiols—with dialkyl carbonates, diaryl carbonates or phosgene.
[0065] Preferred diols are polyesterdiols and polycarbonatediols.
[0066] Particularly preferred diols are polyesterdiols, in particular a mixture of an amorphous and a crystalline or semicrystalline polyesterdiol, or a mixture of a polyesterdiol which is liquid at room temperature and a crystalline or semicrystalline polyesterdiol, or a mixture of a semicrystalline and a crystalline polyesterdiol. If a polyesterdiol which is liquid at room temperature is used, this is solid not far below room temperature, in particular at a temperature of from 0° C. to 25° C.
[0067] Commercially available aliphatic, cycloaliphatic or aromatic diisocyanates can be used as diisocyanates for the preparation of a polyurethane polymer D containing isocyanate groups, for example the following:
[0068] 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene 1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, lysine diisocyanate and lysine ester diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (=isophorone diisocyanate or IPDI), perhydro-2,4,- and 4,4′-diphenylmethane diisocyanate (HMDI or H 12 MDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3- and 1,4-xylylene diisocyanate (m- and p-TMXDI), bis(1-isocyanato-1-methylethyl)naphthalene, 2,4- and 2,6-toluoylene diisocyanate and any desired mixtures of these isomers (TDI), 4,4′-, 2,4′- and 2,2′-diphenylmethane diisocyanate and any desired mixtures of these isomers (MDI), 1,3- and 1,4-phenylene diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-diisocyanatobiphenyl (TOBI), oligomers and polymers of the abovementioned isocyanates, and any desired mixtures of the abovementioned isocyanates. MDI, TDI, HDI, H 12 MDI and IPDI are preferred.
[0069] The preparation of the polyurethane polymer D is effected in a known manner directly from the diisocyanates and the diols, or by stepwise addition processes, which are also known as chain extension reactions.
[0070] What is important is that the polyurethane polymer D has isocyanate groups and is solid at room temperature. In a preferred embodiment, the polyurethane polymer D is prepared via a reaction of at least one diisocyanate and at least one diol, the isocyanate groups being present in stoichiometric excess relative to the hydroxyl groups. Advantageously, the ratio between isocyanate and hydroxyl groups, referred to as “NCO/OH ratio” for short, is from 1.3 to 2.5, in particular from 1.5 to 2.2.
[0071] The polyurethane polymer D has a molecular weight of, preferably, more than 1000 g/mol, in particular one of from 1200 to 50 000 g/mol, preferably one of from 2000 to 30 000 g/mol. Furthermore, the polyurethane polymer D has (p+q) isocyanate groups, (p+q) being 2.
[0072] It is clear to the person skilled in the art that the diols used for the preparation of the polyurethane polymer D are generally of industrial quality and are therefore mixtures of oligomers of different chain length, monomer composition and OH functionality. Thus, owing to the preparation process, industrial diols, in particular polyetherdiols, contain not only a predominant proportion of diols but also monools, so that their average OH functionality is not exactly 2, but, for example, somewhat less than 2. On the other hand, industrial diols may also contain small proportions of triols in addition to diols and monools, for example owing to the concomitant use of trifunctional initiators, monomers or crosslinking agents, so that their average OH functionality may also be somewhat higher than 2.
[0073] The reaction between the aldimine of the formula (XI) and the polyurethane polymer D to give the polyurethane polymer of the formula (I) which has aldimino groups is effected under known conditions, as are typically used for reactions between the reactive groups involved in the respective reaction, for example at a temperature of from 20° C. to 100° C. It is preferably effected at a temperature at which the polyurethane polymer D is present in liquid form. The reaction is effected with the use of a solvent or preferably in the absence of a solvent. If appropriate, auxiliaries, such as, for example, catalysts, initiators or stabilizers, can be concomitantly used. The reaction is preferably carried out without a catalyst for aminoaldimines, whereas use of a catalyst as used for the urethanization reaction between isocyanates and alcohols, for example an organotin compound, a bismuth complex, a tertiary amine compound or a combination of such catalysts, may be expedient for hydroxy-, mercapto- and ureaaldimines.
[0074] If the addition reaction between the aldimine of the formula (XI) and the polyurethane polymer D to give the polyurethane polymer of the formula (I) is carried out stoichiometrically, i.e. with one mole equivalent of active hydrogen of the aldimine (XI) per mole equivalent of isocyanate groups of the polyurethane polymer D—with the result that the reactive groups thereof are completely reacted—a dialdimine is obtained as the adduct of the formula (I).
[0075] Preferably, however, the addition reaction between the aldimine of the formula (XI) and the polyurethane polymer D is carried out substoichiometrically, i.e. with less than one mole equivalent of active hydrogen of the aldimine (XI) per mole equivalent of isocyanate groups of the polyurethane polymer D. Thus, the isocyanate groups are only partially reacted, which leads to at least one polyurethane polymer of the formula (I) which has aldimino groups and which likewise has isocyanate groups, i.e. with q=1.
[0076] Preferred polyurethane polymers of the formula (I) which have aldimino groups are those of the formulae (I a), (I b) and (I c)
[0000]
[0000] in which R 1 , R 2 , R 3 , R 4 and R 5 have the above-mentioned meanings, and R 8 is a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, sulfone or sulfonic acid ester group.
[0077] The polyurethane polymers of the formula (I) which have aldimino groups are odorless, like the aldimines of the formula (XI). They have a long shelf-life under suitable conditions, in particular in the absence of moisture.
[0078] On admission of moisture, the aldimino groups can hydrolyze via intermediates formally to give amino groups, the corresponding aldehyde A used for the preparation of the aldimine of the formula (XI) being liberated. In the absence of isocyanate groups, i.e. in the case of polyurethane polymers of the formula (I) where q=0, it is to be assumed that only a part of the aldimino groups undergo partial or complete hydrolysis, since the hydrolysis reaction is reversible and the chemical equilibrium is substantially on the aldimine side. In the case of polyurethane polymers of the formula (I) where q=1, on the other hand, the liberated amino groups react with the isocyanate groups, which leads to crosslinking of the polyurethane polymer. The reaction of the isocyanate groups with the hydrolyzing aldimino groups need not necessarily be effected via amino groups. Of course, reactions with intermediates of the hydrolysis reaction are also possible. For example, it is conceivable for a hydrolyzing aldimino group in the form of a hemiaminal to react directly with an isocyanate group.
[0079] Throughout the document, the terms “crosslinking” or “crosslinking reaction” designate the process of the formation of high molecular weight polyurethane plastics, initiated by the chemical reaction of isocyanate groups, even when predominantly chains form thereby.
[0080] The compositions described may optionally contain a polyurethane polymer P having isocyanate groups.
[0081] This is preferably a polyurethane polymer D as has already been described for the preparation of a polyurethane polymer of the formula (I) which has aldimino groups, i.e. a polyurethane polymer which is solid at room temperature and has isocyanate groups.
[0082] The aldimino groups present in the composition are typically present in a slightly superstoichiometric, stoichiometric or substoichiometeric ratio relative to the isocyanate groups present in the composition.
[0083] Advantageously, the ratio between aldimino groups and isocyanate groups is from 0.3 to 1.1, in particular from 0.5 to 1.05. If the polyurethane polymer of the formula (I) which has aldimino groups has no isocyanate groups, i.e. q in formula (I) is zero, or if the polyurethane polymer of the formula (I) which has aldimino groups has two or more aldimino groups, i.e. is, for example, a compound of the formula (I c), the composition inevitably contains a polyurethane polymer P having isocyanate groups. In this way, a suitable ratio of aldimino groups to isocyanate groups, as described above, is achieved.
[0084] If the polyurethane polymer of the formula (I) which has aldimino groups has only one aldimino group and one isocyanate group, i.e. is, for example, a compound of the formula (I a) or (I b), the presence of a polyurethane polymer P is optional since in this case a composition without polyurethane polymer P also has a suitable ratio of aldimino groups to isocyanate groups.
[0085] The composition described has a surprisingly low content of monomeric diisocyanates. This is particularly advantageous for the use as hotmelt adhesive since monomeric diisocyanates are expelled in gaseous form during the application and, as irritant, sensitizing or toxic substances, may be a health hazard for the processor. The content of monomeric diisocyanates is very low particularly when the composition contains, as a polyurethane polymer, mainly a polyurethane polymer of the formula (I) which was prepared by the substoichiometric reaction of a polyurethane polymer D with an aldimine of the formula (XI), in particular with less than a half mole equivalent of active hydrogen of the aldimine (XI) per mole equivalent of isocyanate groups of the polyurethane polymer D.
[0086] In a preferred preparation process for the composition described, all components of the composition which contain monomeric diisocyanates are present in the reaction mixture in the reaction of the aldimines of the formula (XI) with the polyurethane polymer D having isocyanate groups. Compositions prepared in this manner have the lowest content of monomeric diisocyanates.
[0087] Preferably, the composition described has a content of monomeric diisocyanates of ≦0.3% by weight, particularly preferably of ≦0.2% by weight and in particular of ≦0.1% by weight.
[0088] The composition described optionally contains further constituents as are usually used according to the prior art, in particular:
unreactive thermoplastic polymers, such as, for example, homo- or copolymers of unsaturated monomers, in particular from the group consisting of ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or higher esters thereof, and (meth)acrylate, ethylene/vinyl acetate copolymers (EVA), atactic poly-α-olefins (APAO), polypropylene (PP) and polyethylene (PE) being particularly suitable; catalysts for the reaction of the aldimino groups and/or of the isocyanate groups, in particular acids or compounds hydrolyzable to acids, for example organic carboxylic acids, such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic anhydrides, such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic carboxylic acids, organic sulfonic acids, such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, or further organic or inorganic acids; metal compounds, for example tin compounds, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dioctyltin dilaurate, dibutyltin dichloride and dibutyltin oxide, tin(II) carboxylates, stannoxanes, such as lauryl stannoxane, bismuth compounds, such as bismuth(III) octanoate, bismuth(III) neodecanoate or bismuth(III) oxinates; tertiary amines, for example 2, 2′-dimorpholinodiethyl ether and other morpholine ether derivatives, 1,4-diazabicyclo[2.2.2]octane and 1,8-diazabicyclo[5.4.0]undec-7-ene; combinations of said catalysts, in particular mixtures of acids and metal compounds, or of metal compounds and tertiary amines; reactive diluents or crosslinking agents, for example oligomers or polymers of diisocyanates, such as MDI, PMDI, TDI, HDI, 1,12-dodecamethylene diisocyanate, cyclohexane 1,3- or 1,4-diisocyanate, IPDI, perhydro-2,4′- and 4,4′-diphenylmethane diisocyanate (H 12 MDI), 1,3- and 1,4-tetramethylxylylene diisocyanate, in particular isocyanurates, carbodiimides, uretonimines, biurets, allophanates and iminooxadiazinediones of said diisocyanates, adducts of diisocyanates with shortchain polyols, adipic acid dihydrazide and other dihydrazides, and blocked curing agents in the form of polyaldimines, polyketimines, oxazolidines or polyoxazolidines; fillers, plasticizers, adhesion promoters, in particular compounds containing silane groups, UV absorbents, UV or heat stabilizers, antioxidants, flameproofing agents, optical brighteners, pigments, dyes and drying agents, and further substances usually used in isocyanate-containing compositions.
[0093] In a preferred embodiment, the composition described is free of carbon black.
[0094] In a further preferred embodiment, the composition described is completely free of fillers. Such a composition is particularly suitable for the adhesive bonding of substrates in which at least one of the substrates to be adhesively bonded is transparent or translucent.
[0095] The sum of the polyurethane polymer of the formula (I) which is solid at room temperature and has aldimino groups and of the polyurethane polymer P having isocyanate groups is suitably from 40 to 100% by weight, in particular from 75 to 100% by weight, preferably from 80 to 100% by weight, based on the total composition.
[0096] The composition described is prepared and stored in the absence of moisture. In a suitable, climatically tight packaging or arrangement, such as, for example, in a drum, bag or cartridge, it has an outstanding shelf-life. In the present document, the terms “having a long shelf-life” and “shelf-life” in association with a composition designates that the viscosity of the composition at the application temperature on suitable storage in the time span considered does not increase or at most increases to such an extent that the composition remains usable in the intended manner.
[0097] For the mode of action of a reactive hotmelt adhesive, it is important that the adhesive is capable of being melted, i.e. that it has a sufficiently low viscosity at the application temperature in order to be capable of being applied, and that, on cooling, it builds up a sufficient adhesive strength as rapidly as possible even before the crosslinking reaction with atmospheric humidity is complete (initial strength). It has been found that the compositions described have a viscosity which can be readily handled at the application temperatures in the range from 85° C. to 200° C., typically from 120° C. to 160° C., which are customary for hotmelt adhesives, and that, on cooling, they build up a good adhesive strength sufficiently rapidly.
[0098] On application, the composition described comes into contact with moisture, in particular in the form of atmospheric humidity. Simultaneously with the physical hardening due to solidification during cooling, the chemical crosslinking with moisture also begins, mainly by virtue of the fact that the aldimino groups present are hydrolyzed by moisture and react in the manner described above rapidly with isocyanate groups present.
[0099] Excess isocyanate groups likewise crosslink with moisture in a known manner.
[0100] The moisture required for the chemical crosslinking may either originate from the air (atmospheric humidity) or the composition can be brought into contact with a water-containing component, for example by coating or by spraying, or a water-containing component, for example in the form of a water-containing paste, which is mixed in, for example via a static mixer, can be added to the composition during the application.
[0101] The compositions described show a greatly reduced tendency to the formation of bubbles during the crosslinking with moisture, since—depending on stoichiometry, little or no carbon dioxide is formed during the crosslinking by the presence of aldimino groups.
[0102] In a preferred embodiment, the composition described is used as a reactive polyurethane hotmelt adhesive, referred to as PU-RHM for short.
[0103] In the application as PU-RHM, the composition is used for the adhesive bonding of a substrate S1 and a substrate S2.
[0104] Such adhesive bonding comprises the steps
[0000] i) heating of a composition as described above to a temperature of from 85° C. to 200° C., in particular from 120° C. to 160° C.;
ii) application of the heated composition to a substrate S1;
iii) bringing of the applied composition into contact with a second substrate S2 within the open time;
the second substrate S2 consisting of a material which is the same as or different from that of the substrate S1.
[0105] The step iii) is typically followed by a step iv) of the chemical crosslinking of the composition with moisture. It is clear to the person skilled in the art that the crosslinking reaction can begin as early as during the adhesive bonding, depending on factors such as the composition used, the substrates, the temperature, the ambient humidity and the adhesion geometry. However, the main part of the crosslinking generally takes place after the adhesive bonding.
[0106] The substrates S1 and/or S2 can, if required, be pretreated before the application of the composition. Such pretreatments comprise in particular physical and/or chemical cleaning and activation methods, for example grinding, sandblasting, brushing, corona treatment, plasma treatment, flame treatment, etching or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, an adhesion promoter solution or a primer.
[0107] The substrates S1 and S2 may comprise a multiplicity of materials. Plastics, organic materials, such as leather, fabrics, paper, wood, resin-bound wood-base materials, resin-textile composite materials, glass, porcelain, ceramic and metals and metal alloys, in particular coated or powder-coated metals and metal alloys, are particularly suitable.
[0108] Suitable plastics are in particular polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding composites), polycarbonate (PC), polyamide (PA), polyester, polyoxymethylene (POM), polyolefins (PO), in particular polyethylene (PE), polypropylene (PP), ethylene/propylene copolymers (EPM) and ethylene/propylene-diene terpolymers (EPDM), preferably PP or PE surface-treated by plasma, corona or flames.
[0109] Transparent materials, in particular transparent plastic films, are considered to be preferred materials for the substrates S1 and S2. Another preferred transparent material is glass, in particular in the form of a sheet.
[0110] The thickness of the adhesive layer (adhesive bond thickness) is typically 10 microns or more. In particular, the adhesive bond thickness is from 10 microns to 20 millimeters, especially from 80 microns to 500 microns. In the case of thick layers, however the crosslinking is usually very slow, owing to the slow water diffusion.
[0111] The composition described is used in particular in an industrial manufacturing process.
[0112] The composition described is particularly suitable as a PU-RHM for adhesive bonds in which the adhesive bonding point is visible. Thus, it is firstly suitable in particular for the adhesive bonding of glass, in particular in vehicle and window construction.
[0113] Secondly, it is suitable in particular for the adhesive bonding of transparent packagings.
[0114] Articles result from the adhesive bonding process. Such articles are firstly in particular articles from the transport, furniture or textile sector. The preferred transport sector is the automotive sector.
[0115] Examples of articles of this type are water or land vehicles, such as automobiles, buses, trucks, trains or ships; automotive interior finishing parts, such as roofs, sun visors, instrument panels, door side parts, rear shelves and the like; wood fiber materials from the shower and bath sector; decorative furniture sheets, membrane sheets with textiles, such as cotton, polyester sheets in the apparel sector or textiles with foams for automotive finishing.
[0116] On the other hand, such articles are in particular articles from the packaging sector. In particular, such an article is a transparent packaging.
[0117] The compositions described, comprising
[0000] a) at least one polyurethane polymer of the formula (I) which is solid at room temperature and has aldimino groups and
b) optionally at least one polyurethane polymer P having isocyanate groups,
have a number of advantages over the prior art when used as reactive hotmelt adhesive compositions.
[0118] Thus, they have a greatly reduced content of monomeric diisocyanates and thus lead to greatly reduced contamination of the processor with health-hazardous diisocyanate vapors during their use. With the compositions described, commercially available hotmelt adhesive compositions based on readily obtainable diisocyanates, such as 4,4′-MDI or IPDI, and having an extremely low content of monomeric diisocyanates are obtainable. The low content of monomeric diisocyanates is achieved by the reaction of polyurethane polymers D with aldimines of the formula (XI), the active hydrogen present in the aldimines evidently preferentially reacting with the monomeric diisocyanates present in the polyurethane polymer D.
[0119] Furthermore, the compositions described have a high crosslinking rate when used as hotmelt adhesive, even if they contain only slowly reacting aliphatic isocyanate groups, such as, for example, those of IPDI or H 12 MDI. PU-RHM according to the prior art, based on purely aliphatic diisocyanates, generally have such a low crosslinking rate that they cannot be used for most applications.
[0120] Furthermore, the compositions described show a greatly reduced tendency to the formation of bubbles, because no carbon dioxide is formed in the crosslinking reaction of isocyanate groups with hydrolyzing aldimino groups, in contrast to the crosslinking of isocyanate groups with moisture.
[0121] In addition to these advantages, when used as hotmelt adhesive, the compositions described have properties that are similarly good compared with those of the systems according to the prior art, namely fast adhesive strength, good heat distortion resistance and a high final strength in combination with good extensibility, it being possible to adapt the final mechanical properties in a very broad range to the needs of an adhesion application.
[0122] In a further aspect, the invention relates to a method for reducing the content of monomeric diisocyanates in polyurethane polymers having isocyanate groups or in compositions which contain polyurethane polymers having isocyanate groups, by reacting the polyurethane polymers having isocyanate groups with at least one aldimine of the formula (XI).
EXAMPLES
a) Description of the Test Methods
[0123] The total content of aldimino groups and free amino groups in the compounds prepared (“amine content”) was determined titrimetrically (with 0.1N HClO 4 in glacial acetic acid, against crystal violet) and is always stated in mmol NH 2 /g (even if not only primary amino groups are referred to).
[0124] The content of monomeric diisocyanates was determined by means of HPLC (detection via photodiode array) and is stated in % by weight, based on the total composition.
[0125] The viscosity was measured at the respective stated temperature using a Brookfield viscometer with spindle number 27 and 10 revolutions per minute.
[0126] The open time was determined as follows: the composition was applied to a silicone-coated paper at a temperature of 150° C. and a thickness of 500 μm. This test specimen was then placed on a substrate at room temperature. As soon as a paper strip pressed lightly onto the adhesive could be detached from the adhesive, the open time had elapsed. Thereafter, the adhesive cured in each case and became solid.
[0127] The tensile strength and the elongation at break were determined on the basis of DIN 53504 on test specimens having a layer thickness of 500 μm and the dimensions 120 mm×20 mm. The films for the production of the test specimen were applied at an adhesive temperature of 140° C. and then stored for 2 weeks at 23° C. and 50% relative humidity.
b) Preparation of Aldimines of the Formula (XI)
Aldimine 1
[0128] 30.13 g (0.106 mol) of 2,2-dimethyl-3-lauroyloxy-propanal were initially introduced under a nitrogen atmosphere in a round-bottomed flask. 15.00 g (0.096 mol) of N-cyclohexyl-1,3-propanediamine were added from a dropping funnel in the course of 5 minutes with vigorous stirring, the temperature of the reaction mixture increasing to 36° C. The volatile constituents were then removed in vacuo (10 mbar, 80° C.). 43.2 g of a colorless, clear and odorless liquid which had a low viscosity at room temperature and an amine content of 4.39 mmol NH 2 /g were obtained.
Aldimine 2
[0129] 28.06 g (0.099 mol) of 2,2-dimethyl-3-lauroyloxy-propanal were initially introduced under a nitrogen atmosphere in a round-bottomed flask. 10.00 g (0.095 mol) of 2-(2-aminoethoxy)ethanol (Diglycolamine® Agent; Huntsman) were added from a dropping funnel in the course of 3 minutes with vigorous stirring, the temperature of the reaction mixture increasing to 40° C. The volatile constituents were then removed in vacuo (10 mbar, 80° C.). 36.3 g of a colorless, clear and odorless liquid which had a low viscosity at room temperature and an amine content of 2.58 mmol NH 2 /g were obtained.
Aldimine 3
[0130] 69.31 g (0.244 mol) of 2,2-dimethyl-3-lauroyloxy-propanal were initially introduced under a nitrogen atmosphere in a round-bottomed flask. 14.72 g (0.112 mol) of dipropylenetriamine were added from a dropping funnel in the course of 5 minutes with vigorous stirring, the temperature of the reaction mixture increasing to 36° C. The volatile constituents were then removed in vacuo (10 mbar, 80° C.). 79.7 g of a colorless, clear and odorless liquid which had a low viscosity at room temperature and an amine content of 4.17 mmol NH 2 /g were obtained.
c) Preparation of Polyurethane Polymers D
[0131] Polyurethane polymer D1
[0132] 800 g of Dynacoll® 7250 (liquid polyesterdiol, OH number 21 mg KOH/g; Degussa), 200 g of Dynacoll® 7360 (crystalline polyesterdiol, OH number 30 mg KOH/g, melting point 55° C.; Degussa) and 102 g of 4,4′-diphenylmethane diisocyanate (4,4′-MDI; Desmodur® 44 MC L, Bayer) were reacted by a known process at 100° C. to give an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined content of 1.5% by weight of free isocyanate groups and was solid at room temperature.
[0000] Polyurethane polymer D2
[0133] The same diol mixture as in polyurethane polymer D1 was reacted with 102 g of 2,4′-diphenylmethane diisocyanate (2,4′-MDI; Lupranat® MCI, BASF) by a known process at 100° C. to give an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined content of 1.5% by weight of free isocyanate groups and was solid at room temperature.
Polyurethane Polymer D3
[0134] The same diol mixture as in polyurethane polymer D1 was reacted with 107 g of 4,4′-methylenedicyclohexyl diisocyanate (H 12 MDI; Desmodur® W, Bayer) by a known process at 100° C. to give an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined content of 1.5% by weight of free isocyanate groups and was solid at room temperature.
Polyurethane Polymer D4
[0135] The same diol mixture as in polyurethane polymer D1 was reacted with 90.4 g of isophorone diisocyanate (IPDI: Vestanat® IPDI, Degussa) by a known process at 100° C. to give an NCO-terminated polyurethane polymer. The reaction product had a titrimetrically determined content of 1.5% by weight of free isocyanate groups and was solid at room temperature.
d) Preparation of Hotmelt Adhesive Compositions
Example 1
[0136] 95.0 parts by weight of polyurethane polymer D1 and 7.7 parts by weight of aldimine 1 were homogeneously mixed at a temperature of 130° C. and left for 1 hour at 130° C. The resulting polyurethane polymer having aldimino and isocyanate groups was stored at room temperature in the absence of moisture.
Example 2
[0137] 95.0 parts by weight of polyurethane polymer D1 and 6.5 parts by weight of aldimine 2 were homogeneously mixed at a temperature of 130° C. and left for 1 hour at 130° C. The resulting polyurethane polymer having aldimino and isocyanate groups was stored at room temperature in the absence of moisture.
Example 3
[0138] 95.0 parts by weight of polyurethane polymer D1 and 8.1 parts by weight of aldimine 3 were homogeneously mixed at a temperature of 130° C. and left for 1 hour at 130° C. The resulting polyurethane polymer having aldimino and isocyanate groups was stored at room temperature in the absence of moisture.
Example 4
Comparison
[0139] 100 parts by weight of polyurethane polymer D1.
[0000]
TABLE 1
Properties of Examples 1 to 4
Example
4
1
2
3
(comparison)
Monomeric 4,4′-diphenyl-
0.24
0.05
0.38
2.42
methane diisocyanate [%]
Viscosity at 90° C. [Pa · s]
43.1
117.3
120.0
23.6
Viscosity at 110° C. [Pa · s]
21.2
24.7
21.1
11.9
Viscosity at 130° C. [Pa · s]
12.4
16.3
14.7
7.0
Open time [min]
3.5
2.5
3.5
2
Tensile strength [MPa]
8.5
6.5
8.8
7.1
Elongation at break [%]
1200
1100
800
1100
Example 5
[0140] Example 5 was carried out like Example 1, the polyurethane polymer D2 being used instead of the polyurethane polymer D1.
Example 6
[0141] Example 6 was carried out like Example 2, the polyurethane polymer D2 being used instead of the polyurethane polymer D1.
Example 7
[0142] Example 7 was carried out like Example 3, the polyurethane polymer D2 being used instead of the polyurethane polymer D1.
Example 8
Comparison
[0143] 100 parts by weight of polyurethane polymer D2.
[0000]
TABLE 2
Properties of Examples 5 to 8
Example
8
5
6
7
(comparison)
Monomeric 2,4′-
0.06
<0.01
0.04
0.94
diphenylmethane diiso-
cyanate [%]
Viscosity at 90° C.
19.0
21.4
19.6
11.5
[Pa · s]
Viscosity at 110° C.
9.3
11.3
9.0
5.9
[Pa · s]
Viscosity at 130° C.
5.6
7.0
5.7
3.5
[Pa · s]
Open time [min]
2.5
3
3.5
1.5
Example 9
[0144] Example 9 was carried out like Example 1, the polyurethane polymer D3 being used instead of the polyurethane polymer D1.
Example 10
[0145] Example 10 was carried out like Example 2, the polyurethane polymer D3 being used instead of the polyurethane polymer D1.
Example 11
[0146] Example 11 was carried out like Example 3, the polyurethane polymer D3 being used instead of the polyurethane polymer D1.
Example 12
Comparison
[0147] 100 parts by weight of polyurethane polymer D3.
[0000]
TABLE 3
Properties of Examples 9 to 12
Example
12
9
10
11
(comparison)
Monomeric H 12 MDI [%]
0.60
0.76
1.07
3.26
Viscosity at 90° C. [Pa · s]
15.0
15.7
18.6
13.5
Viscosity at 110° C.
7.2
7.8
9.1
7.2
[Pa · s]
Viscosity at 130° C.
4.4
5.1
5.0
4.6
[Pa · s]
Open time [min]
3.5
3.5
4
4
Example 13
[0148] Example 13 was carried out like Example 1, the polyurethane polymer D4 being used instead of the polyurethane polymer D1.
Example 14
[0149] Example 14 was carried out like Example 2, the polyurethane polymer D4 being used instead of the polyurethane polymer D1.
Example 15
[0150] Example 15 was carried out like Example 3, the polyurethane polymer D4 being used instead of the polyurethane polymer D1.
Example 16
Comparison
[0151] 100 parts by weight of polyurethane polymer D4.
[0000]
TABLE 4
Properties of Examples 13 to 16
16
Example
13
14
15
(comparison)
Monomeric IPDI [%]
0.26
0.17
0.36
1.77
Viscosity at 90° C. [Pa · s]
15.4
18.7
18.8
11.5
Viscosity at 110° C. [Pa · s]
7.6
9.5
9.3
6.2
Viscosity at 130° C. [Pa · s]
4.4
5.3
5.0
3.9
Open time [min]
2.5
2
3
4.5
[0152] From the examples shown, it is clear that the compositions according to the invention have substantially lower contents of monomeric diisocyanates than the corresponding compositions according to the prior art without aldimino groups, their applicability as reactive hotmelt adhesives being ensured. | The invention relates to relates to moisture-hardened hot melt adhesive which contains at least one polyurethane polymer of formula (I) which comprises aldimine groups and which is solid at room temperature, in addition to at least one polyurethane polymer P which comprises isocyanate groups, if q in formula (I) represents zero, or if X in formula (I) represents N—R 8 with R 8 as a substituent of formula (III). The compositions are characterised in that contain visibly less isocyanate monomers and are therefor particularly advantageous from a work-hygiene point of view. | 2 |
BACKGROUND
[0001] Fasteners, particularly screw type fasteners drive through and/or into two objects, securing them to one another. In sheet metal applications, screw threads may cut into the sheet metal, creating a pigtail-looking burr that is not only sharp and dangerous, but may compromise the integrity of the screw attachment and the sheet metal itself due to the burr damaging the sealing washer typically provided under the screw head, resulting in a defective water seal.
[0002] Previous methods for preventing screws from forming pigtail burrs include mill-cutting the screw-tip. The prior known milled point screws are generally referred to as a “Type 17” point screw, an example 400 of which is shown in FIG. 23 . Here a tip 406 of the screw 400 has a cut area 430 that is cut into a screw tip 406 and threads 420 using a standard right angle milling cutter 500 , shown in FIG. 24 , with generally right-angled teeth 510 . Such a standard cutter may be 3″ in diameter and ⅛″ thick. When the cutter 500 cuts into the screw 400 , a right angle is created in the screw tip 406 and the cut through the threads 420 is similarly at a right angle. This sharp angled cut area 430 helps to break off burrs that form during screw insertion. These screws include a cutting edge milled with a 90° cutter, shown in FIG. 24 . One side of the cutter is can be aligned with the fastener centerline so that the cutting face created is perpendicular. However, installation of these types of fasteners does not consistently result in a burr not being formed.
SUMMARY
[0003] A fastener includes a cylindrical shaft located between a head and a tapered point, threads integrally extending from the shaft and extending along a portion of a length thereof, and a burr cutoff area formed in the shaft near the tapered point and including flank surfaces therein forming an angle α of more than 90 degrees therebetween, and a flattened area between the flank surfaces. This is referred to by applicant as a beveled milled point and applicant has shown that this arrangement reduces the installation torque required due to the reduced surface area of the thread near the point as well as the increased cutting performance due to the beveled point surfaces and also addresses the issue in the prior known milled point fasteners.
[0004] In one aspect, the angle α is from at least 90° to 145°, and more preferably about 105°.
[0005] In one preferred arrangement, a sealing washer located on the shaft under the head.
[0006] In one embodiment, the flank surfaces are arranged at an angle of α/2 from a center of the cutoff area, with the cutoff area being symmetric in cross-section.
[0007] Alternatively, a first one of the flank surfaces can be arranged at an angle α l of about 90° from the flattened area, and a second one of the flank surfaces is arranged at an angle α 2 of about 5° to 50° to the flattened area, more preferably at about 45°.
[0008] Here, the second one of the flank surfaces preferably faces in an advancing direction of the thread.
[0009] In another aspect, a method of forming an anti-burr-forming fastener is provided, which includes the steps of providing a rotating cutting tool with a cutting surface including, in cross-section, two sides set at an angle of greater than 90° to each other, connected by a flat portion; and applying the cutting surface to a screw in an area adjacent to a tip of the screw, cutting a groove generally parallel to an axis of the screw forming a cutoff area with two flank surfaces at an angle of greater than 90° to each other connected by a flattened area.
[0010] In one preferred arrangement, one of the two sides of the cutting tool is arranged at an angle of about 90° to the flat portion.
[0011] Alternatively, the two sides of the cutting tool can be arranged at equal angles to the flat portion.
BRIEF DESCRIPTION OF THE DRAWING(S)
[0012] FIG. 1 is a perspective view of a first embodiment of a screw,
[0013] FIG. 2 is a side view of the screw of FIG. 1 .
[0014] FIG. 3 is a cross-sectional view of the screw of FIG. 1 .
[0015] FIG. 4 is a cross-sectional view taken along line 4 - 4 in FIG. 1 .
[0016] FIG. 5 is a side view of the screw of FIG. 1 shown with a sealing washer under the head.
[0017] FIG. 6 is a cross-sectional view of the screw of FIG. 5 .
[0018] FIG. 7 is a partial side view enlargement of the screw of FIG. 1 .
[0019] FIG. 8 is a view of a milling cutter form forming the cutoff area of the screw of FIG. 1 according to one embodiment of the invention.
[0020] FIGS. 9 and 10 show a beveled grinding wheel being applied to as a part of the manufacturing process to form the cutoff area of the screw of FIG. 1 .
[0021] FIG. 11 shows a side view of the grinding wheel.
[0022] FIG. 12 shows a side view of the grinding wheel.
[0023] FIG. 13 shows an enlargement of the cutting surface of FIG. 12 .
[0024] FIG. 14 is a perspective view of a second embodiment of a screw,
[0025] FIG. 15 is a side view of the screw of FIG. 14 .
[0026] FIG. 16 is a cross-sectional view of the screw of FIG. 14 .
[0027] FIG. 17 is a cross-sectional view taken along line 17 - 17 in FIG. 14 .
[0028] FIG. 18 is a partial side view enlargement of the screw of FIG. 14 .
[0029] FIG. 19 is a view of a milling cutter form forming the cutoff area of the screw of FIG. 14 according to one embodiment of the invention.
[0030] FIG. 20 shows a side view of the grinding wheel.
[0031] FIG. 21 shows a side view of the grinding wheel.
[0032] FIG. 22 shows an enlargement of the cutting surface of FIG. 21 .
[0033] FIG. 23 is a partial side view enlargement of a screw according to the known prior art.
[0034] FIG. 24 is a view of a milling cutter form forming the cutoff area of the prior art screw of FIG. 23 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] FIGS. 1-7 show a first embodiment of a screw 100 described herein. The screw 100 comprises a shaft 102 , head 104 , point or tip 106 , threads 120 , and anti-burr cutoff area 130 . (Although traditionally the plural is used to describe the “threads,” a screw thread 120 is typically one helical connected inclined plane).
[0036] A screw 100 is one of the six classical simple machines, and combines the simple machines of an inclined plane and wedge. The threads 120 of the screw 100 are made of an inclined plane that encircles the cylindrical shaft 102 . The threads 120 or planar inclination allows the screw 100 to fasten more easily and also improves the screw 100 ′s holding power.
[0037] The screw tip 106 acts as a wedge that operates by separating objects. When used with the screw 100 , the wedge tip 106 creates a hole in the material that the screw 100 engages. The sharper the tip 106 , the less force it takes for it to create a hole.
[0038] Once the tip 106 creates a small hole, the threads 120 engage the material and drive it apart. The threads 120 may be wound into existing thread grooves within the previously created hole or they may cut their own grooves during insertion. A rotation force applied to the screw 100 drives the screw through the material. This force may be applied with a driving mechanism like a drill or screwdriver. The threads 120 resting within the grooves create a bind that joins materials engaged along the axis of the screw shaft 102 . This engagement is the result of converting torque to linear force.
[0039] The strength of hold of the screw 100 depends on the width of the threads 120 and the distance between them. The closer and wider the threads 120 , the stronger the hold will be. More threads, however, require more rotations to attach the screw 100 , while wider threads 120 require more force in the rotations.
[0040] As shown, the screw threads 120 taper from their maximum height along the cylindrical shaft 102 along the conical screw portion 107 that leads to the tip 106 . At the tip 106 , the screw thread 120 height diminishes until it meets and/or forms the point.
[0041] Along the length of the screw shaft 102 , the screw threads 120 maintain a constant height in most uses (although this is not necessary).
[0042] Depending on the application, the screw 100 may include one or more sealing washers installed under the head 104 . One preferred arrangement used for sheet metal siding and roofing provides a two part bonded washer with a steel washer 140 that goes under the head 104 and a rubber or elastomer seal 142 that goes under and is preferably bonded or vulcanized to the steel washer 140 to provide sealing around the entry point of the screw 100 into the material being fastened. Alternatively, the washers 140 , 142 could be two separate parts.
[0043] In the screw 100 , a burr cutoff area 130 is provided having an overall angle α of at least 90° to 145°, and more preferably about 105°. The cutoff area 130 is formed with three surfaces, shown most clearly in FIG. 7 , with two flank surfaces 134 a, 134 b that define the angle α therebetween that are connected by a bottom, flattened surface 132 , shown as flat in cross-section in the present embodiment. Here the flank surfaces 134 a, 134 b are each at an angle of α/2 from a center of the cutoff area 130 , forming a symmetric groove. This arrangement results in what applicant terms a “double bevel milled point” screw 100 .
[0044] A beveled milling cutter 300 with teeth 310 that forms the cutoff area 130 in the screw 100 is shown in FIG. 8 . The cutter 300 preferably has a 3″ diameter and is ⅛″ thick. The dimensions of the milling cutter could be varied depending on the particular application. Alternatively, FIGS. 9 and 10 show a beveled cutting wheel 300 ′ formed as a grinding wheel, made of a cutting abrasive, or as a diamond coated surface with cutting surface 310 ′ having the desired profile. In FIGS. 9 and 10 , the cutter 300 ′ is shown being applied to a screw 100 . FIGS. 11-13 show the cutting wheel 300 ′ and the feature that the angled cutting surfaces 310 ′ a and 310 ′ b are at an angle of 105° to each other and the flat surface 310 ′ c is approximately 0.015 inches, as shown. The cutting surface 310 ′ a is used to form the flank surface 134 a, the cutting surface 310 ′ b is used to form the flank surface 134 b, and cutting surface 310 ′ c forms the flat bottom of the burr cutoff area 130 . The flat surface 310 ′ c may be eliminated in some embodiments. The angle between surfaces 310 ′ a and 310 ′ b is preferably between 90 and 135 degrees. The teeth 310 on the cutting wheel 300 would have similar dimensions.
[0045] When the cutting wheel 300 , 300 ′ is applied to the screw 100 , the center axis of the shaft 120 can be aligned with the leading edge of the flat surface 310 ′ c. However, other positioning is possible, depending on the particular profile.
[0046] The reduced cross-sectional area of the point 106 reduces the chance of forming pig tail burrs so that sealing washers put onto the screw 100 are less likely to become damaged (especially the rubber washers 142 ). The anti-burr area 130 helps break off the burr when it does form, yields a larger cutting surface, and helps make a sharper drill point.
[0047] Referring now to FIGS. 14-17 , a second embodiment of a screw 200 is shown. The second embodiment of the screw 200 is similar to the first embodiment 100 , and like elements have been designated with similar reference numbers that are increased by 100 . The screw 200 includes the shaft 202 , a head 204 and a point 206 , as well as threads 220 . The screw threads 220 taper from their maximum height along the cylindrical shaft 202 along the conical screw portion 207 that leads to the tip 206 . As shown in FIGS. 14 , 15 , and 17 , the screw 200 can also be provided with the sealing washers 140 , 142 under the head 204 . The difference between the screw 100 and the screw 200 is in the burr cutoff area 230 . As shown in FIGS. 16 and 18 , the first flank surface 234 a is at an angle α l of about 90° from a radially extending line that extends from the bottom of the cutoff area 230 , and the second flank surface 234 b is at an angle α 2 that is from about 5° to 50° from the radial line, and more preferably about 45°. Preferably α 1 +α 2 =between about 95° and 140°, and more preferably 135°. α 2 can be varied, and α 1 remains at about 90°. The second flank surface 234 b faces in an advancing direction of the thread 220 . A flat can optionally be provided at the bottom of the first and second flank surfaces 234 a, 234 b. This arrangement results in what applicant terms a “hybrid single bevel milled point screw” 200 .
[0048] A beveled milling cutter 320 with teeth 330 that forms the cutoff area 230 in the screw 200 is shown in FIG. 19 . The cutter 320 preferably has a 3″ diameter and is ⅛″ thick. The dimensions of the milling cutter could be varied depending on the particular application. Alternatively, FIGS. 20-22 show a beveled cutting wheel 320 ′ formed as a grinding wheel, made of a cutting abrasive, or as a diamond coated surface with cutting surface 330 ′ having the desired profile. Here cutting surface 330 ′ a is used to form the flank surface 234 a, cutting surface 330 ′ b is used to form the flank surface 234 h.
[0049] The reduced cross-sectional area of the point 206 reduces the chance of forming pig tail burrs so that sealing washers put onto the screw 200 are less likely to become damaged (especially the rubber washers 142 ).
[0050] Having thus described various embodiments of the present anti burr fasteners in detail, it is to be appreciated and will be apparent to those skilled in the art that many physical changes, only a few of which are exemplified in the detailed description above, could be made in the apparatus without altering the inventive concepts and principles embodied therein. 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 to be embraced therein. | A fastener includes a cylindrical shaft located between a head and a tapered point, threads integrally extending from the shaft and extending along a portion of a length thereof, and a burr cutoff area near the tapered point and including flank surfaces therein forming an angle greater than 90° therebetween. A flattened area can be located between the flank surfaces. | 5 |
REFERENCE TO PRIORITY APPLICATION
This application claims priority to Korean Patent Application No. 10-2008-0123762, filed Dec. 8, 2008, the contents of which are hereby incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to integrated circuit devices and, more particularly, to image sensor devices.
BACKGROUND
Conventionally, an efficiency in collecting photocharges is controlled by using a photogate of a MOS structure and the distance from an object can be measured by using the phase difference between emitted light and reflected light. However, in the MOS-type photogate structure using poly-silicon (poly-Si), a light absorption factor is generated in the course of the measurement and thus loss of light efficiency may be generated. When the thickness of poly-Si is made thin in order to restrict the loss, the resistance of poly-silicon increases so that the voltage applied to the photogate may not be sufficiently transferred.
Also, in the MOS type photogate structure, noise due to dark current may be generated because photocharges concentrate at the boundary surface between Si and SiO 2 . Furthermore, the MOS type photogate structure can require a high voltage of 3.3V or higher for stable operation thereof.
SUMMARY
Image sensor devices according to embodiments of the invention include a dual-gated charge storage region within a substrate. The dual-gated charge storage region includes first and second diodes within a common charge generating region. This charge generating region is configured to receive light incident on a surface of the image sensor device. The first and second diodes include respective first conductivity type regions responsive to first and second gate signals, respectively. These first and second gate signals are active during non-overlapping time intervals. The first and second diodes also include respective second conductivity type regions that form non-rectifying semiconductor junctions with the common charge generating region. The image sensor devices further include a first transfer transistor having a first source/drain region electrically coupled to the common charge generating region and a second transfer transistor having a first source/drain region electrically coupled to the common charge generating region.
According to some of these embodiments of the invention, the first conductivity type regions of the first and second diodes are P-type anode regions and the second conductivity type regions are N-type cathode regions. In particular, the first source/drain region of the first transistor may be disposed in the N-type cathode region associated with the first diode.
According to additional embodiments of the invention, the image sensor device includes a substrate having a well region of first conductivity type therein, and the common charge generating region forms a P-N rectifying junction with the well region. The first transfer transistor includes an insulated gate electrode extending opposite respective portions of the well region, the common charge generating region and the N-type cathode region of the first diode.
Image sensor devices according to additional embodiments of the invention include a dual-gated charge storage region within a substrate. The dual-gated charge storage region includes first and second diodes within a common charge generating region, which is configured to receive light incident on a surface of the image sensor device. The first and second diodes have respective first conductivity type anode regions adjacent a light receiving surface of the substrate and second conductivity type cathode regions that form non-rectifying semiconductor junctions with the common charge generating region. According to further aspects of these embodiments, the image sensor device may be configured to drive the first conductivity type anode regions of the first and second diodes with first and second gate signals, respectively, which are active during first and second non-overlapping time intervals, respectively. The image sensor may also include a first transfer transistor having a source/drain region in the cathode region of the first diode, and a second transfer transistor having a source/drain region in the cathode region of the second diode. In some of these embodiments of the invention, the anode region of the first diode includes a first plurality of P-type fingers within the common charge generating region. The anode region of the second diode may also include a second plurality of P-type fingers that are interdigitated with the first plurality of P-type fingers.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the inventive concept will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a cross sectional view of a pixel array of a 3D image sensor according to an exemplary embodiment of the present inventive concept;
FIG. 2 is a timing diagram for explaining a principle to measure the distance from a subject by using the 3D image sensor according to an exemplary embodiment of the present inventive concept;
FIG. 3 is a cross sectional view of a pixel array of the 3D image sensor according to another exemplary embodiment of the present inventive concept;
FIG. 4 is a cross sectional view of a pixel array of the 3D image sensor according to another exemplary embodiment of the present inventive concept;
FIG. 5 is an extended cross sectional view of a pixel array of the 3D image sensor according to another exemplary embodiment of the present inventive concept;
FIGS. 6A-6C are plan views of a pixel array according to an exemplary embodiment of the present inventive concept;
FIG. 7 is a block diagram of a 3D image sensor according to an exemplary embodiment of the present inventive concept; and
FIG. 8 is a block diagram of a semiconductor system having a 3D image sensor according to an exemplary embodiment of the present inventive concept.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The attached drawings for illustrating embodiments of the inventive concept are referred to in order to gain a sufficient understanding of the inventive concept and the merits thereof. Hereinafter, the inventive concept will be described in detail by explaining embodiments of the inventive concept with reference to the attached drawings. Like reference numerals in the drawings denote like elements.
FIG. 1 is a cross sectional view of a pixel array 100 of a 3D image sensor according to an exemplary embodiment of the present inventive concept. Referring to FIG. 1 , the pixel array 100 may include one or more unit pixels. The pixel array 100 may include photocharge storage regions 11 and 12 (or, collectively a photocharge storage region 10 ), storing photocharges, gating regions 21 and 22 (or, collectively a gating region 20 ), controlling the photocharge storage region 10 , and a photocharge generation region 30 providing photocharges to the photocharge storage region 10 .
As shown in FIG. 1 , the photocharge generation region 30 may be doped into a first type, for example, an n-type. Also, the photocharge generation region 30 may absorb externally incident light and generate photocharges in response to the absorbed light. In detail, the photocharge generation region 30 may absorb the incident light emitted by a light source (not shown) and reflected by a subject (not shown). Also, according to an exemplary embodiment, photocharges in an amount proportional to the intensity of the absorbed light may be generated in the photocharge generation region 30 .
The photocharge storage region 10 may store the photocharges generated by the photocharge generation region 30 . The photocharge storage region 10 may be doped into the first type, for example, the n-type. In detail, as illustrated in FIG. 1 , the photocharge storage region 10 may be implemented in form of a buried well. Accordingly, the photocharges generated by the photocharge generation region 30 may be efficiently stored in the photocharge storage region 10 .
The photocharge generation region 30 and the photocharge storage region 10 may be doped into the same type, for example, the n-type. According to an exemplary embodiment, the doping concentration of the photocharge storage region 10 may be higher than that of the photocharge generation region 30 . Also, to gather the photocharges generated in a deep area, the photocharge generation region 30 may be doped at a low concentration or made in an intrinsic state.
The photocharges generated in the photocharge generation region 30 may be selectively transmitted to the photocharge storage region 10 in response to any one of voltages Vgate 1 and Vgate 2 applied to the gating region 20 . The gating region 20 may be formed in one surface of the photocharge storage region 10 . The gate voltages Vgate 1 and Vgate 2 may be respectively input to the gating region 20 . As illustrated in FIG. 1 , the gate region 20 may be doped into a second type, for example, a p-type.
Also, a first voltage, for example, Vgate 1 , applied to a first gating region (or first gate) 21 , for example, and a second voltage, for example, Vgate 2 , applied to a second gating region (or, second gate) 22 , for example, may have a phase difference of 180° from each other. According to an exemplary embodiment, the first and second voltages Vgate 1 and Vgate 2 may be square wave type voltages. Also, according to an exemplary embodiment, the amplitudes of the first and second voltages Vgate 1 and Vgate 2 may be not greater than 1V. Thus, since the square wave voltages having a phase difference of 180° are input to the first and second gates 21 and 22 , the first and second gates 21 and 22 are not gated at the same time. Thus, the pixel array 100 according to the exemplary embodiment of the present inventive concept may be implemented such that the voltage may be selectively supplied to any one of the first and second gates 21 and 22 .
For example, when the first voltage Vgate 1 has a first level, for example, a low level, since the second voltage Vgate 2 has a phase difference of 180° from the first voltage Vgate 1 , the second voltage Vgate 2 may have a second level, for example, a high level. In this case, as the area of a second photocharge storage region 12 , for example a second well 12 formed by contacting the second gate 22 extends and is deepened, the photocharges generated in the photocharge generation region 30 may be accumulated in the second well 12 . Similarly, when the first voltage Vgate 1 has a second level, for example, a high level, the second voltage Vgate 2 may have the first level, for example, the low level. In this case, as the area of a first photocharge storage region 11 , for example a first well 11 formed by contacting the first gate 21 extends and is deepened, the photocharges generated in the photocharge generation region 30 may be accumulated in the first well 11 .
Also, the pixel array 100 according to the present exemplary embodiment may further include a substrate 40 that is formed under the photocharge generation region 30 . The substrate 40 may be doped into the second type, for example, the p-type. Although in FIG. 1 the photocharge generation region 30 and the photocharge storage region 10 are doped into the n-type and the substrate 40 and the gating region 20 are doped into the p-type, the doping types of the elements may be reversely implemented according to an exemplary embodiment.
FIG. 2 is a timing diagram for explaining a principle to measure the distance from a subject by using a 3D image sensor according to an exemplary embodiment of the present inventive concept. Referring to FIGS. 1 and 2 , the light emitted from a light source (not shown) may be reflected by a subject (not shown) and reflected light may be incident on a 3D image sensor according to an exemplary embodiment of the present inventive concept. As illustrated in FIG. 2 , the light emitted from the light source may be a square wave.
When the reflected light reflected from the subject is absorbed in the photocharge generation region 30 , photocharges may be generated in the photocharge generation region 30 . The first voltage Vgate 1 input to the first gate 21 may have the same phase as that of the light emitted from the light source. The second voltage Vgate 2 input to the second gate 22 may have a phase difference of 180° from that of the first voltage Vgate 1 . Thus, while the reflected light is incident on the photocharge generation region 30 , a time period “A” during which the first voltage Vgate 1 applied to the first gate 21 has a second level, for example, a high level, and a time period “B” during which the second voltage Vgate 2 applied to the second gate 22 has the second level, for example, the high level, may be determined.
The photocharges may be stored in the first and second wells 11 and 12 during the time periods “A” and “B”. The distance from the subject may be calculated by using a difference in the amount of photocharges stored in the first and second wells 11 and 12 .
FIG. 3 is a cross sectional view of a pixel array of a 3D image sensor according to another exemplary embodiment of the present inventive concept. Referring to FIGS. 1-3 , the pixel array 100 A according to the present exemplary embodiment may further include a leakage current restriction region 50 which restricts leakage current generated in the gating region 20 .
Since the operations or structures of the substrate 40 , the photocharge generation region 30 , the photocharge storage region 10 , and the gate region 20 are substantially the same as those of ones illustrated in FIG. 1 , detailed descriptions thereof will be omitted herein. According to an exemplary embodiment, when the amplitude of a voltage applied to any one of the first and second gates 21 and 22 is increased, leakage current may be generated between the first and second gates 21 and 22 . Accordingly, the leakage current restriction region 50 may be provided to restrict the generation of leakage current at its maximum.
In detail, as illustrated in FIG. 3 , the leakage current restriction region 50 may be implemented by surrounding each of the first and second gates 21 and 22 or in a space between the first and second gates 21 and 22 . Also, the leakage current restriction region 50 may be doped into the first type, for example, an n-type. The doping concentration of the leakage current restriction region 50 may be lower than that of the first well 11 and the second well 12 and higher than that of the photocharge generation region 30 . Referring to FIGS. 1 and 3 , the size of the photocharge storage region 10 of the FIG. 1 may be smaller than the size of the photocharge storage region 10 ′ of the FIG. 3 . Thus, as the distance between the first and second wells 11 ′ and 12 ′ increases further, a larger potential difference may be generated between the first and second wells 11 ′ and 12 ′.
FIG. 4 is a cross sectional view of a pixel array of a 3D image sensor according to another exemplary embodiment of the present inventive concept. Referring to FIGS. 1-4 , the photocharge storage regions 10 are not separated from each other as in those illustrated in FIGS. 1 and 3 , but are continuously connected to each other. As a voltage is applied to the first and second gates 21 and 22 , the well under the first and second gates 21 and 22 may expand to a buried well. Thus, the pixel array 100 B illustrated in FIG. 4 may obtain substantially the same effect as those of the pixel array 100 illustrated in FIGS. 1 and 3 .
FIG. 5 is an extended cross sectional view of a pixel array of a 3D image sensor according to another exemplary embodiment of the present inventive concept. Referring to FIGS. 1-5 , the pixel array 100 C separately includes a plurality of floating diffusion layers 70 corresponding to the first and second wells 11 and 12 . The photocharges stored in each of the first and second wells 11 and 12 may be transferred to the floating diffusion layers 70 in response to the gating operation of a plurality of transfer gates 60 .
For example, the photocharges stored in the first well 11 in response to a voltage applied to the first gate 21 may be transferred to the floating diffusion layers 70 in response to the gating operation of any one, for example, Transfer Gate 1 , of the transfer gates 60 . That is, an inversion channel is formed between the floating diffusion layers 70 and each of the first and second wells 11 and 12 by the gating operation of the transfer gates Transfer Gate 1 60 . The photocharges stored in each of the first and second wells 11 and 12 may be transferred to the floating diffusion layers 70 along the inversion channel.
The photocharges accumulated in the floating diffusion layers 70 may be sensed by being amplified by a sensing amplifier AMP 90 . After sensing is completed, the photocharges may be reset to the floating diffusion layers 70 by the gating operation of the reset gate 80 . In this case, since one time of sampling may not provide a sufficient amplitude of a signal, the pixel array 100 according to the present exemplary embodiment may be implemented such as the sensing operation can be performed after the photocharge accumulation operation is performed several times. Accordingly, the voltages Vgate 1 and Vgate 2 applied to the first and second gates 21 and 22 may be controlled.
FIGS. 6A-6C are plan views of a pixel array according to an exemplary embodiment of the present inventive concept. FIG. 6A is a plan view of the pixel array 100 C of FIG. 5 , illustrating the structure to transfer the photocharges stored in each of the first and second wells 11 and 12 to the floating diffusion layers 70 in a lateral direction. Also, FIG. 6B illustrates another structure of the pixel array 100 E of the present exemplary embodiment, in which the photocharges stored in each of the first and second wells 11 and 12 may be transferred in a vertical direction, that is, in a direction to penetrate in or out a drawing sheet. For this purpose, any one of the first and second gates 21 and 22 may be disposed at the front surface of the drawing sheet while the other one may be disposed at the rear surface thereof.
FIG. 6C illustrates the structure of the pixel array 100 F according to another exemplary embodiment of the present inventive concept, which is suitable for implementing a pixel of a large area. For example, as illustrated in FIG. 6C , each of the first and second gates 21 and 22 includes a plurality of sub-gates and each sub-gate may be alternately arranged. Thus, each of the first and second gates 21 and 22 may efficiently store the photocharges formed by the light incident on a large area. Also, a pixel array having a large area may be implemented by using a gate in a zigzag format as illustrated in FIG. 6C .
FIG. 7 is a block diagram of a 3D image sensor 200 according to an exemplary embodiment of the present inventive concept. Referring to FIGS. 1-7 , the 3D image sensor 200 may include a photoelectric conversion unit 210 and an image processor (ISP) 230 . Each of the photoelectric conversion unit 210 and the image processor 230 may be implemented by a separate chip or module unit.
The photoelectric conversion unit 210 may generate an image signal of a subject based on the incident light. The photoelectric conversion unit 210 may include a pixel array 211 , a row decoder 212 , a row driver 213 , a correlated double sampling (CDS) block 214 , an output buffer 215 , a column driver 216 , a column decoder 217 , a timing generator 218 , a control register block 219 , and a ramp signal generator 220 .
The pixel array 211 may include any one of the pixel arrays of FIGS. 1 , 3 , 4 , and 5 and a plurality of pixels, in each of which a plurality of row lines (not shown) and a plurality of column lines (not shown) are connected in a matrix format. The row decoder 212 may decode a row control signal, for example, an address signal, generated by the timing generator 218 . The row driver 213 may select at least any one of the row lines included in the pixel array 211 , in response to the decoded row control signal.
The CDS block 214 may perform correlated double sampling with respect to a pixel signal output from a unit pixel connected to any one of the column lines constituting the pixel array 211 to generate a sampling signal (not shown), compare a sampling signal with a ramp signal Vramp, and a digital signal according to a comparison result. The output buffer 215 may buffer and output signals output from the CDS block 214 in response to a column control signal, for example, an address signal, output from the column driver 216 .
The column driver 216 may selectively activate at least any one of the column lines of the pixel array 211 in response to a decoded control signal, for example, an address signal, output from the column decoder 217 . The column decoder 217 may decode a column control signal, for example, an address signal, generated by the timing generator 218 . The timing generator 218 may generate a control signal to control the operation of at least one of the pixel array 211 , the row decoder 212 , the output buffer 215 , the column decoder 217 , and the ramp signal generator 220 , based on a command output from the control register block 219 .
The control register block 219 may generate various commands to control elements constituting the photoelectric conversion unit 210 . The ramp signal generator 220 may output a ramp signal Vramp to the CDS block 214 in response to a command output from the control register block 219 . The image processor 230 may generate an image of the subject based on pixel signals output from the photoelectric conversion unit 210 .
FIG. 8 is a block diagram of a semiconductor system 1 having the 3D image sensor 200 according to an exemplary embodiment of the present inventive concept. For example, the semiconductor system 1 may be a computer system, a camera system, a scanner, a navigation system, a videophone, a supervision system, an automatic focus system, a tracing system, an operation monitoring system, and an image stabilization system, but the present inventive concept may not be limited thereto.
Referring to FIG. 8 , a computer system that is a sort of the semiconductor system 1 may include a bus 500 , a central processing unit (CPU) 300 , a 3D image sensor 200 , and a memory device 400 . Also, the semiconductor system 1 may further include an interface (not shown) that is connected to the bus 500 and capable of communicating with an external device. The interface may be, for example, an I/O interface, and may be a wireless interface.
The CPU 300 may generate a control signal to control the operation of the 3D image sensor 200 and provide the control signal to the 3D image sensor 200 via the bus 500 . The memory device 400 may receive and store an image signal output from the 3D image sensor 200 via the bus 500 .
The 3D image sensor 200 may be integrated with the CPU 300 and the memory device 400 . In some cases, a digital signal processor (DSP) is integrated with the CPU 300 and the memory device 400 or the 3D image sensor 200 only may be integrated in a separate chip.
As described above, since the 3D image sensor according to the present inventive concept includes a pixel having a junction gate structure, a light use efficiency may be increased. Also, according to the 3D image sensor according to the present inventive concept, since the generated photocharges are stored in the well by avoiding the boundary surface of Si or SiO 2 , noise due to dark current may be greatly decreased. Furthermore, the 3D image sensor according to the present inventive concept may be easily implemented because an operation at a low operation voltage is possible.
While the inventive concept has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the following claims. | An image sensor device may include a dual-gated charge storage region within a substrate. The dual-gated charge storage region includes first and second diodes within a common charge generating region. This charge generating region is configured to receive light incident on a surface of the image sensor device. The first and second diodes include respective first conductivity type regions responsive to first and second gate signals, respectively. These first and second gate signals are active during non-overlapping time intervals. | 7 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 11/160,399, filed Jun. 22, 2005 and which is being incorporated in its entirety herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to the field of healthcare and more particularly to the areas of practice quality and cost containment. In greater particularity the present invention relates to the reduction in multiple iterations of the same procedures by practitioners with a historic proclivity towards repeat surgeries or other procedures. In even greater particularity the present invention relates to a method for identifying repeat surgeries and their sources and causes. In even greater particularity the present invention relates to the identification of multiple, serial insurance claims, and grouping of claims, to determine patterns of multiple iterations of procedures or surgeries on the same patient, or groups of patients to identify a common practitioner source or common provider facility source. In like manner the present invention relates to the identification of multiple serial insurance claims, and grouping of claims, to determine patterns of health complications following admission, procedures, treatments, interventions, surgeries and the like on the same patient or groups of patients, to identify a common practitioner source or provider facility source of such complications. In even greater particularity the present invention relates to a method for identifying repeat procedures and surgeries or complication and their sources and causes. In another aspect of the invention, the invention relates to patterns of patient transfers from one provider to another based on insurance specific or date specific rules. In greater particularity the present invention enables the identification of provider transfers by date and time relative to eh expiration of insurance coverage or the convenience of the provider.
Increasing medical costs and insurance costs are one of the leading sources of concern for people of all ages and businesses of all sizes as well as Federal, State and local governments. This includes physicians groups, hospitals, healthcare providers of all types including nursing homes and outpatient facilities, insurers, government agencies, labor groups and investment groups. For the past several decades the rising cost of healthcare and insurance have eaten away at the value of the earnings of all groups. Historically, the trend has been to advise that more research, better facilities, technological advances, and more doctors would solve the dilemma or that public education on medical practices would improve the quality of care patients would expect. All of these things contribute to improving the system, but the rising cost remains unchecked.
SUMMARY OF THE PRESENT INVENTION
This invention addresses sources of medical and insurance costs that can be eliminated or greatly reduced. The savings realized by the implementation of the invention could significantly reduce or even abate the rise in medical and insurance costs. In principal the present invention is based on the understanding that not all patients receive the same quality of care and that not all practitioners have the same level of skill or dedication, even though the practitioner and patient have no statistical tools to evaluate the quality of care or the level of skill. Consequently, among patients for whom a lower quality of care is provided greater instances of repeat surgeries are performed, or repeat hospitalizations for the same condition, or repeat treatments or surgeries for the same underlying condition which lead to increased complications impacting the quality of the patients life, increased billing by the physician or subsequent physicians at the same or subsequent facilities and increased cost to the insurers and insured patients.
Further, the present invention is also based on the realization that financial motives prompt patient discharges which result in increased overall costs due to repetitive procedures at the transferee provider facilities.
The present invention contemplates the use of a dynamic database that will provide the statistical and analytical data for use in identifying the sources of sub-quality care or skill whether by a practitioner or a provider facility. The identification of these sources coupled with the subsequent refusal of services to such sources will cause the sources to improve their services or turn to other endeavors, both of which results in improved healthcare and decreased costs.
Accordingly, the present invention contemplates patient specific data from hospital or insurance records that will identify the nature of the patient's illness, the treating physician and facility, the course of treatment, for the illness, and any recurrences of the illnesses. By way of example, patients suffering from a degenerative joint disease may eventually require joint replacement surgery. If a sufficiently large group of patients having such disease can be monitored and historical data maintained with reference to the treating physician and facility, then trends can be documented and physicians or facilities that treat the patients in will have an independent cross referenced record of outcome. More specifically, physicians or facilities that perform abnormally high repeat surgeries or refer excessive numbers of patients to other surgeons for follow up treatment on the previously “repaired” joint can be identified. In a further modification of the invention, statistical analysis can be performed relative to temporal variations in care by observing and quantifying factors such as the time of day or day of week of events such as transfers from ward to ward or facility to facility.
In a still further variation of the invention biographical and institutional data on facilities can be quantified to determine whether background factors in competency and care can be identified. Each of these quantifications makes it possible for the health care user or insurer to screen physicians and facilities to determine whether the patient should submit to treatment or seek treatment elsewhere. The concept is not to obtain a second opinion regarding the patient, but rather an accurate measure on the level of care to be expected by the patient and the parameters that define the duration of care and termination of care.
These and other objects and advantages of the invention will become apparent from the following detailed description of the preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
An flow chart for the method of the present invention is depicted in the accompanying drawings which form a portion of this disclosure and wherein:
FIG. 1 is an in patient flow diagram of events which may be tracked by the system;
FIG. 2 is an out patient flow diagram of events which may be tracked by the system.
FIG. 3 a is a time of day/day of week
FIG. 3 b is a time of day correlation chart for transfers.
FIG. 4 is a holiday correlation chart for transfers.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As illustrated in the accompanying figures, the present invention utilizes a database P maintained in a memory of a computer in which discrete pieces of data are collected. The term computer includes mainframe computers, personal computers, or a network of computers. The term a memory means a physical component of a computer or network of computers designed to store information and allow its retrieval and use of the stored information. Retrieval and use is accomplished by a software program that searches and correlates data as defined by the user of the system. The parameters discussed herein are used in such search an correlation software, however, the specific software program may vary depending on the platform it is running on, the type of network it is deployed in, the number of electronic addresses each memory component utilizes and a myriad of factors that are within the knowledge of a software designer who would be expected to create such software taking into consideration the specific configuration of the associated hardware.
Each patient presenting to a practitioner for treatment currently provides by necessity information regarding the persons identity, age, race, and medical conditions. This information is usually transmitted by the practitioner to an insurer or a government guarantor for payment. In so doing, the practitioner also provides identifying information about itself as well as the diagnosis and treatment provided to the patient on a specific date. All of this data is available in electronic or near electronic form as it is processed by the insurers or guarantors. Each patient can be universally identified by a code such as the patient's social security number. Each healthcare provider can be likewise identified by SSN or taxpayer id or some other unique reference.
Database P includes a permanent file identified with each patient including patient identification and the nature of each occurrence of illness or injury for which the patient has been treated. The information can be transmitted to the database via an interconnected computer network such as the Internet, Local area network, Wide area network, wireless network, so that data on the same patient may be sent from anywhere the network reaches to the memory containing database P. For each injury or illness transmitted to the database, data on the date, treatment and identity of the healthcare provider or facility will also be included. Accordingly, the minimum data fields required for the system include:
Patient id such as social security number
Facility ID such as Employer tax id number
Procedure ID such as AMA procedure identifier
Date and time of each consultation, admission, referral, transfer, discharge, or procedure.
Cost of each procedure
Paying party Id such as insurance contract number
Patient data files would include fields for each of the above such that each time patient 121-21-2121 is seen by a physician AL12345 at hospital EI 55-55555 and treated for procedure 033333, a record of the date Jan. 1, 2003 and the cost $500 is created showing that payer BC98765-4 paid for the procedure. Each time procedure 033333 is performed on patient 121-21-2121 another record is created in the patient data file with all of the above information. Accordingly a search query of the database can reveal matches for all patients having repeats of the same procedure. Further refinement of the search allows for determination of patients having repeat procedures wherein the procedure was originally performed by the same physician or at the same facility. Each physician in the database can then be searched to determine such things as percentage of repeat procedures on patients or percentage of referrals to other physicians for repeat procedure or remediation of procedures that proved ineffective.
Using the database in this way, a non-biased profile can be created for any physician, facility, or patient. For each physician who performs like procedures, for example arthroscopy, a peer group analysis can be performed, such that each physician can be evaluated as to his standing within the peer group in terms of percentage of repeat procedures or referrals for repeat procedures. By including biographical data on physicians such as medical school, residencies, training rotations, the analysis also provides for analysis of facility effectiveness in training.
The data gathering and sampling aspect of the invention is the precursor to the effective utilization of the invention to reduce costs. Each payer enrolled in the program requires each physician or facility that receives reimbursement from the payer to enroll in the system. Each payer then receives periodic reports identifying each physician or facility whose performance as measured by repeat procedures or referrals for repeat procedures is significantly out of the acceptable range as measured against all other physicians who are expected to have the same skill set. That is to say, internists are measured with internist, podiatrist with podiatrists, cardiovascular surgeons with cardiovascular surgeons, psychiatrist with psychiatrist and so on. The payer then has data with which to evaluate the physicians and make recommendations, such as that physician AL12345 should refrain from performing initial procedures of a certain type or that such procedures should not be performed at facility EI98765-4. Physician AL12345 may thus continue to diagnose and attend to the care of his patients, however, procedures which his performance leads to an inordinate number or repeats would no longer be reimbursable to him by the payer who would advise the facilities utilized by the patients of this fact. For outpatient procedures, the invention requires pre-approval of all procedures by the payer, thus physicians with diagnostic only payment authorization could not receive approval from their payer
Additional factors may also be introduced and tracked with the system including such variables as Length of Stay prior to first discharge for a recurrent treatment, Length of Stay prior to first tracked event; Length of Stay after first tracked event; Length of Stay in subsequent facility; Length of Stay prior to next traced event; Length of Stay after next tracked event. Likewise additional measures can be determined such as mortality rates by physician, facility, activity, or iteration of treatment; physician demographics such as medical school, residency, mentors, year group, experience; or facility demographics such as awards, staffing, licensure, income; and other variables as deemed appropriate.
With respect to FIG. 3 , this represents an expected situation which could be revealed or confirmed through the use of the present invention. Specifically, using the database to correlate discharge times of patients from facilities based on non-treatment related events, such as the expiration of insurance, the time of day, the approach of a holiday, the scheduled recreational events of the provider. In FIG. 3 , the hypothesis is that more patients will be transferred after 5 PM and before 7 AM on most days and shortly afternoon on weekends. Such transfer procedures in and of themselves place a burden on the transferee facility and concomitantly diminish the equality of patient care. Identification of provider transfer patterns can a allow a payer to proscribe and penalize improvident transfers. By way of example, in certain instances reimbursed care for certain individuals is limited to a matter of days, after which there provider hospital and/or physician receives no further compensation or compensation at a diminished rate. The present invention provides a searchable database which will identify any provider who routinely treats such patients for the maximum compensated period and then transfers patients to a second provider on or near the last day of compensation In many cases the transferee provider must run repetitive lab tests or x-rays to determine the proper treatment modality because the transfer did not include the documentation from the transferor hospital or the transferee provider protocol requires admission testing irrespective of the existence of documentation. These transfers are believed to occur primarily at the times shown in FIGS. 3 and 4 .
In practice the system would employ a variation of the following method. Creating a searchable electronic database containing patient, provider, and payer information as described above including the maximum compensable time and rate for each payer; electronically updating the searchable database for each admission, discharge, or transfer of a patient; determining the length of stay for each patient in each facility prior to transfer to another facility; iteratively executing a database management software program correlating the length of stay for each patient with the patients payer and payer's maximum compensable time and/or rate; iteratively executing a software routine for determining a profile for each provider showing transfer histories of patients based on time of day, day of week, proximity to holiday, and payer compensable time and or/rate; periodically providing such provider profiles to payer for review. They system may also be queried on the basis of transferee provider to identify repetitive procedures as noted above to quantify duplicative costs associated with the transfers.
It is to be understood that the form of the invention shown is a preferred embodiment thereof and that various changes and modifications may be made therein without departing from the spirit of the invention or scope as defined in the following claims. | A method for controlling healthcare costs comprising creating associational databases in a computer system containing physician, hospital, patient and payer information; cross-referencing and searching said databases for specific occurrences of treatment, discharge, or transfers with characteristics leading to higher medical costs, and providing statistical information to payers on specific physicians and hospitals such that payer's can determine whether to retain such providers services for specific procedures. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to semiconductor device fabrication methods and, more particularly, to a CMOS and bipolar fabrication process using selective epitaxial growth.
2. Description of the Related Art
As device geometries get smaller, well tried technologies become inadequate for isolating devices of the same or opposite conductivity type. For example, the widely used LOCOS (isoplanar) scheme requires too much silicon area for geometries below one micron, due to the bird's beak encroachment. In addition, latch-up considerations in CMOS prevent putting opposite type devices in very close proximity unless more complex processing is added.
Current state-of-the-art one to two micron level approaches to CMOS isolation include the use of trenches and epitaxial buried layers. Trench isolation has the disadvantage of requiring very complex and costly processing, and it requires some other type of oxide isolation for the majority of the chip's surface (typically LOCOS). Additionally. MOS transistors cannot be set directly against a trench wall because of degradation of device characteristics, thus increasing the area consumed by one transistor. Epitaxial buried layer isolation, while somewhat effective, still has a lower limit of approximately 2.5 micrometers for PMOS to NMOS spacing due to junction breakdown and punch-through.
Recently. CMOS isolation by selective epitaxial growth (SEG) has been proposed. In one method, not necessarily in the prior art, a silicon substrate is etched to form openings in the substrate, and insulators are formed on the side walls of the openings. Thereafter, the substrate is masked and doped to a chosen conductivity type, and an epitaxial layer is grown to fill the openings. A final LOCOS isolation then is performed. The disadvantages of this method are the requirement of etching into the silicon surface and the requirement of LOCOS isolation with the inherent bird's beak encroachment.
In another technique, also not necessarily in the prior art, a silicon dioxide layer is formed over a silicon substrate, and the silicon dioxide layer is etched for forming openings extending to the substrate. The openings are filled by growing epitaxial layers having a selected conductivity type (e.g., N-type) on the substrate. This creates doped wells in which devices of a particular type may be constructed. The wells then are covered by thin thermal oxide layers to protect them from later process steps. The process then is repeated to form wells having an opposite conductivity type (e.g., P-type). Thereafter, the thin oxide layers over the previously formed wells are stripped. Although this method does not require LOCOS isolation, it must be implemented with multiple SEG steps.
SUMMARY OF THE INVENTION
The present invention is directed to a relatively simple front-end process for isolating semiconductor devices wherein the process requires only one SEG step, provides twin buried layers which may be controlled independently, and uses a simple thermal oxidation step for isolation between devices. Active P and N regions are separately formed with self-aligned implants, and with fewer masking steps than conventional techniques. Unlike devices isolated by trenches, the isolation width can be any dimension above the resolution of the patterning tool for MOS devices of the same type, and the resolution of the patterning tool plus one registration tolerance for opposite type devices. Thus, if 0.5 micron is the resolution of the patterning tool, 0.5 micron isolation between same-type devices is achieved, and the process is scalable well into the submicron region. At submicron levels, no other presently known technique can provide a minimum device pitch of twice the resolution of the patterning tool with a planarized surface without substantially more complex processing.
For bipolar devices, the method according to the present invention minimizes collector-base capacitance through the use of oxide isolated collectors while also using a bipolar buried layer, whereas the independent P+ and N+ buried layers minimize the collector-to-substrate capacitance. Punch-through problems are eliminated because of full oxide isolation between devices. Finally, the front end of this process is compatible with the most advanced CMOS and bipolar backend device fabrication processes, such as silicided source-drain-gate areas and contacts/posts overlapping on field oxide for MOS devices, and a polyemitter or a poly-base and emitter for bipolar devices.
In one embodiment of the present invention, a silicon dioxide layer is formed over a silicon substrate. The silicon dioxide layer is etched for forming separate collector and base/emitter regions for a bipolar device, and PMOS and NMOS regions for corresponding PMOS and NMOS devices. Buried layer implants are performed, and an epitaxial layer is grown over the exposed portions of the silicon substrate. The silicon dioxide walls between the devices provide full dielectric isolation between the devices as well as between the collector and base/emitter regions of the bipolar device. Nonetheless, the oxide wall between the collector and base/emitter of the bipolar device is sufficiently small to allow the buried layer implants to join under the wall for forming a conventional buried layer for the bipolar device. Because of the oxide walls, the minimum distance between devices may be 0.5 microns or less.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1-5 illustrate the method according to the present invention for forming CMOS and bipolar devices using selective epitaxial growth.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows one embodiment of a silicon substrate 10 after undergoing preliminary processing according to the present invention. The substrate material is P-type 100 with 100 flat orientation and resistivity greater than 10 ohm-cm. The flat orientation is preferable to achieve the best selectively grown epitaxial layers with minimal faceting and stress. The orientation also helps to reduce fixed charges along the vertical sidewalls of the oxide isolation regions.
First, a silicon dioxide layer 14 is thermally grown to a thickness of from approximately 0.8 to 1.5 microns by placing substrate 10 in an oxygen environment at 1000° C. for approximately 300 minutes, making certain that the oxidation cycle includes conventional denuded zone formation steps. This ensures that the selectively grown epitaxial layer will not have stacking faults along the horizontal surface. Thereafter, a photoresist layer 18 is deposited and developed for forming the openings shown. The portions of silicon dioxide layer 14 beneath the openings in photoresist layer 18 then are etched vertically to the surface of substrate 10 by Reactive Ion Etching (RIE) to form openings 22, 24, and 26. Openings 22 and 24, together with an oxide wall 30 therebetween, define a bipolar region, and opening 26 defines a PMOS region.
Using photoresist layer 18 as a mask, arsenic or arsenic and phosphorous ions are implanted in succession without tilting the wafers in the implanter. In this embodiment, all implants prior to epitaxial growth are performed without wafer tilt. The self-aligned implant in openings 22 and 24 is used to form a buried layer and an N-well for the bipolar device. Opening 22 is used for constructing the collector of the bipolar device, and opening 24 is used to construct the base and emitter of the bipolar device. The self-aligned implant in opening 26 is used to form a buried layer and an N-well for the PMOS device. The concentration of arsenic is approximately 5×10 15 to 1×10 16 atoms/cm 2 , and it is implanted with an energy of approximately 100 KeV. The concentration of phosphorous is approximately 5×10 13 to 5×10 14 atoms/cm 2 , and it is implanted with an energy of approximately 150 KeV. The arsenic implant ensures low resistance of the implanted regions, whereas the faster diffusing phosphorous species ensures formation of the N-wells for the PMOS and bipolar devices.
Next, photoresist layer 18 is removed, and an anneal is performed at 1000° C. in an inert atmosphere, such as nitrogen, for approximately 60 minutes. This eliminates the implant damage prior to SEG. The anneal also creates side diffusion of the phosphorous and arsenic implants to ensure that the buried layers beneath openings 22 and 24 join under oxide wall 30. Preferably, oxide wall 30 has a width of 0.5 microns (e.g., definable by E-beam) or less. If oxide wall 30 is wider, a longer arsenic diffusion may be required prior to epitaxial growth to ensure that the doped regions beneath openings 22 and 24 join.
An alternative to successive arsenic and phosphorous implants is to implant the arsenic, remove photoresist layer 18, anneal and diffuse the arsenic, and then implant phosphorous, taking advantage of the masking of silicon dioxide layer 14 to selectively implant only in the exposed silicon regions.
As shown in FIG. 2, a photoresist layer 40 is deposited and developed. The exposed portions of silicon dioxide layer 14 beneath the openings in photoresist layer 40 are vertically etched to the surface of substrate 10 by RIE to form openings 41. 42, and 43. Then, boron is implanted to a dose of approximately 2×10 13 to 2×10 14 atoms/cm 2 at an energy of approximately 120 KeV and photoresist layer 40 is removed. The implant in openings 41 and 42 is used to form a guard ring around the bipolar device. The bipolar device is separated from the guard ring by oxide walls 44 and 45. The implant in opening 43 is used to ensure a continuous P-well for an NMOS structure after the process is complete. The PMOS device is isolated from the NMOS device by an oxide wall 50, thus providing full dielectric isolation between opposite type MOS transistors. An added benefit of the boron implant is the lowering of substrate resistance R S which is beneficial in latch-up suppression.
Although the P and N regions are separately formed, only two masking steps have been required. This eliminates one masking step from conventional techniques wherein a mask is required for active region definition and for each implant. Additionally, the process according to the present invention avoids the necessity of dealing with a photoresist mask in peaks and valleys of the active regions.
The minimum distance between two adjacent NMOS devices is 0.5 microns or the resolution of the patterning tool. The distance between two adjacent PMOS devices is also 0.5 microns, since they can share the same N-well. If a PMOS device or another bipolar device is directly adjacent to the bipolar device (i.e., no guard ring). wall 45 preferably is wider by 0.4 to 0.6 microns than wall 30 to ensure isolation of the PMOS or the second bipolar device from the adjacent bipolar device. The minimum width for oxide wall 50, which forms the isolation region between the NMOS and PMOS devices, is the larger of (a) the minimum resolution of the patterning tool plus one registration tolerance, or (b) two registration tolerances. Thus, in the future, when both registration tolerances and resolution are reduced, this technology can be scaled below 0.5 microns, with the limit for isolation width then being an acceptable value of threshold voltage of the oxide isolation region.
By separating the regions of arsenic and boron implants, the bipolar collector-substrate capacitance is substantially reduced. The adjustment of this capacitance is by boron and phosphorous implant doses, the width of oxide wall 44, and total heat treatment included in the process. By allowing a wider separation between NMOS and NPN bipolar devices (assuming an NMOS device is located to the left of the bipolar device). this capacitance can be the absolute minimum. On the other hand, some designs may not require an NPN bipolar device next to an NMOS device, thus ensuring a low collector-to-substrate capacitance.
As shown in FIG. 3, undoped epitaxial silicon is selectively grown to the thickness of the remaining portions of silicon dioxide layer 14, 24. 26, 41. 42, and 43. This may be accomplished by a five minute in situ hydrogen bake at 1000° C. and 25 torr, followed by SEG deposition at 850°-950° C. and 25 torr in a hydrogen dichlorosilane and hydrogen chloride ambient to minimize faceting. This forms a collector region 51 in opening 22, a base/emitter region 52 in opening 24, a guard ring region 53 in opening 41 and 42, a PMOS region 54 in opening 26, and an NMOS region 55 in opening 43. Although guard ring region 53 is shown as separate regions in cross section, it is actually a continuous region encircling collector region 51 and base/emitter region 52. Thereafter, a thin silicon dioxide layer 48 is grown to a thickness of approximately 200-300 angstroms to alleviate the stress at the epi-isolation oxide interface. Oxide layer 48 also is used as a sacrificial oxide for gate oxide integrity improvement.
Proceeding to FIG. 4, a photoresist layer (not shown) is deposited and developed for exposing collector region 51, base/emitter region 52, and PMOS region 54. The exposed regions then are implanted with phosphorous to a concentration of approximately 1×10 12 to 4×10 12 atoms/cm 2 at an energy of 150 KeV for setting the N-well impurity profile at the surfaces of the P-channel devices and bipolar devices if necessary. The photoresist layer is removed, and a new photoresist layer 56 is deposited and developed to expose guard ring region 53 and NMOS region 55. The exposed regions then are implanted with boron for setting the impurity profile for the bipolar guard ring and the P-well for the N-channel devices. In some cases, photoresist layer 56 may not be necessary, and a blanket V T implant may be all that is required to set the correct P-channel and N-channel threshold voltages and to dope the bipolar guard rings.
Next, substrate 10 is placed in an inert environment at 1050° C. for approximately 60 minutes so that the substrate buried layers join with their respective N-well and P-well surface implants. After the drive-in, a V T implant is performed with BF 2 to a concentration of 1×10 12 to 3×10 12 atoms/cm 2 . The thin sacrificial oxide layer 48 then is removed, and a gate oxide layer 60 having a thickness of 120-150 angstroms is grown, as shown in FIG. 5. This thin oxidation is the only oxidation step that the impurities will see, and thus segregation and depletion of boron on the sidewalls of isolation regions are minimized. No birds-beak encroachment is encountered in this process; thus, defined active and isolation dimensions will be the true electrical dimensions of the device and can be 0.5 micron or even less.
After the gate oxidation step, conventional gate material deposition and definition follow. The gate material can be polysilicon, silicide, or a combination of the two. For 0.5 micron devices. P+ polysilicon for P-channels and N+ polysilicon for N-channels are desirable. This is accomplished by doping the polysilicon at the time of the source/drain implants. The two types of polysilicon can be shorted by a silicide or a metal strap. At the time of the source/drain implantation, contacts to the N-well and substrate can be implemented, although they are not shown in these figures. These contacts are presumed to be in planes perpendicular to the plane of the cross sections. Sidewall spacers on gates are formed, and source-drain-gate silicidation is performed. Posts or unguarded contacts can be used for minimizing the interconnect real estate.
A guard ring should be formed for each bipolar transistor, but the precision of the present process allows the guard ring to be accurately spaced to provide very high performance.
After gate oxide layer is grown, the base is implanted, and base/emitter contacts (e.g., polysilicon buried contacts) are formed. After gate oxide layer 48 is grown, and before the N-well mask and implant, a collector sink mask, phosphorous implant (in collector region 5) to a concentration of 1×10 15 to 1×10 16 atoms/cm 2 and a drivein may be performed for performance improvement.
While the above is a complete description of a preferred embodiment of the present invention, various modifications may be employed. For example, bipolar devices may be omitted. Consequently, the scope of the invention should not be limited except as properly described in the claims. | A CMOS and bipolar fabrication process wherein a silicon dioxide layer initially formed over a silicon substrate is etched for forming separate collector and base/emitter regions for a bipolar device, and PMOS and NMOS regions for corresponding PMOS and NMOS devices. Buried layer implants are performed using a minimum number of masks, and then an epitaxial layer is grown over the exposed portions of the silicon substrate. The silicon dioxide walls between the devices provide full dielectric isolation between the devices, as well as between the collector and base/emitter regions of the bipolar device. Nonetheless, the oxide wall between the collector and base/emitter of the bipolar device is sufficiently small to allow the buried layer implants to joint under the wall for forming a conventional buried layer for the bipolar device. Because of the oxide walls, the minimum distance between devices may be 0.5 microns or less. | 7 |
RELATED APPLICATION
[0001] This application incorporates and claims the full benefit of Provisional Application No. 60/339,005 filed Dec. 7, 2001.
TECHNICAL FIELD
[0002] This invention relates to appliance housings and other shapes which are stamped or otherwise fabricated or formed from steel strip, and particularly to methods of making electrocoated steel appliance housing preforms and other types of preforms including automotive parts. More broadly, the invention comprises a method of depositing a resin-containing coating on a steel object by electrocoating the steel object having a chrome surface in a bath containing a cationic polymer.
BACKGROUND OF THE INVENTION
[0003] The manufacture of appliance cabinets and other parts from steel sheet or strip is a capital-intensive, multi-step process. A simplified recitation of the conventional steps would include forming the incipient housing, cabinet or automotive part from the steel strip, cleaning it, rinsing it, applying a phosphate coating, rinsing again, electrocoating, rinsing, and baking. It should be remembered that housings and cabinet parts for laundry washers and dryers, for example, are large and cumbersome to move in and out of the various coating, drying, immersing and baking areas. In addition, conditions in the electrolytic bath must be monitored and/or controlled. Quality control rejections of large parts such as appliance cabinets can be quite expensive.
[0004] Filiform corrosion too often appears between the metal and the final coating, forming iron oxides in thread-like lines emanating from an anodic nucleus where oxygen is able to penetrate through the paint or other coating. To guard against filiform corrosion, phosphate treatment, usually in the form of zinc phosphate, is undertaken to place a phosphate coating on it for corrosion control, but is not entirely effective in that the parts are still undesirably subject to a risk of filiform corrosion.
[0005] Such a complicated and demanding process, having many steps and numerous conditions to maintain, necessarily provides many opportunities for error and mishap. The industry would benefit from a simple process with as few steps as possible as well as from obtaining a process which significantly reduces the incidence of filiform corrosion.
[0006] Containers made from ECCS (electrocoated chrome/chrome oxide strip, sometimes known as tin-free steel), both three-piece fabricated cans and “D&I”, or drawn and ironed cans, without phosphate coatings, have been proposed for electrocoating in a resin-containing bath. See Seiler U.S. Pat. No. 4,303,488 and Colberg's U.S. Pat. No. 3,939,110, both describing polycarboxylic resins for use in electrocoating of cans acting as the anode. Cans are typically quite thin-walled; conventionally, they are clear lacquered.
SUMMARY OF THE INVENTION
[0007] We have invented a process which obviates the necessity for several steps in the conventional process, and the use of a phosphate treatment in particular. Our invention includes a method of making an appliance cabinet preform comprising (a) providing a desired two-dimensional shape from a steel strip, the steel strip having on it a layer of chromium metal (b) forming the two-dimensional shape into a desired three-dimensional shape which is at least part of an incipient applicance housing, (c) immersing the three-dimensional shape into an electrolytic cell containing a coating bath comprising a cationic polymer (d) holding the three-dimensional shape in the electrolytic cell for a period sufficient to form an adherent coating on the three-dimensional shape, (e) removing the three-dimensional shape from the bath, and (f) baking the three-dimensional shape to cure the adherent coating.
[0008] If the steel strip as received at the electrodeposition facility is ECCS—that is, if it has a chromium/chromium oxide coating, the chromium oxide coating may be removed (“stripped”) prior to or after the two-dimensional piece is cut from the strip.
[0009] Also, our invention includes an appliance housing comprising a piece of steel strip, the piece of steel strip having been formed into a three-dimensional form, and a (preferably crosslinked) cationic polymer deposited from an aqueous electrolytic bath on top of the chromium undercoat (that is, a coating of chromium between the steel and the polymer-containing outer coating). More succinctly, our invention includes a process for coating steel comprising electrocoating electrolytic chromium coated steel, substantially free of phosphate, in a bath comprising a cationic polymer. The electrolytic chromium coated steel need not be in a three-dimensional form, may be of any practical gauge, may be free of the chromium oxide layer typical of ECCS, and may be in a form for uses other than making appliance cabinets, such as automotive, shelving, tubing and architectural panels. A major advantage of our invention is that the substrate steel may be used as received from the manufacturer—that is, it needs no further treatment to be placed in the appropriate cationic resin-containing bath—and the resulting coating has excellent adhesion characteristics.
[0010] If, as received at the resin coating facility, the steel strip is more or less conventional ECCS (electrolytic chrome/chrome oxide steel), the oxide in the chrome oxide layer may be substantially removed Removal of the oxide may be accomplished in any practical manner, as by rinsing it in a solution of sodium hydroxide. Preferably, however, the steel as received can be steel strip which has been treated to form the chrome layer but not the additional chrome oxide layer. Clearly, this will save two steps—the addition of the chrome oxide by the supplier and the removal of the chrome oxide, or a substantial portion thereof.
[0011] When used herein, we intend for the following terms to have the meanings indicated: “appliance housing” or “appliance cabinet” means the coated metal housing or cabinet, or an appliance such as a washing machine, dryer, dishwasher, or other similar appliance; “preform” means a piece of steel strip which has been cut and bent, folded, fabricated, crimped, stamped, drawn, molded, or otherwise conformed to a shape useful as at least a part of an incipient appliance housing or cabinet, including doors, fronts, back panels, toe panels and brackets, or an end product other than for applicance; “three-dimensional shape,” as applied to an appliance housing or cabinet to a preform means the non-flat shape of a piece of steel strip useful as at least a part of an appliance housing or cabinet or a preform. “Cabinet” and “housing” have the same meaning herein.
DETAILED DESCRIPTION OF THE INVENTION
[0012] Electrolytic chromium coated steel (“ECCS”), sometimes referred to as tin-free steel (“TFS”), is black plate or low carbon sheet steel processed and thinly electrolytically plated with metallic chromium together with an outside surface of a chromium oxide film. The typical practice for making ECCS is to prepare an electrolyte containing 70 to 120 grams per liter of CrO 3 (chromic acid) together with small amounts of sulfate ions (about 0.2-0.8 grams per liter) and fluoride ions (about 1-5 grams per liter). See Allen, U.S. Pat. No. 3,642,587. The steel to be chromium-coated is the cathode. Much lower concentrations of chromic acid can be used according to the method of Ersan Ilgar disclosed in U.S. Pat. No. 6,331,241. In any case, a light coating of both metallic chromium and chromium oxide is normally placed on the steel sheet, almost always in the form of strip run more or less continuously through the electrolytic bath. In our invention, we may use electrolytic chromium coated steel (ECCS) having a coating weight of 2-20 mg/ft 2 , preferably 5 mg(±1.5 mg)/ft 2 , and most preferably 5 mg(±0.5 mg)/ft 2 , of metallic chromium but with chromium oxide completely absent or present in limited amounts up to 2 mg/ft 2 . The chromium may be applied in any known manner from an electrolytic bath (plating solution). While conventional ECCS may be used, we prefer that the sheet steel have a chromium coat as above described but is substantially free of chromium oxide. Our use of the term “tin-free steel” includes unfinished ECCS, meaning that only the chromium coating is placed on it, not the chromium oxide.
[0013] The chromium may be in the form of Cr(VI) or Cr(III), but Cr(III) is preferred, as Cr(VI) is generally criticized for its potential toxicity. The above recited coating weights are determined as trivalent chromium.
[0014] The resin-containing coating bath to be used in our invention may be any coating bath including a cationic polymer which may be deposited onto the chrome-coated substrate from an electrolytic bath.
[0015] Aqueous electrolytic coating baths useful in our invention—that is, containing cationic polymers which may be deposited onto the chrome-coated substrate from an electrolytic bath—include coating compositions described as useful in electrolytic bath applications in the following US Patents, which are hereby incorporated by reference in their entirety: Bosso et al U.S. Pat. Nos. 4,170,579 and 4,610,769, Corrigan et al U.S. Pat. No. 5,096,556, Moriarity et al U.S. Pat. No. 4,432,850, Roue et al U.S. Pat. No. 4,689,131, Kaylo et al U.S. Pat. Nos. 6,093,298, and 6,033,545, Karabin et al U.S. Pat. No. 6,190,525, McMurdie et al U.S. Pat. No. 6,110,341, Boyd et al U.S. Pat. No. 6,017,432, Augustini et al U.S. Pat. No. 6,017,431, Kaufman et al U.S. Pat. Nos. 5,820,987 and 5,936,012, Scott et al U.S. Pat. No. 5,464,887 and Valko et al U.S. Pat. No. 5,074,979. In our invention, we may use any coating containing a cationic polymer which may be electrodeposited on steel acting as a cathode, including all such compositions described in the above patents. The anode may be a carbon anode or any other anode useful in the art. The compositions are placed in a bath and the incipient appliance cabinet or housing parts, preforms, or other forms of steel as described herein are immersed in it and then subjected to an electric current in any effective manner, preferably the commonly used manner for coating appliance parts and other such workpieces including automotive parts and/or any other parts or partially fabricated forms made from steel. Most preferably the steel preforms or articles are substantially free of chrome oxide. The bath compositions described as useful for cationic electrodeposition in the above incorporated patents may be used with or without the various additives or adjustments to the basic bath formulation which may be the subject of the particular patents, such as a particular curing agent or crater control agent, the blocked isocyanate groups of Valko et al '979 or Boyd et al '432, a flatting agent such as described by Scott et al '887, a bactericide of Augustini '431, the microgels of Corrigan '556, the yttrium of Karabin '525, or organic phosphorous of McMurdie '341. Numerous other optional ingredients as are known in the art may be used in the coating bath.
[0016] The cationic polymer may, in some cases, be described as not dissolved, but in suspension in association with anionic moieties such as anionic surfactants; the polymer is generally in an aqueous base. The aqueous base may include pigments, dyes, and preferably a crosslinker for the cationic polymer; total solids will generally range from 10% by weight to 20% by weight but may vary considerably outside of this range.
[0017] In the electrodeposition of resins, the deposition rate at a given point on the surface of the cathodic workpiece will vary not only with its distance from the anode but with the shape of the workpiece—that is, whether the current must travel an indirect path through the bath to get to it; in addition, the process may be said to be dynamic in that the rate of deposition at a given point will vary with the insulating effects of the newly laid coating on other portions of the substrate. The ability of a process to coat a relatively inaccessible part of the surface of a workpiece has been the subject of much study. This phenomenon is observed, measured or known as throwpower, throwing power, or similar expressions, and is generally a factor to consider in the evaluation of resin-containing bath compositions. As defined in U.S. Pat. No. 4,933,056, throwpower is the property of the electrodeposition composition to coat out at varying distances from the counter-electrode with substantially the same density of product. Persons skilled in the art have measured throwpower in various ways, almost always in order to judge the acceptability of a coating composition used in an electrolytic bath. See Donald R. Hays and Charles W. White, “Electrodeposition of Paint: Deposition Parameters” Journal of Paint Technology vol. 41, No. 535 pages 461-471, August 1969; Motier et al U.S. Pat. No. 3,884,856; Hou et al U.S. Pat. No. 3,846,356; Davis et al U.S. Pat. No. 3,898,145; Blank U.S. Pat. No. 4,057,523; Corrigan U.S. Pat. No. 4,933,056; Bernards U.S. Pat. No. 5,068,013 (see the data in the tables at the top of column 8, expressing throwpower in terms of the ratio of current at one point to the current at another point); Moriarity et al U.S. Pat. No. 5,202,383, and Chung U.S. Pat. No. 5,314,594. Our invention, using a substantially phosphate-free chromium plated steel, with or without a chromium oxide coating, and using a cationic polymer-containing coating bath, generally not only evinces a throwpower substantially equivalent to that of prior art substrates in equivalent baths, but in some instances, particularly where there is no chromium oxide layer, can show substantial improvement in throwpower. Improvements in throwpower can enhance productivity rates, allow better coating thickness control, and/or provide substantial savings in electric power, depending on how the improvements are used. Since our invention may permit the use of less electric power to achieve a given throwpower ratio, it may be used to achieve more versatile economic as well as technical control over the entire resin electrocoating process. Thus, our invention includes a method of operating an electrolytic coating line wherein a steel object to be coated is placed as a cathode in a bath of coating composition comprising a cationic polymer in an electrolytic cell and subjected to an electric current in the bath for a residence time therein until a coating of a desired thickness on at least a first target area of the surface of the steel object is achieved for drying or curing, comprising (a) utilizing as the steel object an object made of steel having a coating of chromium metal and being substantially free of phosphate (b) determining a range of residence times necessary to achieve the desired coating on the object under a range of power conditions, and (c) employing a selected combination of power and residence time for said object within the bath.
[0018] According to Suematsu's U.S. Pat. No. 3,928,157, the adhesion of a coating to a steel substrate having a chrome surface is enhanced if the substrate has an Open Circuit Potential (“OCP”) of greater than −420 mVSCE, where SCE denotes a saturated calomel electrode and the measurement is taken after 15 seconds in 0.1 citric acid/0.2 M sodium hydrogen phosphate (pH 4.7). The Suematsu patent reports increases in the OCP after longer periods of time up to 48 hours. Suematsu's substrate included a layer of nickel.
[0019] For a comparison of our process to Suematsu's observations, chromium oxide was stripped from some samples of conventional ECCS (hereafter called “stripped” samples), and other samples were obtained of tin-free steel having been treated only to plate with chromium and not additionally with chrome oxide (hereafter called “not stripped”).
[0020] The oxide was stripped from the line trial material in 10M sodium hydroxide at 180° F. for 2 minutes, rinsed in warm tap water, rinsed in distilled water and dried under hot air. Within 5 minutes, an area on the sample was immersed in the prescribed electrolyte while the OCP vs. SCE was recorded. The samples were then exposed to the ambient laboratory environment and the OCP was recorded after 24 hours and 7 days at a different location on the sample. Line trial samples with intact oxides were tested as well. Circulation cell material was produced using a dilute plating chemistry consisting primarily of chromate acid ions, following the methods of Ilgar's U.S. Pat. No. 6,331,241, which minimizes hexavalent chromium concentrations.
[0021] Three replicates per condition were tested for the line trial material, while duplicate measurements were made for the circulation cell material. Table 1 shows the OCP values after 15 seconds. In general, no significant change in the OCP was observed for the stripped panels. Immediately after stripping, the OCP was approximately −670 mV SCE , then decreased slightly to approximately 680 after 24 hours. After 7 days exposure the OCP was between −660 and −665 mV SCE . The OCP of the unstripped TFS sheet was approximately −670, similar to that observed at 24 hours after stripping. The OCP of the circulation cell is similar to those observed for the stripped samples after 24 hours in the atmosphere.
OCP(mV SCE ) OCP OCP t = 0 h OCP OCP Not Circ. Sample Post−strip T = 24 h T = 7 d stripped Cell 1 −670 −684 −661 −672 −683 2 −673 −681 −665 −669 −687 3 −672 −678 −664 −670
[0022] Contrary to implications of Suematsu's results, finished painted (electrocoated) steel made by our process has been found to have both excellent detergent resistance and humidity resistance. We prefer that the chrome-coated steel used in our process should have an OCP lower (more negative) than −500 mV SCE .
[0023] In addition, our invention virtually eliminates filiform corrosion. To demonstrate this, a filiform corrosion test was based on ASTM D 2803, Filiform Corrosion Resistance of Organic Coatings on Metal. Panels used included ECCS panels free of phosphate and having a commercial resin electrocoat. The scribe was made in the middle of the e-coated panel. The panels were placed in the ASTM B 117 salt spray cabinet for 24 hours. The panels were rinsed with D.I. water and then placed in 80 percent relative humidity at 80° F. for 500 hours. All three samples of phosphate-free ECCS evidenced no filiform corrosion at all. In a 1000 hour filiform corrosion test at 80% relative humidity panels coated according to our invention again showed no filiform corrosion. | Steel cabinet parts and other steel objects are electrocoated in a cationic resin-containing bath. The steel objects are chromium-coated, free of phosphate and preferably free of chromium oxide. The products are not significantly subject to filiform corrosion, and the process is economically beneficial because throwpower is more easily controlled than in previous processes. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/221,624, filed Jul. 28, 2000.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
This invention was made with Government Support under Grant No. DAAD19-00-1-0400, awarded by the Department of the Army, and Grant No. N00014-96-1-G014, awarded by the Office of Naval Research. The Government has certain rights in this invention.
FIELD OF THE INVENTION
This invention relates to the detection of a molecular species using heterodyned laser light.
BACKGROUND OF THE INVENTION
There has been long recognized a desire to automate the analysis of a wide variety of substances including chemical and biochemical materials, contaminants, biological warfare agents, and generally any substance, the presence and/or amount of which is desired to be determined. In recent years, on-chip systems have been developed for molecular diagnostics, e.g., for the detection of antigens by combination with antibodies or the analysis of nucleic acids via hybridization. The systems require the mixing of conjugate antibodies or the use of fluorescent antibodies or hybridizing fluorescent molecules during preparation, and, while being miniaturized nevertheless still require macroscopic techniques such as external light sources, external electro-optical detectors, and electronic instrumentation, all of which significantly limit the size and flexibility of such on-chip devices. Particularly as would be applied to military operations there is a need for fully integrated, field portable, and sensitive chip technology which can work reliably in demanding situations. Simply scaling down existing technologies, such as fluorescent measurement schemes, to the chip scale does not provide effective solutions. Moreover, any new technology must minimize meticulous sample preparation and handling steps, which limits the robustness of current technologies.
There has also been a growing need to develop microscale devices that can manipulate and transport relatively small volumes of fluids. These devices have applications in many areas of engineering, including propulsion and powered generation of micro-satellites, micro-air vehicles, inkjet printer heads, and bioanalytical instruments. See for example “PIV measurements of a microchannel flow” by C. D. Meinhart et al., Experiments in Fluids (1999) 414-419, the disclosure of which is incorporated herein by reference. When dealing with minute quantities of contaminants, for example, methods of separating or isolating the molecules to be diagnosed become important. Electrophoretic systems have been developed which aid in such techniques. Such systems separate molecules by their unique directed motions in an electric field.
In recent years, lasers have been put to use in molecular diagnostics. Robert Frankel et al. U.S. Pat. No. 5,637,458 (the disclosure of which is incorporated herein by reference) describes a system for biomolecular separation and detection of a molecular species that uses a solid state laser detector formed with a sample channel. The presence of a molecular species is indicated by a frequency shift in the laser's output which is detected by optical heterodyning the laser's output with the output of a reference laser. The interior of the sample channel can, optionally, be coated with a ligand for binding a molecular species of interest. The system involves rather complex preprocessing of the sample by electro-osmotic separation in channels that are lithographically formed in a two dimensional planar substrate and/or by a nanostructural molecular sieve formed of spaced apart posts defining narrow channels. Although an attempt at integrated system is provided by U.S. Pat. No. 5,637,458, it does not entirely provide a fully integrated optical chip device.
Also recently, highly coherent semiconductors, lasers and laser arrays have been developed primarily for telecommunications applications. See for example, C. E. Zah et al., IEEE Photon. Technol. Lett. Vol. 8 pp. 864-866, July 1996. In addition, widely tunable semiconductor lasers have been developed, in particular, sampled-grating distributed Bagg reflector (SGDBR) lasers. See, for example “Tunable Sampled-Grading DBR Lasers with Integrated Wavelength Monitors,” by B. Mason et al., IEEE Photonics Technology Letters , Vol. 10, No. 8 August 1998; 1085-1087 and “Ridge Waveguide Sampled Grating DBR Lasers with 22-nm Quasi-Continuous Tuning Range,” by B. Mason et al., IEEE Photonics Technology Letters , Vol. 10, No. 9 September 1998, 1211-1213. These widely tunable lasers are based on the use of two-multi-element mirrors as described in Coldren, U.S. Pat. No. 4,896,325. The foregoing also includes a Y-branch splitter with a detector in each branch for wavelength determination: Disclosures of the foregoing three publications and Coldren, U.S. Pat. No. 4,896,325 are incorporated herein by reference.
SUMMARY OF THE INVENTION
The present invention provides a fully integrated optical sensor for on-chip analysis of immunoassays and molecular diagnostics. The present invention measures minute changes in the index of refraction (−10 −7 ), within one micron of a microchannel surface, which can be the result of a specific heterogeneous chemical reaction or an antigen-antibody binding event.
The present invention does not require mixing of conjugate antibodies or fluorescent molecules during sample preparation as used in related art devices and techniques. Further, the present invention does not require external devices such as external light sources, fluorescent filters, or external recording optics. Unlike fluorescence imaging, which is a macroscopic technique that is applied to bio-chips, the present invention operates at the microscopic scale. The system has sensitivities that can detect single molecules, is fully integratable into the chip, and avoids mixing steps during sample preparation.
In particular, an integrated optical chip device usable for molecular diagnostics in what we term a tunable laser cavity sensor (TLCS) is flip chip bonded to a microfluidic chip. The TLCS is formed from a reference laser and a sensor laser, each comprising a waveguide having a gain section, a partially transmissive mirror section, and a coherent light beam output section, one or both of the waveguides having a phase control section. The light beam output sections of the reference and sensor lasers are joined to enable the coherent light from these sections to interfere, providing a heterodyned frequency. The sensor laser has a thinned waveguide region exposing evanescent field material to form a cavity and which detects the presence of a molecule by a heterodyned frequency shift.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of an assembled biosensor/analyzer showing the optical sensor flip-chip bonded to the biofluidic chip;
FIG. 2 is a top plan schematic view of a heterodyned tunable reference and sensor lasers with an intracavity sensor region;
FIG. 3 is a schematic, cross-sectional vertical view of a microfluidic chip of this invention and the optical sensor flip-chip bonded thereto;
FIG. 4 is a bottom perspective view showing the tunable laser cavity sensor with control electrodes for gain, phase, and mirror currents;
FIG. 5 shows an exploded perspective view of the assembled biosensor/analyzer, similar to FIG. 1 , but showing how the tunable laser cavity sensor is flip-chip bonded to the microfluidic chip;
FIG. 6 is a cross-section of a vertical schematic view of the assembled tunable laser cavity chip and microfluidic chip showing electrical and gasket connection and the interaction region thereof;
FIG. 7 is a top plan schematic view of a one-dimensional tunable laser cavity sensor array composed of multiple heterodyne tunable lasers with intracavity interaction regions;
FIG. 8 is a schematic plan view of the tunable laser cavity sensor of FIG. 4 ;
FIG. 9 is a cross-sectional, schematic view of a ridge waveguide usable in the present invention;
FIG. 10 is a cross sectional perspective view of reference and sensor ridge waveguides;
FIG. 11 is a cross sectional schematic view of a buried rib waveguide usable in the present invention;
FIG. 12 is a cross sectional perspective schematic view of reference and sensor buried-rib waveguides;
FIG. 13 is a schematic plan view of the tunable laser cavity sensor of FIG. 4 ; and
FIG. 14 is a schematic plan view of the tunable laser cavity sensor similar to that of FIG. 13 , but with left and right side sampled-grating mirrors.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 an integrated optical chip device 10 in accordance with this invention is formed by flip-chip bonding an InP-based laser/detector chip 12 to a Si-biofluidic chip 14 . The InP optical sensor chip measures slight frequency shifts due to evanescent wave interactions with fluidic medium in a laser cavity, as will be described in more detail below, and can be referred to as a tunable laser cavity sensor (TLCS).
Referring additionally to FIG. 3 , the biofluidic chip 14 contains a microfabricated flow cell with an opening 16 adjacent a cavity in the sensor chip 12 as will be described below in more detail. Microchannel 18 feeds fluid to the opening 16 and an outlet microchannel 20 removes effluent from the opening 16 . The opening 16 and the sensor cavity (not shown in FIGS. 1 and 3 ) serve as a sample chamber, a diffusion-dominated region, where analyte can diffuse to a wall of the sensor cavity. An adsorbent, such as a capture antibody for immunoassays, or a ligand for a chemically reactive species, is provided, e.g., by deposition, adjacent the sensor cavity. When a particular reaction occurs on the surface, or an antigen binds to an antibody on the surface, a change in index of refraction will occur adjacent the surface and this changes the lasing frequency of the tunable laser cavity sensor, which is detected by a heterodyne detector, again as will be described in more detail below.
The fluidic channels 18 and 20 can be formed by deep reactive ion etching (DRIE) into a 300 micron thick Si wafer. DRIE provides an excellent means for machining high aspect ratio channels with good tolerances. Access ports 19 and 21 respectively, for the inlet and outlet channels 18 and 20 are etched into the bottom of the Si substrate. The inlet and outlet channels 18 and 20 are etched through the entire depth of the wafer. The opening 16 which connects to the sensor laser cavity is formed by a nominally 100×100 micron channel etched between the inlet and outlet channels 18 and 20 on the top surface of the chip 14 . A glass cover slip 23 seals the access ports 19 and 20 and is provided with corresponding openings 25 and 27 .
In the embodiment shown in FIG. 3 , a pressure gradient, such as a syringe pump can be used to propel fluid through the device. See, for example, C. D. Meinhart et al., supra.
The TLCS optical sensor element is shown schematically in FIG. 2 . Two distributed-bragg reflector (DBR) tunable lasers 22 and 24 are integrated with a Y-branch coupler 26 and a photodetector 28 . One of the DBR tunable lasers 22 is a reference laser, the other 24 being a sensor laser. The photodetector 28 provides heterodyne detection of small changes in amplitude or frequency of the sensor laser 24 relative to the reference laser 22 . As is known, the frequencies of the reference and sensor lasers can be set, as indicated at 30 and 31 by adjustment of the control sections, more particularly by adjustment of the respective gain 32 , 34 and phase 36 , 38 sections of the waveguides. Each waveguide has a partially transmissive grating mirror section 40 and 42 and a coherent light beam output section 44 and 46 which are joined at the mixer detector section 28 .
The interactive region 29 of the sensor waveguide is formed between the gain and phase control sections, respectively 34 and 38 , and the sampled grating mirror section 42 . However, the particular order of the components between the mirrors is not critical and other configurations are equally useable. Thus, all permutations of the locations of the gain section 34 , phase control section 38 and interactive region 29 can be used. For example, the order from the cleaved facet 24 ( FIG. 4 ) can be phase control section 42 , gain section 38 and interactive region 29 , etc. Also, while a phase control section is shown on both the reference laser 22 and sensor laser 24 , it is sufficient to have it on only one of the lasers in order to tune one to the other. As indicated, the left ends of the lasers 22 and 24 are formed by cleaved facets. Both the left end facet mirrors and the right side grating mirrors can be sampled-grating mirrors to provide for wider tunability of the lasers output wavelength, in which case, the opposed sampled-grating mirrors would preferably have different sampling periods. Using lasers with different sampled grating periods is described in the aforementioned Coldren, U.S. Pat. No. 4,896,325.
As shown, the frequency output of the sensor waveguide differs by ±Δλ from the frequency of their reference waveguide. By adjusting the tuning electrodes as shown in FIG. 2 , one can enhance the measurement resolution by tuning to possible molecular bond resonances, e.g. in the 1550 nm wavelength range. Researchers at the University of California in Santa Barbara have pioneered DBR lasers with extended tuning ranges—so called sampled grating-DBR lasers. The lasing wavelengths of these lasers can be tuned up to 100 nm, enabling the measurement of the index of the perturbing species versus wavelength over a relatively wide range to better identify their chemical nature.
FIGS. 13 and 14 show schematic plan views of TLCSs using either a simple DBR partially transmissive mirror or two SGDBRs, respectively. The TLCS of FIG. 13 is that of FIG. 4 shown in plan view, with corresponding lead lines. In the TLCS of FIG. 14 , the SGDBR configuration replaces the simple grating on the right side as well as the opposite laser facet mirror with sampled grating mirrors, respectively 57 and 59 , for extended tuning range.
Referring to FIG. 4 , the TLCS is shown in more detail. The tunable cavity sensor is fabricated by integrating a tunable DBR sensor laser 22 with a reference laser 24 and combining them into a heterodyning detector 28 to accurately monitor changes in the modal index for loss due to adsorbates or interactions at the surface of a thinned interaction region 48 on the sensor laser 22 . The InP chip 12 is formed with reference and sensor lasers 22 and 24 , as will be described in more detail hereinafter, each of which carries gain control electrodes, respectively, 50 , 52 and phase control electrodes, respectively, 54 , 56 spaced from mirror control electrodes, respectively, 58 , 60 overlying a partially transmissive grating mirror 43 . As described with respect to FIG. 4 , the reference and sensor coherent light beam output sections 62 and 64 join to deliver interfering light beams at the detector 28 , sensed at a detector electrode 66 thereon. Although a “Y-branch” waveguide combiner element 62 and 64 is shown, another type of waveguide combiner such as a “Multimode-interference” element, may also be employed as is well known to those skilled in the art. The cladding of the sensor laser waveguide 24 is thinned to form the sensor cavity 48 to expose the evanescent fields of the lasing mode, and provide an interaction region.
As in Frankel et al., U.S. Pat. No. 5,637,458, the surface of the cavity 48 can be coated with various ligands, such as capture antibodies, various binding molecules, or reactive molecules. After flip-chip bonding to the Si microfluidic chip, as described hereinafter, the thin waveguide region 48 then forms one side of an interaction chamber in which analytes can diffuse to the treated surface. When a particular reaction occurs on the surface, or an antigen binds to an antibody adsorbate on the surface, a change in index of refraction, Δn s , will occur at the region just above the surface. Since a portion of the laser mode, Γ xy , fills this transverse region, the modal index is changed by an amount, Γ xy Δn. Also, the interaction region extends along the axis of the laser to fill an axial fraction Γ z , of the cavity, so that the net fill-factor for region in which the perturbation takes place is Γ xy Γ z .
Since the lasing wavelength changes in direct proportion to the net weighted change in index (and frequency as the direct negative), the relative change in laser output wavelength, λ, (or frequency, f) is given by:
Δλ λ = Γ xy Γ z Δ n s n _ = - Δ f f
For a typical sensing configuration, Δn s ,=0.01, and Γ xy Γ z ,=0.01, and assuming the average index of the laser cavity is n=3.3, then Δλ=0.05 nm, or Δf=−6 GHz@λ=1550 nm. Now, if this deviation were to be measured in the optical domain, a quarter-meter or larger spectrometer would be necessary to obtain sufficient resolution to see the effect, which would be very difficult at the chip level. However, with an integrated heterodyne detector, the shifted optical frequency can be down converted to the VHF radio frequency range where simple frequency counters can be used to measure the difference frequency with 1 Hz accuracy. Using heterodyne detection with two semiconductor lasers, a 6 GHz frequency shift can be measured with an accuracy of about 10 MHz, because this is the approximate linewidth of such lasers.
Put another way, again assuming the index shift in the small perturbation region, ns=0.1, the net fill-factor of this region relative to the volume of the guided mode can be as small as □xy□z,=(10 MHz)(3.3)/(0.1)(193 THz)=1.7×10 6 . Then, for example, if the transverse over lap, □xy is only 0.1% (very conservative estimate of the evanescent field), the axial □z can be as small as 0.17%. Therefore, with a net laser cavity length of 500 μm, single submicron particles can be detected.
FIG. 5 depicts flip-chip bonding of the InP TLCS 10 to the Si-biofluidic chip 14 . In this embodiment, the biofluidic chip 14 is formed with integrated inlet and outlet channels, respectively, 68 and 70 leading to and from a sample cavity 72 having the gain and phase control circuitry 11 and heterodyne detection circuitry 13 integrated therewith, connecting to the InP chip components via the conductive lines, respectively, 15 and 17 , as previously shown in FIG. 1 .
In this fully-integrated design, the channels are sufficiently small so that capillary forces can be used to fill them or alternatively, an onboard pump could be used to propel the fluid.
Details of connection and operation of the integrated optical chip of the present invention are shown in FIG. 6 . The microfluidic chip 14 is shown with the direction of microchannel flow out of the plane. The chip 14 carries electrical contacts 74 and 76 , respectively, for the gain and phase control of the TLCS. The sample cavity 72 of the biofluidic chip 14 , (the thinned sensor cavity 48 of the TLCS) is interconnected by a gasket 78 to form a sample chamber 80 defining an interaction region. The exposed evanescent field material of the sensor chamber 48 is provided with an adsorbate layer 82 . The laser guided mode is illustrated at 84 showing propagation of the laser beam along the waveguide to and from the sensor mirror section 42 adjacent the sampled grating mirror 43 .
As shown, the InP optical sensor chip measures slight frequency shifts due to evanescent wave interactions with the fluid medium in the sample chamber 80 , which serves as a diffusion-dominated region where analytes can diffuse to the adsorbate layer 82 . The adsorbate layer, which can be referred to as an interaction layer, can be formed as a capture antibody for immunoassays for a ligand for some chemically reactive species. When a particular reaction occurs on its surface, or an antigen binds to an antibody on the surface, a change in index of refraction will occur adjacent the surface, and this changes the lasing frequency. The inclusion of an “interaction region within the cavity 48 of the sensor laser provides for a change in the modal index of refraction (gain or loss) within this region due to the surface absorption or chemical interaction, which overlap the evanescent fields of the laser mode.
The relative frequency change, Δf/f, of the laser is just equal to the relative modal index change times a fill factor, ΓΔn/n, and this frequency change, Δf, can be measured very accurately in the radio frequency (RF) range after down conversion by mixing with the unperturbed laser in the heterodyne detector, to measure changes in modal index of refraction inside the sensor laser cavity 48 with a resolution estimated at about Δf/f=10 MHz/200 THz˜10 −7 .
Antibody immobilization strategies utilizable with this invention can exhibit high sensitivity and high selectivity. For example, using antibodies immobilized to polystyrene and using waveguide illumination of fluorescence, it has previously been demonstrated that cTnI (troponinI) can be detected down to 1 pm. Sensitivity has been reported in the literature down to the fM range using thin-film silicon oxynitride waveguides approximately 1 micron thick; see Plowman et al., 1996. In a similar fashion, DNA has been detected down to the 50 fM level using evanescent planar waveguides with covalently attached capture oligonucleotides probes within twelve minutes; see Bucach et al. 1999.
In many situations it may be desired to detect more than one kind of molecular species or more than one kind of interaction. This may be possible by sweeping the wavelengths of the reference and sensor lasers by applying suitable currents to the control electrodes and observing characteristic resonances in the index measurement vs. λ. The use of a widely-tunable laser such as a sampled-grating DBR will facilitate this option.
Another approach to detect a multiplicity of species is to use a one-dimensional TLCS array on the same chip, as illustrated in FIG. 7. A plurality of TLCSs which can be a dozen or more, but of which only three TLCSs 86 , 88 and 90 are shown. The TLCSs form an array interconnected by an elongate sample chamber 94 . The sample chamber can be contained on a Si biofluidic chip with separate sample cavities aligned with each sensor laser cavity, and/or a single gasket can surround a single sample cavity that runs across all of the TLCSs, forming a succession of sample chambers with successive interactive regions 98 , 100 and 102 , whereby fluid flows serially from the first interactive region 98 to the last interactive region 102 , as shown by the arrow 104 .
Depending upon the binding chemistry deposited on the sensor cavity, each sensor cavity could measure a different constituent of the flow, such as pH, temperature, antigen, etc. A single fluidic flow cell doses each interaction region TLCS. The practical number of TLCS array elements and thus sensed properties, is mainly limited by the desired to finite chip size. The active elements, including the two DBR lasers are spaced, e.g., by about 500 μm so as to allow space for flip-chip contacts and to avoid cross talk. Thus, the device is applicable to the analysis of a broad range of chemical and biological assays. For example, one could test for such biological warfare agents as Botulinium Toxin, Ebala and Anthrax, by using Ovalbumin, MSZ and Bacillus Globigil to simulate the invasion by such warfare agents into a human bloodstream. Again, spectral index information can also supplement the index information at each element if the wavelengths are varied across some range.
In a further embodiment of the invention, illustrated in FIG. 8 , a series of electrodes for dielectrophoresis (DEP) can be fabricated in the microchannel sample cavity 72 and, with the sensor cavity 48 , forms the sample chamber 80 (all with reference to the components of FIG. 6 ). Many biological particles (such as cells and large macromolecules) exhibit both positive and negative diaelectrophoretic, constants, depending upon the frequency of applied electric field. See Jones, 1995. By changing the frequency and intensity of the electric field, dielectrophoresis can be used to induce biological particles toward or away from the DEP electrodes and the sensor. The force due to DEP is proportional to particle volume, and therefore will be more effective for large particles.
When a biological particle exhibits a positive dielectrophoretic constant, the particles can be induced toward the DEP electrodes and will be less likely to deposit on the laser sensor cavity area. FIG. 8 , shows the application of force to a fluid, at 106 , carrying particles 108 . When sensing analytes with low particle concentrations, the frequency of the electric field can be adjusted to increase the concentration of particles near the sensor area, as shown at 110 , making the measurements more sensitive. Considering the situation where one is continuously monitoring particle concentrations in a flowing fluid by observing the concentration of particles attached to the sensor wall, and knowing a prior the equilibrium constant for the reaction at the wall, the particle concentration can be measured most accurately over a limited range, depending on the optimum measurement concentration at the sensor. This range can be extended using DEP and the TLCS for feedback control. This system can be calibrated by applying known particle concentrations, varying DEP frequency and amplitude, and monitoring measurements from the TLCS.
DEP has been used to increase particle concentrations, separate particles, and capture particles with relatively low voltages compared to electrophoresis. Miles et al., (1999) used DEP to manipulate DNA, Bacillus globigii spores and Erwinia herbicola bacteria. They demonstrated the feasibility of capturing DNA molecules using DEP, with a relatively simple microfluidic device. While Washizu et al. (1994, 1995), used DEP to stretch and position DNA molecules and biopolymers. DEP coupled with field-flow-fractionation has been used successfully to separate polystyrene beads. Wang et al (1998), and to separate human breast cancer cells from normal blood cells, Yang et al. (1999). The technique of this invention therefore builds upon established technology in the field of optical immunosensors. These sensors use optical detection techniques to determine the presence and concentration of antigens by monitoring antigen/antibody binding reactions to capture antibodies that are immobilized to a wall, Rabbany et al. (1994).
The dielectrophoresis force of a lossless dielectric sphere is given by Jones (1995) as
F DEP = 2 πɛ 1 R 3 K V _ E o 2 ( I )
where ε 1 and ε 2 are the permittivity of the fluid medium and the lossles dielectric sphere, R is the radius of the sphere, E o is the applied electric field. The dielectric constant K can be written using the Clausius-Mossotti function (Jones, 1995)
K = ɛ 2 - ɛ 1 ɛ 2 + ɛ 2
Equation (I) indicates the DEP force is proportional and parallel to the gradient of the electric field squared, and proportional to the cube of the sphere radius. The DEP force is present only for spatially varying electric fields and works in either AC or DC fields. If the permittivity of a particle is greater than its surrounding medium, then K>0 and the particle is said to have a positive dielectrophoretic constant and is attracted in increasing electric fields.
Bahaj and Bailey (1979) state that for geometrically similar electrodes, the DEP force scales as
F DEP ≈ V 2 L e 3 ( 3 )
where V is the magnitude of the applied voltage and L e is the effective length of the electrodes. Therefore, smaller geometries will increase the sensitivity of a particle to the dielectrophoretic effect (Jones, 1995). In addition, for a constant DEP force decreasing the geometric length scale, allows for a reduction in the applied voltage.
In the case of conductive losses, the DEP constant K can be a function of the applied voltage frequency. Therefore, the magnitude and direction of the DEP force can be manipulated by varying the voltage frequency. The biological particles that exhibit K<0 can be passively levitated using DEP so that they will be less likely to deposit on channel walls. When high-sensitivity detection is desired, the electric field can be adjusted (i.e. in magnitude and frequency) so that the concentration of particles near the laser sensor interface is increased, making the molecular detection more sensitive.
In fabricating the TLCS chip, known InP growth and fabrication procedures and DBR laser fabrication characterization procedures can be used. Existing 3-D beam propagation modeling (BPM) software can be utilized to provide inclusion of lateral and transverse variations in straight guides, such as in the interaction region, as well as the actual variations in bends, such as in the Y-branches offset regions for gain and detector circuitry, as shown in FIG. 5 , will be used.
Referring to FIGS. 9 and 10 , after a first growth, the lower band gap gain/detector layers are removed in the passive sections and the grating lines are etched into the underlying passive guide in the grating mirror section. FIG. 9 , a transverse cross section of a ridge waveguide is shown. The InGaAsP waveguide 112 is formed on an n-InP buffer and substrate 114 . A p-InP ridge waveguide 116 is formed on the InGaAsP waveguide (regrowth) to provide the top cladding and contact layers, the latter formed by InGaAs. Sampled grating lasers can be made with the same procedure. See for example Mason et al. (1998).
Referring to FIG. 10 , to form the sensor cavity 48 containing the interaction region, the cladding over the optical waveguide is thinned to expose the vertical evanescent optical field. This results in a much smaller ridge height over the center of the guide but some lateral ridge structure must remain to provide lateral waveguiding. The resultant TLCS with its reference waveguide 116 and sensor waveguide 118 are thus formed. Inert polymer 120 is left at the corners of the ridge guides 116 and 118 to eliminate interactions with the fluid, which is especially important for the reference laser which is not to be affected by the fluid.
Referring to FIGS. 11 and 12 , in another embodiment of the invention, the waveguides can be buried-rib waveguides formed by etching away all the layers outside of the desired optical channel. As shown in FIG. 11 , the n-InP substrate 122 carries a waveguide 124 and adjacent quantum well 128 in a p-InP layer contained in an implanted region 126 under a SiNx layer 130 , an InGaAs contact layer 132 and Ti/Pt/Au contact layer 134 providing electrical contact.
As shown in FIG. 12 , for the buried-rib embodiment, thinning results in a uniform lateral surface 136 , obtained by removing the passive waveguide layer beneath the surface. The result is a TLCS 138 containing reference and sensor waveguides 140 and 142 with the sensor cavity 144 defining the interactive region of the TLCS.
Referring again to FIG. 6 , to form the adsorbent layer 82 , one can coat the InP laser cavity with a thin film of silicone or other hydrophobic polymer material. For example, antitroponin I can be deposited onto the thin film of silicone. Pluronics, block co-polymers, can be used as an intermediate in binding antibody to a surface. In one embodiment, the coated surfaces passivated or blocked with a sugar/protein mixture to both stabilize the deposited antibody and to cover portions of the InP surface where antibodies are not present. Ideally, the application process and drying process are optimized to the thinnest layer possible to make the surface immediately active, to minimize non-specific binding and to stabilize the antibody activity. The passivating can be sprayed onto the antibody-coated surface in a fine mist until the surface is wetted. The wetted surface can then be washed thoroughly with a buffer solution to remove excess protein and sugar, and antibody that has been loosened in the passivating process. A final layer of passivating material can then be applied to maximize the stability of the active antibody.
The captured chemistry can be deposited on the small 3 μm×500 μm interaction region of the laser cavity sensor. When an array of multiple laser cavity sensors are used in a single microfluidic channel, adjacent laser cavities, which are positioned approximately 500 μm apart, are each coated with a separate reference chemistry.
The detector signal from the heterodyne-mixed laser cavity sensor will contain a beat frequency, which will correspond to the amount of bound target analyte. The relationship between the beat-frequency versus time occurred and the target species concentration can be characterized. One way of handling the beat -frequency versus time relationship is to measure the time evolution of the beat frequency. One can then correlate the curve to a known concentrate of analyte, and a known flow condition.
While the invention has been described in terms of specific embodiments, various modifications can be made without departing from the scope of the invention.
REFERENCES
The following references are each incorporated herein by reference:
Bahaj, A. S., & Bailey, A. G. 1979. Dielectrophoresis of small particles, Proc. IEEE/IAS Annual Meeting, Cleveland, Ohio, October, pp. 154-157.
Bucach, et al. 1999. Anal. Chem. Vol. 71, pp. 3347-3355.
Duffy, D. C., McDonald, J. C., Schueller, O. J., & Whitesides, G. M. 1998. Rapid prototyping of microfluidic systems in Poly(dimethyl siloxane), Anal. Chem ., Vol. 70, pp. 4974-4984.
Fish, G. A., B. Mason, L. A. Coldren, and S. P. DenBaars, 1999. Monlithic InP optical cross connects: 4×4 and beyond Photonics in Switching '99, Santa Barbara, Calif., #JWB2, 339341, July 19-23.
Fontana, E., R. J. Pantell & S. Strober. 1990. Surface plasmon immunoassy. Ap. Opt ., 29, 4694-4703.
Jones, T. 1995 . Electromechanics of particles , Cambridge University Press, New York, N.Y.
Jorgenson, R. C. & S. S. Yee. 1994. Control of the dynamic range and sensitivity of a surface plasmon resonance based fiber optic sensor, Sensors and Actuators A , 43, 44-48.
Lee, H., et al. 1998. Microchip platform for automated biochemical analysis, Poster, Solid State Sensors and Actuators Workshop, Hilton Head, S.C., June 7-11.
Leidberg, B., C. Nylander & I. Lundstrom. 1983. Surface plasmon resonance for gas detection and biosensing, Sensors and Actuators , 4, 299-304.
Liu, R. H, Sharp, K. V., Olsen, M. G., Stremler, M, Santiago, J. G., Adrian, R. J., Aref, H., Beebe, D. J., 1999. A passive micromixer: 3-D serpentine microchannel, 10 th International Conference on Solid - State Sensors & Actuators: Transducers '99, Sendai, Japan, pp. 730-733.
Mangru, S., Harrison, D. J. 1998. Chemiluminescence detection in integrated post-separation reactors for microchip-based capillary electrophoresis and affinity electrophoresis, Electrophoresis , Vol. 19, pp. 2301-2307.
Mason, B., S. P. DenBaars, and L. A. Coldren, 1998. Tunable sampled grating DBR lasers with integrated wavelength monitors, IEEE Photon. Techn. Letts ., 10, (8), 1085-1087, August.
Mason, B., G. A. Fish, S. P. DenBaars, and L. A. Coldren, 1999. Widely Tunable Sampled Grating DBR laser with integrated electroabdorption modulator, IEEE Photon. Techn. Letts ., 11, (6), 638-640, June.
Meinhart, C. D., S. T. Wereley, and J. G. Santiago 1999 PIV Measurements of a Microchannel Flow. In press Exp. in Fluids
Miles, R., P. Belgrader, K. Bettencourt, J. Hamilton, S. Nasarabadi 1999. Dielectrophoretic manipulation of particles for use in microfluidic devices, MEMS - Vol. 1 , Microelectromechanical Systems ( MEMS ), Proceedings of the ASME International Mechanical Engineering Congress and Exposition , Nashville, Tenn., Nov. 14-19.
Ocvirk, G., Tang, T., Harrion, D. J. 1998. Optimization of confocal epifluorescence microscopy for microchip-based miniaturization total analysis systems. The Analyst , Vol. 123, pp. 1429-1434.
Paulus, A. 1998. Capillary electrophoresis of DNA using capillaries and micromachined chips. American Laboratory , April Issue.
Plowman, T. E., W. M. Reichert, C. R. Peters, H. K. Wang, D. A. Christensen & J. N. Herron. 1996 . Biosensors & Bioelectronics , Vol. 11, No. 1/2, pp. 149-160.
Rabbany, S. Y., B. L. Donner & F. S. Ligler. 1994. Optical Immunosensors. Critical Reviews in Biomedical Engineering , 22 (5/6), 307-346.
Rogers, et al. Constructing single- and multiple-hellical microcoils and characterizing their performance as components of microinductors and microelectromagnes, JMEMS, Vol. 6, pp. 184-192.
Santiago, J. G. S. Wereley, C. D. Meinhart, D. J. Beebe, & R. J. Adrian 1998. A PIV system for microfluidics. Exp. Fluids , Vol. 25 No.4, pp. 316-319.
Schueller, et al. 1997. Fabrication and characterization of classy carbon MEMS. Chem. Mater . Vol. 9, pp. 1399-1406.
Stremler, M. A., Aref, H. 1998. Chaotic advection in a static microscale mixer. 51 st Annual Meeting of the American Physical Society's Division of Fluid Dynamics , pp. 2131.
M. Volpert, C. D. Meinhart, I. Mezic, and M. Dahleh 1999. An actively controlled micromixer. ASME—IMECE '99 MEMS symposium , Nashville, Tenn.
Wang, X-B, Vykoukal, J., Becker, F. & Gascoyne, P. 1998. Separation of polystyrene microbeads using dielectrophoretic/gravitational field-flow-fractionation. Biophysical Journal , Vol. 74, pp. 2689-2701.
Washizu, M., S. Suzuki, O. Kurosawa, T. Nishizaka, and T. Shinohara, 1994. Molecular dielectrophoresis of biopolymers, IEEE Transactions on Industry Applications , Vol. 30, No. 4, pp. 835-842.
Washizu, M., O. Kurosawa, I. Arai, S. Suzuki, N. Shimamoto, 1995 Applications of electrostatic stretch and positioning of DNA, IEEE Transactions on Industry Applications , Vol. 32, No. 3, pp. 447-445.
Yang, J. Huang, Y., Wang, X., Wang, X-B, Becker, F. Gascoyne, P. 1999. Dielectric properties of human leukocyte subpopulations determined by electrorotation as a cell separation criterion. Biophysical Journal , Vol. 76, pp. 3307-3314. | An integrated optical chip device for molecular diagnostics comprising a tunable laser cavity sensor chip using heterodyned detection at the juncture of a sensor laser and a reference laser, and including a microfluid chip to which the sensor chip is flip-chip bonded to form a sample chamber that includes exposed evanescent field material of the tunable laser cavity to which fluid to be diagnosed is directed. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 10/364,358, filed Feb. 12, 2003, now U.S. Pat. No. 7,207,335, which is a continuation of U.S. application Ser. No. 09/021,541, filed Feb. 10, 1998, now U.S. Pat. No. 6,561,190, which claims the benefit of Australian Application No. PO5045, filed Feb. 10, 1997, each incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to a mask and a vent assembly therefor.
The mask and vent assembly according to the invention have been developed primarily for the venting of washout gas in the application of continuous positive airway pressure (CPAP) treatment in conjunction with a system for supplying breathable gas pressurised above atmospheric pressure to a human or animal. Such a system is used, for example, in the treatment of obstructive sleep apnea (OSA) and similar sleep disordered breathing conditions. However, the invention is also suitable for other purposes including, for example, the application of assisted ventilation or respiration.
The term “mask” is herein intended to include face a, nose masks, mouth masks, nasal pillows, appendages in the vicinity of any of these devices and the like.
BACKGROUND OF THE INVENTION
Treatment of OSA by CPAP flow generator systems involves the continuous delivery of air (or other breathable gas) pressurised above atmospheric pressure to a patient's airways via a conduit and a mask.
For either the treatment of OSA or the application of assisted ventilation, the pressure of the gas delivered to a patient can be at a constant level, bi-level (ie. in synchronism with patient inspiration and expiration) or autosetting in level to match therapeutic need. Throughout this specification the reference to CPAP is intended to incorporate a reference to any one of, or combinations of, these forms of pressure delivery.
The masks used in CPAP treatment generally include a vent for washout of the gas to atmosphere. The vent is normally located in the mask or in the gas delivery conduit adjacent the mask. The washout of gas through the vent is essential for removal of exhaled gases from the breathing circuit to prevent carbon dioxide “re-breathing” or build-up, both of which represent a health risk to the mask wearer. Adequate gas washout is achieved by selecting a vent size and configuration that will allow a minimum safe gas flow at the lowest operating CPAP pressure, which, typically can be as low as around 4 cm H 2 O for adults and 2 cm H 2 O in paediatric applications.
Prior art masks are generally comprised of a rigid plastic shell which covers the wearer's nose and/or mouth. A flexible or resilient rim (or cushion) is attached to the periphery of the shell which abuts and seals against the wearer's face to provide a gas-tight seal around the nose and/or mouth.
A prior art washout vent utilized one or more holes or slits in the rigid shell or in a rigid portion of the delivery conduit to allow the washout gas to vent to atmosphere. In some masks, the holes or slits were formed during the moulding process. In others, they were drilled or cut as a separate step after the shell or conduit had been moulded.
The flow of gas out the holes or slits in the shell or conduit to atmosphere creates noise and turbulence at the hole or slit outlet as the delivered gas, and upon expiration, the patient-expired gas (including CO 2 ) exits. Bi-level and autosetting gas delivery regimes tend to generate more noise than a constant level gas delivery regime. This is thought to be due to the extra turbulence created by the gas accelerating and decelerating as it cycles between relatively low and relatively high pressures. The noise adversely affects patient and bed-partner comfort.
Another prior art vent included hollow rivets or plugs manufactured from stainless steel or other rigid materials attached to openings in the rigid shell. The outer edges of die rivers were rounded to help reduce noise. However, his approach was expensive, required an extra production step and did not prove effective in reducing noise.
Another approach to reduce noise involved the use of sintered filters at the gas outlet of the mask shell. However, the filters were prone to blocking, especially in the presence of moisture. Accordingly, sintered filters were impractical for use in CPAP treatment as they were easily blocked by the moisture from the patient's respiratory system or humidifiers or during the necessary regular cleaning of the mask and associated componentry.
Foam filters wrapped around the air outlets in the shell were also attempted. However, they also suffered from the disadvantages of being prone to blocking, difficult to clean and requiring constant replacement.
Remote outlet tubes have been used to distance the noise source from the patient. However, these tubes are difficult to clean, are prone to entanglement by the patient and/or their bed partner and suffer the ether disadvantage that a volume of exhausted gas is retained in the tube adjacent the mask.
It is all object of the present invention to substantially overcome or at least ameliorate the prior art disadvantages and, in particular, to reduce the noise generated by gas washout through a mask.
SUMMARY OF THE INVENTION
Accordingly, the invention, in a first aspect, discloses a mask for use with a system for supplying breathable gas pressurised above atmospheric pressure to a human or animal's airways, the mask includes a mask shell which is, in use, in fluid communication with a gas supply conduit, a gas washout vent assembly, wherein at least the region of the mask shell or conduit surrounding or adjacent the vent assembly is formed from a relatively flexible elastomeric material.
In an embodiment, the entire mask is formed from the elastomeric material.
In another embodiment, the mask shell and/or conduit is formed from a relatively rigid material and the region surrounding or adjacent the vent assembly is formed from the relatively flexible elastomeric material.
In a second aspect, the invention discloses a vent assembly for the washout of gas from a mask or conduit used with a system for supplying breathable gas pressure above atmospheric pressure to a human or animal, wherein the vent assembly is formed from the relatively flexible elastomeric material.
In a preferred embodiment, the vent assembly is an insert of relatively flexible elastomeric material, wherein the insert is attachable to the mask shell or conduit. The insert preferably has at least one orifice therethrough.
In a preferred form, the rigid plastics mask shell is formed from polycarbonate and the insert is formed from SILASTIC™ or SANTOPRENE™.
Desirably, the insert is substantially crescent-shaped and includes a plurality of orifices therethrough.
The insert preferably includes a groove around its periphery, the groove adapted to locate the insert against a correspondingly sized rim of an opening formed in the mask shell or conduit.
In other embodiments, the insert is substantially circular, triangular, cross or peanut shaped.
The mask shell and/or the conduit can desirably also include one or more inserts.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention will now be described, by way of examples only, with reference to the accompanying drawings in which:
FIG. 1 is a perspective view of a first embodiment;
FIG. 2 is a perspective view of a second embodiment;
FIG. 3 is a perspective view of a third embodiment;
FIG. 4 is a perspective view of a fourth embodiment;
FIG. 5 is a perspective view of a fifth embodiment;
FIG. 6 is a perspective view of a sixth embodiment;
FIG. 7 is a perspective view of a seventh embodiment;
FIG. 8 is a partial cross-sectional view of the first embodiment along the line 8 - 8 of FIG. 1 ;
FIG. 9 is a perspective view of an eighth embodiment;
FIG. 10 is a plan view of the insert of the third embodiment;
FIG. 11 is a cross-sectional view of the third embodiment insert along the line 11 - 11 of FIG. 10 ; and
FIG. 12 is a partial cross-sectional view of the third embodiment insert along the line 12 - 12 of FIG. 10 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring firstly to FIG. 1 , there is shown a mask 10 for use with a system (not shown) for supplying breathable gas pressurised above atmospheric pressure to a human or animal's airways. The mask includes a rigid plastics shell 12 having an inlet tube 14 for connection to a supply conduit to communicate breathable gas from a flow generator (not shown) to the nasal passages of the mask wearer. The mask shell 12 also includes a flexible sealing membrane 16 which is used to provide a gas tight seal between the face of the wearer and the interior of the shell 12 . The shell 12 also includes lugs 18 for connecting the mask 10 to a head strap (not shown) to retain the mask in place.
The mask includes a SILASTIC™ insert 20 through which is provided an orifice 22 for gas washout. As best shown in FIG. 8 , the insert 20 has a recess or groove 24 around its periphery. A correspondingly sized opening 26 bounded by a rim 28 is provided in the shell 12 to enable the insert 20 to be retained in place in the fashion of a grommet. The opening 26 can be moulded in the shell 12 or drilled or punched as a post-moulding step. The flexibility of the SILASTIC™ allows the insert 20 to be initially squeezed through the opening 26 before resiliently expanding to the configuration shown in FIG. 8 and engaging the rim 28 .
As seen in FIG. 8 , orifice 22 has a cross-sectional contour from a face side of the orifice to an atmosphere side of the orifice. In FIG. 8 , the contour is shown as being symmetrical between the face side of the orifice and the atmosphere side of the orifice with a central portion of the orifice contour being of constant diameter. After the insert 20 is positioned in opening 26 of mask shell 12 , the contour remains substantially constant in size as gas is passed therethrough.
FIGS. 2 to 7 show further embodiments in which corresponding reference numerals are used to indicate like features. In all these embodiments the insert 20 has an external groove or recess 24 which engages the rim 28 of a corresponding shaped opening 26 in the mask shell 12 to retain the insert 20 in place.
In the embodiment shown in FIGS. 2 to 5 and 7 the insert 20 includes more than one orifice 22 . In the embodiment shown in FIG. 6 , two inserts 20 are provided in the shell 12 .
In the embodiment shown in FIG. 9 , the insert 20 is provided in a gas supply conduit 30 .
FIGS. 10 to 12 show the insert 20 of the third embodiment of FIG. 3 . The dimensions 32 , 34 , 36 , 38 , 40 , 42 and 45 are approximately diameter 1.73 mm, diameter 3.30 mm, 28.80 mm, 19.00 mm, 1.20 mm, 1.20 mm and 3.60 mm respectively.
The side 44 of the insert 20 faces the patient's face in use and the side 46 faces atmosphere.
The mask shell 12 is manufactured from polycarbonate. Other rigid plastics materials can equally be used. The insert 20 can be manufactured from an elastomer sold as SILASTIC™ produced by the Dow Corning Corporation) or a thermoplastic elastomer sold as SANTOPRENE™ (produced by Monsanto). Other flexible elastomeric materials can be used also.
The mask 10 produces less noise than an identical mask having a similar sized and shaped orifice(s) formed directly in the mask shell 12 instead of formed in the flexible insert 20 . It is thought that the noise reduction occurs due to the flexible insert 20 damping vibrations caused by air passage through the orifice(s) 22 which produce vibrations or similar in the mask shell 12 .
A prototype of the embodiment of the invention shown in FIG. 3 has been tested over a range of constant and bi-level CPAP treatment pressures. For comparison purposes, an identical mask to that shown in FIG. 3 but formed entirely from polycarbonate and having six identical arcuately spaced holes 22 drilled directly through the mask shell was also tested. In both masks the six holes had a diameter of 1.7 mm. The results of the test are summarised in the Tables below:
TABLE 1
Constant level gas delivery
Pressure
Noise levels 1 m from mask (dBA)
(cm H 2 O)
With flexible insert
Without flexible insert
4
26.8
35.2
10
33.4
43.1
18
39.3
49.2
TABLE 2
Bi-level gas delivery
Pressure
Noise levels 1 m from mask (dBA)
(cm H 2 O)
With flexible insert
Without flexible insert
5-10
30.8-38.5
37.2-43.0
10-15
38.6-43.7
42.9-47.9
As the result show, the mask shown in FIG. 3 produced less radiated noise than a similar mask not including the flexible elastomeric insert 20 representing a significant advantage in terms of the comfort of the mask wearer and their bed partner.
In addition to the noise reduction discussed above, the masks 10 possesses other advantages over those of the prior art. Firstly, the insert 20 is very easy to install into the mask shell 12 during either assembly of the mask which, is often supplied in kit form, or before and after cleaning which is regularly required and often carried out in the home environment. Secondly, the mask shell 12 may be produced with a single size of opening 26 and provided with a range of different inserts 20 which allows the outlet size to be “tuned” to give an optimum gas washout rate for a particular patient's treatment pressure level.
Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art, that the invention may be embodied in many other forms. | A mask ( 10 ) for use with a system for supplying breathable gas pressurized above atmospheric pressure to a human or animal's airways. The mask ( 10 ) includes a mask shell ( 12 ) which is, in use, in fluid communication with a gas supply conduit ( 30 ), and a gas washout vent assembly ( 20 ). At least the region of the mask shell ( 12 ) or conduit ( 30 ) surrounding or adjacent the vent assembly is formed from a relatively flexible elastomeric material. | 0 |
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 61/199,495 filed Nov. 17, 2008, hereby incorporated by reference in their entirety for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates in part to the recovery of lithium from lithium-containing solutions, e.g., such as feed streams used in the manufacture of lithium ion batteries, as well as feed streams resulting from lithium extraction from ore based materials.
BACKGROUND OF THE INVENTION
[0003] Lithium containing batteries have become preferred batteries in a wide variety of existing and proposed new applications due to their high energy density to weight ratio, as well as their relatively long useful life when compared to other types of batteries. Lithium ion batteries are used for numerous applications, e.g., cell phones, laptop computers, medical devices and implants such as cardiac pacemakers.
[0004] Lithium ion batteries are also becoming extremely useful energy-source options in the development of new automobiles, e.g., hybrid and electric vehicles, which are both environmentally friendly and “green” because of the reduced emissions and decrease reliance on hydrocarbon fuels. This is clearly an advantage, as use of these batteries eliminate or reduces the need for hydrocarbon fuels and the resultant green house gas emissions and other associated environmental damage attributed to the burning of fossil fuels in internal combustion engines. Again, the selection of lithium-ion batteries for use in vehicles is due in large part to the high energy density to weight ratio, reducing the weight of batteries compared to other batteries, and important factor in the manufacture of vehicles.
[0005] Lithium ion batteries are typically made of three primary components: 1) a carbon anode, 2) a separator, and 3) a lithium containing cathode material. Preferred lithium containing cathode materials include lithium and metal oxide materials such as lithium cobalt oxide, lithium nickel-cobalt oxide, lithium manganese oxide and lithium iron phosphate, but other lithium compounds may be used as well.
[0006] Lithium iron phosphate is a particularly preferred compound for use as a lithium containing cathode material, as it provides an improved safety profile, acceptable operating characteristics, and is less toxic when compared to the other mentioned cathode materials. This is especially true for relatively large battery sizes, such as would be used in electric vehicles. The improved safety characteristics come from the ability of the Lithium Iron Phosphate (also called LIP) to avoid the overheating that other lithium ion batteries have been prone to. This is especially important as the batteries get larger. At the same time the battery operating characteristics of the LIP batteries are equal to that of the other compounds that are in current use. Other lithium compounds offer the reduction in overheating tendencies, however at the expense of the operating characteristics. Lithium iron phosphate sulfates are similar to LIP and are also used in batteries.
[0007] Lithium iron phosphate can be prepared using a wet chemistry process using an aqueous feed stream containing lithium ions from a lithium source, e.g., lithium carbonate, lithium hydroxide monohydrate, lithium nitrate, etc. A typical reaction scheme is described by Yang et al., Journal of Power Sources 146 (2005) 539-543 proceeds as follows:
[0000] 3LiNO 3 +3Fe(NO 3 ) 2 .n H 2 O+3(NH 4 ) 2 HPO 4 →Fe 3 (PO 4 ) 2 .n H 2 O Li 3 PO 4 +6NH 3 +9HNO 3 (I)
[0000] Fe 3 (PO 4 ) 2 .n H 2 O+Li 3 PO 4 →3LiFePO 4 +n H 2 O (II)
[0008] Lithium iron phosphate can be prepared using a wet chemistry process using an aqueous feed stream containing lithium ions from a lithium source, e.g., lithium carbonate, lithium hydroxide monohydrate, lithium nitrate, etc. Lithium iron phosphate sulfates are prepared similarly but a source of sulfate is needed for production. For example, U.S. Pat. No. 5,910,382 to Goodenough et al. and U.S. Pat. No. 6,514,640 to Armand et al. each describe the aqueous preparation of lithium iron phosphates. Generally, due to process inefficiencies, these wet chemistry methods of producing lithium iron phosphate result in an aqueous stream that contains a significant amount of lithium ions, along with other impurities. The composition of a typical stream that results from wet chemical preparation of lithium iron phosphate is given below:
[0000]
Range in PPM
Chemical Element
(unless otherwise noted)
Al
2-10
B
<3-3
Ba
<1-1
Ca
3-5
Cu
1-3
Fe
1-1.5
K
<10-10
Li
1.4-1.5%
Mg
<1-1
Na
20-25
P
40-60
S
3.4-3.5%
Si
25-35
Zn
<1-2
Cd, Co, Cr, Mn, Mo,
<1-<2
Ni, Pb, Sn, Sr, Ti, V
[0009] Since lithium is one of the primary and more valuable components of the lithium iron phosphate material, it would be desirable to recover any excess lithium to reuse in the wet chemistry manufacture of lithium iron phosphate, particularly if a relatively large excess of lithium is provided during the manufacturing process for producing the lithium iron phosphate product. A lithium recovery and purification processes from lithium battery waste material is known from Published PCT application WO 98/59385, but improved and alternative methods of lithium recovery are desired in the art.
OBJECTS AND SUMMARY OF THE INVENTION
[0010] The present invention satisfies this objective and others utilizing a bipolar electrodialysis, which is also known as salt splitting technology to recover lithium from feed streams. The lithium is recovered as a lithium hydroxide solution which can be recycled into feed streams used to produce the lithium iron phosphate using a wet chemical process. A sulfuric acid solution also results from the process, which can be recovered and used in other processes or sold commercially. In preferred embodiments, any phosphate ion in the feed stream is reduced, or, more preferably, removed, prior to bipolar electrodialysis of the feed stream because it has been discovered that phosphate tends to foul the membranes, reducing the yield of lithium hydroxide or preventing formation of it altogether. Alternatively in the sulfuric acid reduction of lithium bearing ore, the resultant purified lithium sulfate stream can also be processed in this manner. This has the advantage of also producing a sulfuric acid stream, which if concentrated, may be used to offset the purchase cost of the required sulfuric acid.
[0011] Bipolar membrane electrodialysis utilizes separate chambers and membranes to produce the acid and base of the respective salt solution introduced. According to this process, ion exchange membranes separate ionic species in solution via an electrical field. The bipolar membrane dissociates water into positively charged hydrogen ions (H + , present in the form of H 3 O + (hydronium ions) in aqueous solution) and negatively charged hydroxyl anions (OH).
[0012] Bipolar membranes are typically formed from an anion-exchange layer and a cation-exchange layer, which are bound together. A water diffusion layer or interface is provided wherein the water from the outer aqueous salt solution diffuses.
[0013] Selectively permeable anion and cation membranes are further provided to direct the separation of the salt ions, e.g., the lithium and sulfate ions, as desired. Thus, there is typically a three membrane system used in bipolar membrane electrodialysis.
[0014] Membranes from commercially available sources, e.g., Astom's ACM, CMB, AAV and BP1 membranes or FumaTech FKB membranes may be used in combination of their resistance to back migration of undesired ion (either H+ or OH−), low electric resistivity and resistance to the potentially corrosive nature of the resultant acid and base solution. These membranes are positioned between electrodes, i.e., an anode and a cathode, and a direct current (DC) is applied across the electrodes.
[0015] Preferred cell manufacturers include Eurodia, and EUR20 and EUR40 are preferred.
[0016] A preferred arrangement using bipolar membrane technology for recovery of lithium as lithium hydroxide from a stream containing lithium sulfate is shown in FIG. 4 . As shown in FIG. 4 , “A” is an anion permeable membrane; “C” is a cation permeable membrane. “B” is a bipolar membrane. The anion membrane allows the negatively charge sulfate ion to pass but hinders passage of the positively charged lithium ion. Conversely, the cation membrane allows the positively charged lithium ion to cross but hinders passage of the negative sulfate ion. A pre-charged acid and base reservoir are shown in the middle, with resultant H+ on OH− ions combining with the evolved negatively charge sulfate ion and positively charge lithium ion. Thus, lithium hydroxide solution is produced which can be fed into the process stream for preparing the lithium iron phosphate. A sulfuric acid solution results on the cathode side.
[0017] A lithium sulfate solution of the type previously described is preferably pretreated to a relatively high pH, typically to a pH of from 10 and 11, by addition of a suitable base, preferably an alkali hydroxide. Hydroxides of Li, Na, K are particularly preferred. Adjusting the pH to this range allows for removal of impurities, as precipitates, especially phosphates that are likely to interfere with the electrochemical reactions in the electrodialysis apparatus. It is especially preferred to remove at least phosphate from the feed, as it has been discovered that this impurity in particular leads to fouling of the membrane, impairing the process. These precipitates are filtered from the solution prior to feeding into the bipolar electrodialysis cell. The solution may then be adjusted to a lower pH, for example to 1-4 pH, and preferably 2-3, preferably utilizing the resultant acid from the process, as required and then fed into the electrodialysis cell. As explained above, during this process, the lithium ions cross the cation membrane resulting in a lithium hydroxide stream and the sulfate crosses the anion membrane producing a sulfuric acid stream. (See FIG. 4 ).
[0018] The resultant LiOH and sulfuric acid streams are relatively weak streams in terms of molar content of the respective components. For example, testing showed average ranges as follows:
[0000] LiOH: 1.6-1.85 M H 2 SO 4 : 0.57-1.1 M
[0019] Another aspect of the invention relates to the purity of the lithium hydroxide product, as purified lithium hydroxide product is highly desirable.
[0020] It has been found that a reduction in the sulfuric acid product concentration of about 50% results in the sulfate concentration in the hydroxide solution dropping by a corresponding amount (from 430 ppm to 200 ppm). Additionally the current efficiency, relative to acid production increased by about 10% with the reduction in acid concentration.
[0021] The block diagram of the above-mentioned process is shown in FIG. 1 .
[0022] More specifically with respect to FIG. 1 , a feed stream containing lithium sulfate, preferably from the production of a lithium battery component, is purified by removing any solid impurities by adjusting the pH to about 10 to about 11 to precipitate any solid impurities from the stream. The resultant purified lithium sulfate feed stream is then subjected to bipolar dialysis, preferably after adjusting the pH to about 2-3.5 with sulfuric acid, with a suitable bipolar membrane that will allow for the separation of lithium from the stream, which will be recovered as lithium hydroxide. In a preferred embodiment, prior to subjecting the lithium sulfate feed stream to bipolar electrodialysis, to the purification step or perhaps during the purification step, any phosphate is removed by, e.g., adjusting the pH to remove phosphate salts or by using an appropriate ion exchange membrane to remove the phosphate from solution. Alternatively a lithium sulfate stream from the sulfuric acid ore extraction process, proper purified by practices known in the art, may be subjected to bipolar dialysis, preferably after adjusting the pH to about 2-3.5 with sulfuric acid, with a suitable bipolar membrane that will allow for the separation of lithium from the stream, which will be recovered as lithium hydroxide.
[0023] It is thought that the current inefficiencies, particularly as they relate to the cation membrane, result in high localized pHs adjacent to the membrane causing precipitates to form in the central feed compartment. This can also be seen external to the cell by deliberately raising the pH of the feed to 10 and allowing the precipitate to form. Table 1 shows the composition of the solids collected from a 10 L batch of the feed lithium sulfate solution that had been pH adjusted to 10, left overnight and filtered. A total of 3.02 g of solid were recovered. A portion of the solids (0.3035 g) were re-dissolved in 100 ml of 1M HCl for analysis by ICP2. As can be seen from the Table 1 below, the major impurities in the precipitate appear to be Fe, Cu, P, Si, Zn and Mn3.
[0000]
TABLE 1
ICP Analysis of redissolved solids (mg/L)
Al
11
Ca
9.2
Cu
21.0
Fe
22.4
Li
391.0
Mn
58.4
Ni
1.2
P
351.0
S
231.0
Si
46.6
Sr
0.2
Zn
22.9
[0024] Bipolar dialysis of the lithium sulfate feed stream with a suitable bipolar membrane yields a lithium hydroxide solution and a sulfuric acid solution as shown on the right and left hand sides of FIG. 1 , respectively.
[0025] The lithium hydroxide solution can be recovered, or, preferably, may be directly introduced into a process for preparing LiFePO 4 or other lithium-containing salts or products. Of course the lithium hydroxide may be recovered and used, e.g., as a base in suitable chemical reactions, or to adjust the pH of the initial feed stream to remove impurities such as phosphate.
[0026] The lithium hydroxide solution that is recovered my be concentrated as desired before use, or, if necessary, subjected to additional purification steps.
[0027] Turing now to the left hand side of FIG. 1 , the sulfuric acid solution is recovered and sold or used as an acid in suitable chemical and industrial processes. Alternatively it can be concentrated and used to offset associated purchase costs of the sulfuric acid needed in the acid extraction of lithium from lithium bearing ores.
[0028] FIG. 2 shows an alternative embodiment of the present invention, in which both the lithium hydroxide and sulfuric acid streams are recovered and used in a process for the manufacture of lithium iron phosphate, which essentially makes the process a continuous process. Since the iron in the process is added in the form of an iron sulfate, the use of the recovered sulfuric acid stream to form iron sulfate is a possibility. This will depend on the purity requirements of the iron sulfate as well as concentration levels required. According to this method, however, an alternate iron source than iron sulfate could be utilized, with the sulfuric acid solution providing the sulfate source.
[0029] More specifically, in FIG. 2 a lithium sulfate feed stream is purified as described above by adjusting the pH to from 10 to 11 and the pH is then readjusted downward to from 2 to 3.5 before being subject to electrodialysis.
[0030] As with FIG. 1 , the purified bipolar electrodialysis with a suitable membrane to form an aqueous sulfuric acid stream and an aqueous lithium hydroxide feed stream. In this embodiment, focus is on recovering both the sulfuric acid and lithium hydroxide feed streams and returning them for use in the production of a lithium product, especially lithium iron phosphate. Focusing now on the left side of FIG. 2 , the aqueous sulfuric acid stream is converted to iron sulfate by addition of an iron source into the sulfuric acid solution. The source may be any suitable source, including metallic iron found in naturally occurring iron ore. iron sulfate is a preferred iron salt since the solution already contains sulfate ion. Addition of the iron yields an iron phosphate solution, which is then ultimately mixed with the lithium hydroxide solution recovered from the bipolar electrodialysis process, and a phosphate source, to yield lithium iron phosphate.
[0031] As shown on the right side of FIG. 2 , the lithium hydroxide solution is preferably adjusted to the required level of lithium hydroxide by introduction of lithium hydroxide from another source, or by concentrating the recovered stream.
[0032] Another preferred embodiment is shown in FIG. 3 . In this option, a lithium source other than lithium hydroxide, e.g., lithium carbonate is used in the process. In this embodiment, the sulfuric acid stream is reacted with lithium carbonate of a predetermined purity, to produce additional lithium sulfate solution that would then be added to the original recycle solution prior to feeding into the bipolar electrolysis cells. This process is shown at the left hand side of the flow diagram in FIG. 3 . Thus, different lithium sources can be used to yield a lithium solution from which lithium hydroxide can be extracted. The pH adjustment steps of the LiSO 4 feed stream are as described above.
[0033] Note that iron sulfate is shown to be added to all or a portion of the sulfuric acid stream to yield an iron sulfate solution which is along with the recovered lithium hydroxide solution to produce lithium iron phosphate according to a wet chemical process such as described herein.
BRIEF DESCRIPTION OF THE FIGURES
[0034] FIG. 1 :
[0035] A block diagram of a simplified lithium sulfate bipolar electrodialysis recycle process for recycling lithium hydroxide lithium sulfate into a process of manufacturing lithium iron phosphate.
[0036] FIG. 2 :
[0037] A block diagram of a lithium sulfate bipolar electrodialysis recycle process for recycling both lithium hydroxide and sulfuric acid into a process of manufacturing lithium iron phosphate.
[0038] FIG. 3 :
[0039] A block diagram of a lithium sulfate bipolar electrodialysis recycle process for using recycled lithium hydroxide, sulfuric acid, and lithium hydroxide generated from an additional lithium source to manufacture lithium iron phosphate.
[0040] FIG. 4 :
[0041] A schematic diagram of a bipolar electrodialysis cell used for recover of lithium as lithium hydroxide from a stream containing lithium sulfate.
[0042] FIG. 5 :
[0043] A plot of current density as a function of time during the process of running pH 10 pre-treated feed solutions through an electrodialysis cell containing Astom membranes.
[0044] FIG. 6 :
[0045] A plot of current density and concentrations of acid and base products as a function of time during the process of running pH 11 pre-treated feed solutions through an electrodialysis cell.
[0046] FIG. 7 :
[0047] A plot of current density as a function of time during the process of running feed solutions through an Eurodia EUR-2C electrodialysis cell operating at a constant voltage.
DESCRIPTION OF PREFERRED EMBODIMENTS
Example 1
[0048] An EUR-2C electrodialysis cell commercially available from Euroduce was modified to include Astom bipolar membranes (BP1) and FuMaTech anion and cation membranes (FAB and FKB respectively). The cell was run with a feed solution that had been pre-treated by pH adjustment to10 to precipitate phosphate and other impurities followed by filtration to remove the precipitates. The pH was then adjusted to pH 3.5 before feeding it into the cell.
[0049] As can be seen from Table 2, the cation membrane generated up to 2.16M LiOH at current efficiencies of approximately 75%. The anion exchange membrane yielded current efficiencies of 40% for a 0.6M H 2 SO 4 product solution. The average current density throughout the run was nearly almost 62 mA/cm 2 while operating the cell at a constant voltage of 25V. (This voltage is applied across all seven sets of membranes and the electrode rinse compartment). No solids were seen in the cell in this short term operation, indicating that the pretreatment adjustment of pH to 10 prior to introduction into the cell improved results compared to using the feed solution without pH adjustment.
[0050] The overall efficiency of the cell appears to be dictated by the lowest current efficiency of any particular membrane since we have to use one of the product streams was used to maintain the pH in the central compartment. So, in Example 1 it was necessary to add some of the product LiOH back into the central compartment to neutralize the back-migrating proton from the acid compartment. Hence the overall current efficiency for the cell would have been 40% negating the advantage of the FKB membrane.
Example 2-5
[0051] Example 2 through 5 were all run with Astom membranes (ACM, CMB and BPD. Examples 2 and 3 were short term experiments using lithium sulfate feed solutions that had been pretreated to pH 10 as described previously. Both examples yielded acid and base current efficiencies close to 60% and maintained good current densities over the short term indicating that the pretreatment improved results compared to prior runs. Example 4 was an overnight experiment run with the same conditions and showed a marked drop in current density, probably due to membrane fouling with phosphate or other precipitates.
[0052] FIG. 5 shows the current density for all three runs. After 1250 minutes the cell was paused and the pumps turned off to allow sampling. Upon restarting the system the current density recovered dramatically indicating that the drop in current was due to small amounts of precipitate that were subsequently washed out of the cell.
[0053] Since the pretreatment at pH 10 seemed to leave some foulant in the feed stream, Example 5 used a solution that had been pretreated to pH 11 for three days and was then filtered. As shown in FIG. 6 , the current density being maintained for over 24 hours a clearly improved result. The final drop in current is thought to be due to the lithium sulfate in the feed becoming exhausted, as this was run as a single large batch.
[0054] FIG. 6 also shows that the acid and base concentrations were maintained fairly constant by constant water addition. Thus, it is desirable and sometimes necessary to add product acid or base to control the pH in the central feed compartment. To facilitate control of this compartment, a higher acid concentration was chosen to thereby lowering the acid current efficiency so that the pH in the central compartment could be controlled at 3.5 solely by the addition of LiOH. The average current efficiency for the hydroxide formation was almost 60%.
[0055] FIG. 6 shows the sulfate concentration in all three compartments as a function of time. The central compartment was run as a single batch and by the end of the experiment the concentration had reached about 0.2M. The sulfate in the LiOH was approximately 400 mg/L which accounts for approximately 0.85% of the current. Reducing the sulfuric acid concentration would reduce the sulfate content in the LiOH could be reduced further.
Examples 6-10
[0056] In Example 6-10 the Eurodia EUR-2C electrodialysis cell was used to demonstrate the feasibility of a three compartment salt splitting of lithium sulfate. The cell was assembled with seven sets of cation, anion and bipolar membranes configured as shown in FIG. 4 . Each membrane has an active area of 0.02 m 2 .
[0057] It is believed lithium phosphate which is formed in high pH regions adjacent to the cation membrane due to back migration of hydroxide ion is primarily responsible for membrane fouling when it occurs. Pretreatment of the feed solution to remove phosphate and other impurities by raising the pH to 11 precipitates most of these salts and yields improved results compared to adjustment to a pH of only 10.
[0058] Example 9 is representative and is described in detail below. A 1M lithium sulfate starting solution was pretreated to remove insoluble phosphate salts by raising the pH to 11 with 4M LiOH at a ratio of approximately 1L of LiOH to 60L of 1M Li 2 SO 4 . The treated lithium sulfate was mixed well and the precipitate was allowed to settle overnight before filtering through glass fiber filter paper (1 μm pore size). The filtered Li 2 SO 4 pH was readjusted to 2 pH with the addition of approximately 12 mL of 4M sulfuric acid per liter of Li 2 SO 4 .
[0059] The starting volume of pretreated Li 2 SO 4 feed was 8 L and was preheated to approximately 60° C. before transferring to a 20 L glass feed reservoir. The initial LiOH base was a heel of 3 liters from Example 8 which was analyzed at the start of the experiment at 1.8M LiOH. The initial acid was a heel of 2 L H 2 SO 4 also from Example 8 and analyzed at 0.93M H 2 SO 4 . The electrode rinse was 2 liters of 50 mM sulfuric acid. The solutions were pumped through a Eurodia cell (EUR-2C-BP7) at approximately 0.5 L/minicompartment (3-4 L/min total flow) with equal back pressure maintained on each compartment (3-4 psi) to prevent excessive pressure on any one membrane which could lead to internal leaking. The flow rates and pressures of each were monitored along with feed temperature, feed pH, cell current, voltage, charge passed and feed volume.
[0060] The electrodialysis operated at a constant 25 volts. The Li 2 SO 4 feed temperature was controlled at 35° C. The pumps (TE-MDK-MT3, Kynar March Pump) and ED cell provided sufficient heating to maintain the temperature. The 20 liter feed tank was jacketed so that cooling water could be pumped through the jacket via a solenoid valve and temperature controller (OMEGA CN76000) when the temperature exceeded 35° C.
[0061] The cell membranes provided sufficient for heat transfer to cool the other compartments. To run this experiment continuously for 20 hours, the Li 2 SO 4 feed was replenished pumping in pretreated pH 2, 1M Li 2 SO 4 feed at a continuous rate of 10 mL/minute. The proton back migration across the ACM membrane was greater than the hydroxide back migration across the FKB cation membrane, so the central compartment pH would normally drop. The pH of the central compartment was controlled by the addition of 4M LiOH using a high sodium pH of electrode and a JENCO pH/ORP controller set to pH 2. Electronic data logging of feed pH every minute over the 20 hour experiment showed a variation in pH of from 1.9 to 2.1, thus a total of 3.67 L of 4M LiOH was added to the feed to neutralize hydroxide back migrating. The feed volume increased from 8 L to 15.3 L after 20 hour of operation due to the addition of 11.8 L of Li 2 SO 4 and 3.7 L LiOH, and 6.8 L of water transport to the acid and 0.7 L of water transport to the base.
[0062] The LiOH base was circulated through the cell from a 1 gallon closed polypropylene tank. The 3 liter volume was maintained by drawing off the top using tubing fixed at the surface of the LiOH and using a peristaltic pump to collect the LiOH product in a 15 gal overflow container. The concentration of the LiOH was maintained at 1.85M LiOH concentration by the addition water to the LiOH tank at a constant rate of 17 mL/minute.
[0063] The sulfuric acid was circulated through the acid compartment of the cell from a 2 L glass reservoir. An overflow port near the top of the reservoir maintained a constant volume of 2.2 L of H 2 SO 4 over-flowing the acid product to a 15 gal tank. The concentration of the H 2 SO 4 was held constant at 1.9M with the addition of water at a constant rate of 16 mL/minute.
[0064] The electrode rinse (50 mM H 2 SO 4 ) was circulated through both the anolyte and catholyte end compartments and recombined at the outlet of the cell in the top of a 2 liter polypropylene tank where O 2 and H 2 gases produced at the electrodes were vented to the back of a fume hood.
[0065] Several samples were taken during the experiment to insure that the water addition rates to the acid and base were sufficient to hold the concentrations constant over the course of the experiment. At the end of the 19.9 hour experiment the power was turned off, the tanks were drained and the volumes of the final products were measured along with the final Li 2 SO 4 and electrode rinse. The total LiOH made was 30.1 L of 1.86 M LiOH (including 3L heel), and 21.1 L of 1.92M H 2 SO 4 (including 2 L heel). The final feed was 15.3 liters of 0.28M Li 2 SO 4 , and a final electrode rinse containing 1.5 L of 67 mM H 2 SO 4 . There was 0.5 L of water transport from the electrode rinse across the cation membrane to the acid. The total amount of water added was 18.6 liters to the acid and 20.4 liters to the base. The total charge passed was 975660 coulombs (70.78 moles) with 33.8 mole H back migration, 20.2 moles OH − back migration, and 14.97 moles of LiOH added to the feed. The average current density for this experiment was 67.8 mA/cm 2 . The H2SO4 current efficiency was 52.5% based on analysis of sulfate accumulation in the acid, and LiOH current efficiency was 72.4% based on the analysis of Li+ in the LiOH product.
[0066] The start and end samples were analyzed for SO 4 2− by using a Dionex DX600 equipped with an GP50 gradient pump, AS 17 analytical column, ASRS300 anion suppressor, a CD25 conductivity detector, EG40 KOH eluent generator and an AS40 autosampler. A 25 μL sample is injected onto the separator column where anions are eluted at 1.5 mL/min using a concentration gradient of 1 mM to 30 mM KOH with a 5 mM/min ramp. Sulfate concentration was determined by using the peak area generated from the conductivity detection verses a four point calibration curve ranging from 2 to 200 mg/L SO 4 2− . Sample analysis for Li + were done by a similar technique using a Dionex DX320 IC equipped with IC25A isocratic pump, CS 12a analytical column, CSRS300 cation suppressor, a IC25 conductivity detector, ECG II MSA eluent generator and an AS40 autosampler. A 25 μL sample was injected onto the separator column where anions are eluted at 1.0 mL/min using a concentration gradient of 20 mM to 30 mM methanesulfonic acid (MSA). Lithium concentration was determined by using the peak area generated from the conductivity detection versus a four point calibration curve ranging from 10 to 200 mg/L Li + The H 2 SO 4 acid concentration was determined by a pH titration with standardized 1.0N sodium hydroxide to pH 7. The base concentration was determined by titration with standardized 0.50N sulfuric acid to pH 7 using a microburrete.
[0067] Table 3 summarizes the results from electrodialysis experiments run with the Astom ACM membrane. Example 6 also used the Astom CMB and BPI cation and bipolar membrane respectively. The lithium sulfate feed solution was pre-treated to pH 11, filtered and then readjusted to pH 3.5 prior to running in the cell. The results are comparable to those reported last month in terms of current efficiency; however, the average current density is lower than previous runs indicating that we are still seeing some fouling. A pH gradient at the cation membrane at pH 3.5 appeared to be causing a precipitation issue, the pH of the feed compartment was reduced to a pH of 2 and FuMaTech FKB cation membrane, which has have less hydroxide back migration, was used. The pairing of the FI(13 and ACM membranes means that the pH in the central compartment is dominated by the back migration of proton across the ACM and pH control is accomplished solely by the addition of LiOH.
[0068] Example 7 to 9 are repeat runs with the FKB/ACM/BP1 combination giving a total of 70 hours of operation in three batches. It can be seen from Table 1 that the reproducibility of these runs is excellent with the current efficiency for LiOH measured three different ways at 71-75% (measured by Li+ loss from the feed, Li+ and hydroxide ion gain in the base compartment). Likewise the acid current efficiency is 50-52% by all three measurement methods. Data from these examples show consistency of the average current density. FIG. 7 shows this graphically where the initial current densities match each other very well. The deviations at the end of each batch are due to different batch sizes, and, therefore, different final lithium sulfate concentrations.
[0069] The high current efficiency of the FKB membrane appears to help avoid precipitation problems at the boundary layer on the feed side of the cation membrane. The overall current efficiency of the process is determined by the poorest performing membrane. That is, the inefficiency of the ACM membrane must be compensated for by the addition of LiOH from the base compartment back into the feed compartment thereby lowering the overall efficiency to that of the anion membrane. In an effort to increase the efficiency of the anion membrane, the acid concentration was reduced in the product acid compartment. Example 10 was run with 0.61 M sulfuric acid which has the effect of increasing the acid current efficiency by almost 10% to 62%. (See Table 3).
Examples 11-12
[0070] In an effort to further increase the acid current efficiency, the cell was modified with an AAV alternate anion membrane from Astom in Examples 11 and 12. The AAV membrane is an acid blocker membrane formerly available from Ashahi Chemical. Table 4 shows a summary of the data from these experiments using a combination of FKB, AAV and the BP-1 bipolar membrane.
[0071] Current efficiencies for both acid and base from these membranes are very similar to the combination of Examples 7-9. There was about a 10% increase in the acid current efficiency when using a lower acid concentration. The average current density for this membrane combination is slightly lower than when the ACM membrane was used (approximately 10 mA/cm 2 for the same acid concentration and operating at a constant stack voltage of 25V). External AC impedance measurements confirmed that the resistance of the AAV is higher than the ACM when measured in Li 2 SO 4 solution.
[0072] The purity of the lithium hydroxide product to be recycled into the process for making lithium iron phosphate is of great importance. The major impurity in the LiOH stream using this salt splitting technique will be sulfate ion that is transported across the bipolar membrane from the acid compartment into the base. The amount of transport should be directly related to the acid concentration. This can clearly be seen by comparing Example 9 with Example 10 (See Table 3) and Example 11 with Example 12 (Table 4). In each case the sulfate contamination in the 1.88M LiOH was approximately reduced by half when the acid concentration was reduced from 1M to 0.6M. The steady state sulfate concentrations are 430 and 200 ppm respectively.
[0073] As sulfate and lithium ions are transported across the ion exchange membranes, water is also transferred due to the hydration of the ions (electro-osmosis), and osmosis. However, the water transport out of the central compartment is not sufficient to keep the concentration constant. This is illustrated by considering the water transfer in Example 8. For every lithium ion that transferred across the cation membrane, 7 waters are also transferred. Similarly, an average 1.8 waters net were transferred with the sulfate ion giving a total of 15.8 waters for each lithium sulfate. Since the feed solution was only one molar in lithium sulfate, it contains almost 55 moles of water for each lithium sulfate which will lead to a continual dilution of the lithium sulfate in the central compartment. Removing water from the feed compartment can control this and can be done by, e.g., reverse osmosis for example.
[0074] All references cited herein are incorporated by reference in their entireties for all purposes. | A method for recovering lithium as lithium hydroxide by feeding an aqueous stream containing lithium ions to a bipolar electrodialysis cell, wherein the cell forms a lithium hydroxide solution. An apparatus or system for practicing the method is also provided. | 8 |
This invention was made with government support under Contract No. W-7405-ENG-36 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
RELATED CASES
This application claims the benefit of the filing date of U.S. provisional application S. No. 60/025,857, filed Sep. 9, 1996.
BACKGROUND OF THE INVENTION
This invention relates to traveling wave devices, and more particularly, to stable operating regimes for high power traveling wave devices.
The free-electron laser (FEL) and the traveling-wave tube (TWT) are both traveling wave devices (TWDs) in which a traveling radio frequency (RF) wave is in synchronism with an electron beam and exponentially extracts power from the electron beam. In a FEL, the RF wave travels faster than the electrons, but the synchronism is established either by wiggling the electrons (in a standard FEL) or by wiggling the RF (in an axial free-electron laser). In a TWT, the RF wave is slowed down in a "slow-wave structure," and no wiggling is required to establish synchronism.
Free-electron lasers (FELs) have demonstrated both high beam-to-radio-frequency (RF) power extraction efficiences (˜30%) and high output power (on the order of gigawatts), and have been considered as candidates to drive high-frequency advanced accelerators like those proposed for linear colliders. However, poor phase stability has been measured for FELs. Typical accelerator applications require RF phase stability on the order of 5° of phase, and advanced accelerator applications, such as bunch compression and short-wavelength FELs, require stability to 1° or less. At low frequencies, klystrons can meet these requirements, which is one reason they are used so extensively for driving accelerators.
Phase noise in microwave FELs arises from fluctuations in tube voltage, current, confining magnetic field strength, and other tube parameters. Typically, the largest effect is from voltage fluctuations. Electron beams for practical FELs used as RF sources will have diode voltages of 1/2 to 1 MV with voltage stabilities on the order of 1/4%. Measured and simulated FEL phase stability to date, which has all been done at high frequencies, has been on the order of 20° to 40° shift per percent voltage fluctuation. This level of phase stability does not satisfy advanced accelerator requirements.
The magnitude of the phase dependency on the beam voltage is easily understood by considering how the output phase is related to the transit time of the electron beam as it travels through the microwave device. In addition, for an FEL, the growing mode's phase velocity depends on several other factors that are dependent on the beam voltage, such as current, plasma frequency, and interaction strength between the electrons and the RF field.
It has been shown for cyclotron autoresonance maser (CARM) amplifiers that it is possible to introduce a correlation in the transverse motion of the electrons with respect to the beam voltage by using a bifilar helical wiggler. The interaction strength is then a function of beam voltage, and it is possible to design the device such that phase variations due to changes in the beam's transit time effectively cancel variations in the phase due to changes in the interaction strength as the beam voltage fluctuates. The proper correlation has been analyzed for the case of negligible space charge forces for a CARM amplifier. This phenomena was named autophase stability.
It is not always easy or convenient to provide a correlation of the interaction strength that will provide autophase stability, particularly for non-CARM interactions. For example, the interaction strength of most TWDs using mildly relativistic electron beams with constant perveance guns has only a weak dependence on the beam voltage. However, in accordance with the present invention, it is relatively easy to generate a correlation with the space-charge wave of the beam that will provide autophase stability simply by detuning the nominal beam energy away from synchronism for interaction strengths that are even independent of the beam voltage. For typical interaction strength dependencies on the beam voltage, low-energy TWDs can be made phase stable, both in the low- and high-gain regimes.
Practical FEL RF sources for linear collider applications need to produce at least several hundreds of megawatts of RF power. In order to accomplish this, the electron beam needs to contain several kiloamperes of current and must be annular to prevent exceeding the space-charge limiting current. In another aspect of the present invention, an off-axis or annular electron beam for a Raman-region FEL introduces the ability to control the reduced plasma frequency of the beam by decreasing the beam wall spacing, thereby shunting the beam's space-charge field to the beam pipe wall and increasing the so-called "plasma reduction factor."
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
SUMMARY OF THE INVENTION
To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein, this invention may comprise a method for providing autophase stability for a traveling wave device (TWD) electron beam for amplifying an RF electromagnetic wave in walls defining a waveguide having a first radius for the electromagnetic wave. An off-axis electron beam is generated at a selected energy and has an energy noise inherently arising from an electron gun. A RF electromagnetic wave is introduced into the waveguide. The off-axis electron beam is introduced into the waveguide at a second radius. The waveguide structure is provided to obtain a selected detuning of the electron beam. The off-axis electron beam is provided with a velocity and with the second radius to place the electron beam at a selected distance from the walls defining the waveguide structure, wherein changes in a density of the electron beam due to the RF electromagnetic wave are independent of the energy of the electron beam to provide a concomitant stable operating regime relative to the energy noise.
BRIEF DESCRIPTION OF THE DRAWINGS
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 description, serve to explain the principles of the invention. In the drawings:
FIG. 1 is a pictorial illustration in cross-section for a traveling wave device according to one embodiment of the present invention.
FIG. 2 schematically depicts the relationship between an electron beam, RF axial electric field and a waveguide according to one aspect of the present invention.
FIGS. 3A and 3B graphically depict the sensitivity of phase and of gain to beam energy as a function of space-charge wave number.
FIGS. 4A-4C graphically depicts the sensitivity to phase on beam energy for three detuning perturbations.
FIG. 4D graphically depicts gain as a function of detuning for the phase-stable cases shown in FIGS. 3A-C.
FIG. 5 graphically the sensitivity of phase to beam energy for a medium-gain, low-energy case.
FIG. 6 is a schematic representation of a helix slow-wave structure traveling wave tube.
FIG. 7 is a schematic representation of a dielectric-lined traveling wave tube.
FIG. 8 is a schematic representation of a transverse FEL with a helical wiggler.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, it is shown that, in the Raman regime, a correlation between the interaction strength (interaction of an off-axis electron beam having a constant radial position and a rippled RF wave) and an electron beam velocity is not needed to find a first-order phase and gain stable operating condition. In general, an electron beam detuning can be found for a Raman-regime TWD that will lead to phase stability for an arbitrary correlation of the interaction strength with beam velocity by introducing the effect of the space-charge wave, i.e., an autophase condition. The gain of the autophase stable condition can be kept large by proper manipulation of the plasma reduction factor which is only possible if the electron beam is off-axis and near the beam pipe wall. As used herein, the term "off-axis" means an electron beam that is radially displaced from the centerline of the TWD, where the electron beam is a single beam or is an annular beam. These effects are demonstrated with numerical solutions of the dispersion relation.
A traveling wave device (TWD) is operated in a phase stable regime using a combination of detuning and a correlation in the beam's space-charge wave where the dependence of the strength of the electron beam/RF interaction on the beam velocity is small in both the low-gain and high gain regions. The effect of the space-charge wave and the transit time of the electron beam are not separable in a TWD as they are in a klystron. This introduces new physical effects, one of which uses fluctuations in the space-charge wave to counter fluctuations in the beam's transit time through the device.
Phase noise can originate from variations in the mode propagation constant during the small-signal part of the tube. Assume that the mode has a jωt-Γz exponential behavior, where the real part of the mode propagation constant Γ represents the growth (or attenuation) of the RF mode and the imaginary part represents the phase evolution. For sufficiently narrow-bandwidth drive sources it is assumed that there is no variation in ω during the small-signal exponential growth and the only source of phase variation comes from ##EQU1## where ν o is the beam's axial velocity.
U.S. Pat. application Ser. No. 08/626,661, filed Apr. 2, 1996, and incorporated herein by reference, describes an FEL, an exemplary TWD, with an axial interaction between an off-axis electron beam and an injected RF field for the generation of gigawatt microwave radiation. In this exemplary FEL device 10, shown in FIG. 1, electron beam source 16 generates an off-axis electron beam 14, which may be an annular beam, that is introduced axially along waveguide 18 for interaction with an electrical field introduced by RF drive 12. The spacing between electron beam 14 and the walls of waveguide 18 is shown below to be one parameter available for operating in a stable regime. Focusing magnets 15 and 17 are conventionally provided for directing an off-axis or annular beam within waveguide 18. The radius of beam 14 from axis 20 is adjusted by adjusting the currents in focusing coils 15, 17 with concomitant control of the spacing between electron beam 14 and the walls of waveguide 18.
Waveguide 18 is provided with rippled wall 22, i.e., a smoothly varying wall radius, with a resulting ripple in the radial position of a null in the axial field, i.e., a radial wiggle in the axial electric field, as more particularly discussed with reference to FIG. 2. The average radius of wall 22 may taper along axis 20. The electron beam velocity is less than the phase velocity of the electric field so that the electric field "slips" by along the electron beam 14. Electron beam 14 then sees a gradient in the axial electric field at the beam location from the radial wiggling of the axial electric field. Solenoid magnet 24 produces an axial magnetic guide field to constrain the electrons in electron beam 14 to move axially at a constant radius within waveguide 18. The radial wiggling of the axial electric field, along with the phase slippage, provides a net interaction between the axial electric field of the RF mode and the axial velocity of off-axis electron beam 14. The RF mode in the waveguide is amplified by this interaction. After the interaction, the axial magnetic field decreases and the electron beam is intercepted by the wall of waveguide 18. Amplified RF 26 propagates out the end of waveguide 18 to a desired application.
As further shown in FIG. 2, an annular electron beam 14 interacts with the axial electric field 32 of a TM On mode in a circular waveguide 18 (FIG. 1). The radius 34 of waveguide wall 22 is periodically rippled, which causes the RF mode to expand and contract radially. The ripple amplitude is only a few percent of the average radius, and the mode is able to conform adiabatically to the gradual change in waveguide radius 34.
The axial FEL interaction for a synchronous particle is shown also in FIG. 2. Annular electron beam 14 is located at a radius corresponding to a zero of the axial electric field 32 of the RF mode propagating within waveguide walls 22 having a mean radius 34. When an electron is at an axial position 36, corresponding to a smallest waveguide radius, the axial electric field at the location of the electron opposes the motion of the electron. As the electron travels to a region of larger radius the RF slips by the electron. When the electron is at a location corresponding to a next maximum waveguide radius 38, one half of a RF wavelength has slipped by, resulting in a sign change in the fields of the propagating mode. Additionally, the electron is experiencing the electric field at a radius larger than the axial field null instead of at a smaller radius. The switch of the null 32 of the axial electric field from one side of electron beam 14 to the other provides another sign change in the axial field at the location of the electron, and the electric field is again opposing the electron's motion.
This interaction is equivalent to the interaction of a transverse-coupling FEL except the RF field is wiggled instead of the electrons to provide synchronism. This interaction is with the RF field fast wave, and is not a slow-wave interaction. This axial interaction is adopted for the following phase-stability analysis instead of the more common transverse-coupling FEL interaction, because the transverse wiggle velocity is typically a complicated function of beam voltage in an FEL using a helical wiggler, which would unnecessarily complicate the analysis. But the conclusions apply to both types of interactions, as well as for traveling wave tubes.
When the equations of motion are averaged over a wiggler period (small-gain assumption), the equation of motion become functionally identical to those for a traveling-wave tube (TWT). This averaging is a standard approximation for deriving the dispersion relation for the Raman regime. The only analytical differences between an axial FEL and a TWT are in the definition for the effective circuit impedance so that the following analysis applies generally to TWDs. As a result, this phase-stability scheme applies equally well to traveling-wave tubes and transversely wiggling FELs with off-axis electron beams as to the axial FEL with an off-axis electron beam used for the following analysis. The only differences are in some minor identifications of a few of the variables used to describe the gain of the device; in practice, this phase-stability scheme is implemented in identical manners, i.e., by adjusting the beam-wall spacing and the reduced mode phase velocity (either through the rf ripple period, the electron beam wiggle period, or the traveling-wave slow wave structure).
Standard microwave notation is used in this analysis, which differs slightly from conventional FEL notation. The reference to beam RF parameters (current, density, velocity) is to electron beam parameters that vary at the RF frequency. The analysis assumes that the beam RF current and velocity and the traveling RF wave amplitude all have the same time and axial functional form, e j ωt-Γz, where ω is the RF frequency, t is time, Γ is the growth of RF quantities (current, density, electric field, RF velocity), and z is the axial position along the RF beam, with the exception that the RF wave also has a phase slippage. A relationship exists between the beam RF density and the wave amplitude from both the Lorentz force equation and the RF wave equation. Setting the ratios equal, there is a quartic equation for Γ, known as the dispersion relation. Γ is in general complex, with the real part corresponding to a growing (or decaying wave) and the imaginary part corresponding to the mode phase shift per unit length.
For most combinations of parameters, all four roots of the dispersion relation lead to purely imaginary Γ; thus, there is no growing mode. However, close to resonance, two solutions appear that have real parts. For this case the four solutions correspond to (1) a constant-amplitude backward traveling wave (which is not excited if the TWD device output port is properly matched to the output load), (2) a constant-amplitude wave traveling faster than the electrons, (3) a decaying wave traveling slower than the electrons, and (4) a growing wave traveling slower than the electrons. Wave (4) is the one involved in the electron beam interaction. Note that the initial boundary conditions are some input RF power, zero RF beam current, and zero RF beam velocity. These boundary conditions are satisfied if the initial RF voltage is split evenly between waves (2), (3) and (4), assuming wave (1) is not excited. Thus, the initial power in the desired wave is only 1/9 of the input power, and a plot of power versus position along the device shows a -9.54 dB drop in the power right at the RF injection, characteristic of all forward traveling-wave devices.
Assume that the RF current density i, RF axial velocity ν, RF beam density ρ, and the axial electric field E at the beam's location can be written in the form
i.sub.τ =i.sub.o +ie.sup.jωt-Γz,
ν.sub.τ =ν.sub.o +νe.sup.jωt-Γz
ρ.sub.τ =ρ.sub.o +ρe.sup.jωt-Γz
E.sub.τ =Ee.sup.jωt-Γz-jk.sbsp.s.sup.z cos (k.sub.w z),(2)
where the subscript ν indicates a total including the steady state or direct-current (DC) components and k w is 2 π divided by the ripple period (or wiggle period for a standard FEL). The term jk s z is included in the expression for the axial field in order to allow slippage, where k s is the slippage wave number.
The essential difference in the physics of an axial and a transverse-coupling FEL is how the beam current drives the RF mode. The transverse-coupling FEL interacts through the transverse motion of electrons. The transverse current density results only from charge-density variations during the wiggle motion; the RF velocity ν is axial and does not contribute to the transverse current density. However, the axial FEL interacts through the total axial RF current, i, defined in Eq. (2).
One relationship between ρ and E is obtained by using the continuity equation, the definition of RF current, and the Lorentz force equation (known as the electronic equation). A second relationship is obtained from the wave equation (known as the circuit equation). Integrating the Lorentz force equation over several periods also gives k s =-k w .
Setting the two relationships between E and ρ equal, the dispersion relation becomes:
{(β.sub.e =jΓ).sup.2 -[(jΓ).sup.2 -k.sup.2 ]β.sub.q.sup.2 }[(Γ-jk.sub.w).sup.2 -Γ.sub.1.sup.2 ]-2β.sub.1.sup.4 C.sup.3 =0, (3)
where C is Pierce's gain parameter, defined by ##EQU2## R 0 is the beam impedance; β e is the beam propagation constant (ω/Vo); K is coupling impedance; β 1 is a mode propagation constant (ω/V phase ), k is the free space number ω/c, k c is the cutoff wave number as determined by the transverse dimensions of the waveguide (k c 2 =k 2 -β 1 2 ); Γ 1 =jβ 1 ; and β q 2 is the normalized space-charge wavenumber,
β.sub.q.sup.2 =2χI In(r.sub.w /r.sub.b)/I.sub.A γ.sup.3 β.sup.3, (4)
where χ is a geometrical factor close to unity, I is the beam current, I A is about 17 kA, r w is the wall radius, r b is the beam radius, γ is the relativistic mass factor, and β is the beam's axial velocity normalized to the speed of light. As noted above, the only difference between a FEL and a TWT is the coupling impedance K.
Since the dispersion relation is a quartic relation, there are four Γ solutions, of which at most one represents a growing mode. For the solution Γ of the dispersion relation that leads to a growing mode (real part of Γ negative), Γ is itself the exponential growth rate of the RF mode and the phase evolution is given by the imaginary part of Γ. Phase stability is defined by d/dv o Im(Γ)=0.
Note that the interaction strength 2C 3 β 1 4 scales as I/γβ 3 where I is the average beam current and γ(γ 2 =1/(1-β 2 )) is the relativistic factor for the beam. In general, the interaction strength is a function of the beam energy; however, for most common dependencies of the current on the beam voltage the interaction strength is a weak function of the beam energy. For example, if the diode has a constant perveance, the current scales as the beam voltage to the 3/2 power. For this case the derivative of the interaction strength with respect to γ is ##EQU3## which makes (dC/dγ)(γ-1) vanish if the beam is nonrelativistic, or if γ≈1. The (γ-1) factor appears because relative voltage fluctuations appear in the form δγ/(γ-1).
In the absence of space charge, resonance is established when β e =β 1 +k w . For small C 3 and the absence of space charge, the dispersion equation can be approximated by a cubic equation with roots ##EQU4## With space charge, resonance is typically established in accordance with the present invention when the beam velocity is slightly detuned, β e =β 1 +k w +Δ. Fluctuations in the beam voltage lead to changes in both β e and β q 2 (and minor changes in C), leading to a different solution Γ of the dispersion relation. The present invention uses the detuning Δ, which is adjusted by beam velocity and wall ripple spacing, and the beam-wall spacing (which changes β q 2 ), where changes in β e from changes in the beam velocity cancel changes in β q 2 in the dispersion relation, so that the solution of Γ (from Eq. (3)) does not change, thereby establishing stability.
By adjusting both Δ and β q 2 , both d/dv o Re(Γ)=0 (amplitude stability) and d/dv o Im(Γ)=0 (phase stability) can be achieved. This effect physically arises from how the RF electric field E drives changes in the RF beam density ρ. As the beam energy is increased, the inertia of the electrons is increased, leading to a lesser growth in the beam RF density for the same RF electric field. However, as the beam energy is increased, the opposing force from the space-charge wave is also decreased, leading to a greater growth of the RF density for the same RF electric field. By matching the amplitudes of these opposing effects (by adjusting the detuning and the beam-wall spacing), the net growth of ρ due to E can be made independent of energy, thereby leading to autostability.
For the case of high energy and low gain, the following relationships can be shown to result in both amplitude and phase stability in the Raman regime by detuning:
Δ=-β.sub.e /γ=β.sub.e -β.sub.1 -k.sub.w,(7)
where Δ is a detuning perturbation, β e and β 1 are selected electron and RF beam propagation constants, γ and k w =2 π/spacing of wiggles are known; ##EQU5## where β q 2 is the normalized space charge wave number and is functionally related to the ratio of the wall radius to the beam radius. These relationships are valid where the interaction strength is independent of beam energy and only make sense for γ on the order of 10 or greater.
For an exemplary case, γ=100, β e =300 m -1 , and C=0.03, this solution is given by Δ=-3 m -1 and β q 2 =6.7×10 -5 . FIGS. 3A and 3B, respectively, graphically depict the derivatives of the phase change per unit length and the amplitude growth with respect to beam energy, respectively, as calculated numerically for Δ=-3 m -1 while varying β q 2 , i.e., beam-to-wall spacing, and while assuming that the interaction strength is independent of beam energy and that the beam has constant perveance. The derivatives indicate the sensitivity of phase (FIG. 3A) and of gain (FIG. 3B), respectively, to beam energy for the low-gain, high-energy case of Eq. (8) as a function of space-charge wave number. As predicted, both derivatives are zero at β q 2 =6.7×10 -5 which is an autophase stable operating point.
If the solution in Eqs. (7) and (8) are tried for lower beam energy, say γ=10, the solution does not correspond to a growing mode (the detuning is so large it pushes the circuit admittance onto the lower branch of the electronic admittance). However, a phase stable solution does still occur [d/dv 0 Im(Γ)=0] if Eq. (7) is satisfied with smaller detunings. Then, ##EQU6## where a and b are components of δ 0 =-a+jb, where δ 0 =(jβ 1 +jk w -Γ)/Cβ 1 is the normalized growth parameter and a and b both are positive and typically on the order of unity. Eq. (9) reduces to Eq. (8) if the derivative of the gain parameter vanishes and if Eq. (7) is satisfied.
Consider a constant perveance case with these parameters: γ=10, C=0.015, and very small detuning. Eq. (9) predicts the proper space-charge wave number by assuming the solution for the growing mode is the small-gain, no space-charge solution given by Eq. (6) to Eq. (9), where a=√3/2 and b=1/2. The predicted phase-stable space-charge wave number for the zero detuning case is β q 2 =4.5×10 -3 and, for the case where Eq. (7) is satisfied, is β q 2 =5.5×10 -3 .
FIGS. 4A, 4B, and 4C show the derivative of the phase change per unit length as a function of β q 2 plotted for detunings of -2, -3.5, and -5 m -1 respectively. In all cases the numerically calculated solution is phase stable (zero derivative value) near these predicted solutions (β q 2 ≅4.3×10 -3 ). For these low-gain parameters, a growing mode only exists in the presence of a space-charge wave with β q 2 ˜5×10 -3 for detunings from -2 to -5 m -1 .
In FIG. 4D, the gain of the mode versus detuning is plotted for the phase stable solutions. The dashed line for detunings between 0 and -2 m -1 indicate that no phase-stable growing mode exists for those detunings. Note that the amplitude of the growing mode is only slightly affected by the introduction of the space-charge wave. This space-charge wave number corresponds to about 500 A for the parameters r w =3.6 cm and r b =3.2 cm. Note also that the term in the numerator of Eq. (9) containing the derivative of the gain parameter scales as -γ 3 and becomes less than -1 if the gain is greater than 0.09 for γ=10, which prevents any solution for a phase-stable space-charge wave number (since β q 2 must be a positive number). The strong scaling with beam energy makes this phase-stability technique hard to implement for high beam energies if the gain is a function of beam energy.
Consider another constant perveance case with γ=2 at 13 GHz (so the beam propagation constant is about 300 m -1 ), an output power of about 1 GW and with a device length of about 1 m. Using the definition for the interaction strength [Eq. (4)] the gain constant C is on the order of 0.1. A detuning of Δ=-50 m -1 is a convenient operating condition for these parameters. Assuming the low-gain, no-space-charge solution [Eq. (6)] for the constants a and b in Eq. (9), the detuning term in Eq. (9) is about 0.4, the gain parameter term is about -0.3 and the detuning term in the denominator is about 2.5. These values lead to phase-stable operation at a predicted space-charge wave number of about 0.08.
This detuning is plotted in FIG. 5, which shows the derivative of the phase change per unit length with respect to beam energy as a function of the space-charge wave number numerically calculated from the dispersion relationship. The calculated growth rate is about 11 m -1 or about a factor of 2 per wiggler period if the wiggle wave number is k w =100 m -1 (a 6 cm wiggler period), and phase-stable operation is achieved with a beam current of about 5 kA at nearly the predicted space-charge wave number. For this case the approximations used to derive Eq. (9) are marginally satisfied, but the prediction for the phase-stable space-charge wave number is still quite good.
As a final example consider the high gain case where C>1. Eq. (10) provides an estimate of the gain required to achieve phase stability in the absence of a space-charge wave(β q 2 =0): ##EQU7## For γ=2 and (dC/dγ)/C˜0.17, the growing mode is phase stable near C=1.25 Eq. (10) is only strictly valid when C is much greater than unity.
A more detailed treatment of the above analysis is presented in B.E. Carlsten, "Enhanced phase stability for a Raman free-electron laser amplifier in the exponential growth regime," 2 Phys. Plasmas (10), pp. 3880-3892 (October 1995), incorporated herein by reference.
This phase-stability scheme applies generally to traveling-wave devices having off-axis electron beams; in particular, to traveling wave tubes (TWTs) 50 and 68 (FIGS. 6 and 7) and transversely wiggling FELs 82 (FIG. 8) with off-axis electron beams 58, 72, 86, respectively, in addition to the axial FELs, described above. In TWT 50, shown in FIG. 6, electron beam gum 56 produces an annular or off-axis electron beam 58 for interaction with an rf electromagnetic field, which is input at port 52 and output through port 54, and a magnetic field B produced by a current in an external solenoid (not shown). Helix 62 is a slow-wave structure that slows the rf phase velocity below the speed of light.
In TWT 68, shown in FIG. 7, electron beam gun 70 produces an off-axis electron beam 72 for interaction with an rf electromagnetic field input at port 74 and a magnetic field produced by current in coils and a magnetic field produced by an external coil 76. Dielectric liner 78 produces a slow-wave structure to slow the rf phase velocity below the speed of light.
The TWT structures shown in FIGS. 6 and 7 both produce interactions that are classified as slow-wave interactions, as opposed to a fast-wave interaction in FELs. FIG. 8 more particularly depicts a transverse interaction FEL 82. Electron beam gun 84 outputs an annular or off-axis electron beam 86 for interaction with the magnetic field produced by permanent magnet wiggler 92. Solenoid 88 produces an axial magnetic field to cause rotation of electrons in electron beam 86.
The above analysis for the phase-stability criteria (Equations (2)-(10)) is still valid for a traveling-wave tube, with the modifications that the total electric field in Equation (2) is just E t =Ee j ωt-Γz, the coupling impedance term K and the gain term C are defined somewhat differently, and k w is the amount the mode's wavenumber is increased by the slow-wave structure (the mode's phase velocity in the slow-wave structure is given by k w +β 1 , where β 1 is the mode's unperturbed propagation constant). With these identifications, Equations (9) and (10) still describe how to achieve phase-stable operation. In practice, the same considerations are used to implement this scheme as in an axial FEL: (1) the slow-wave structure is designed such that the slowed phase velocity of the wave provides the correct detuning from the single-particle resonance, and (2) the beam-wall spacing is adjusted to obtain the desired space-charge wavenumber.
FIG. 8 shows a common representation of a transverse wiggler FEL 82 with the transverse wiggling induced by a helical wiggler magnet 92 arrangement. The above analysis for the phase-stability criteria (Equations (2)-(10)) is virtually unchanged (the coupling impedance term K and the gain term C are defined somewhat differently as with the traveling-wave case, and k w is now the wiggler wavenumber (wiggler period divided by 2 π). With these identifications, Equations (9) and (10) still describe how to achieve phase-stable operation. As with the axial FEL case, this scheme is implemented by (1) choosing the correct helix wiggle period, such that detuning is correct, and (2) adjusting the beam-wall spacing to obtain the desired space-charge wavenumber.
The foregoing description of the invention has been presented for purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto. | Autophase stability is provided for a traveling wave device (TWD) electron beam for amplifying an RF electromagnetic wave in walls defining a waveguide for said electromagnetic wave. An off-axis electron beam is generated at a selected energy and has an energy noise inherently arising from electron gun. The off-axis electron beam is introduced into the waveguide. The off-axis electron beam is introduced into the waveguide at a second radius. The waveguide structure is designed to obtain a selected detuning of the electron beam. The off-axis electron beam has a velocity and the second radius to place the electron beam at a selected distance from the walls defining the waveguide, wherein changes in a density of the electron beam due to the RF electromagnetic wave are independent of the energy of the electron beam to provide a concomitant stable operating regime relative to the energy noise. | 7 |
FIELD OF THE INVENTION
[0001] This invention relates generally to ophthalmic surgical instruments, and particularly to ophthalmic injectors by means of which segments of material can be inserted into incisions in the eye. It is more particularly concerned with instruments for the surgical treatment of conditions such as hyperopia and presbyopia where segments of material are inserted into the eye-for corrective treatment.
[0002] Hyperopia is a condition in which visual images come to a focus behind the retina of the eye because of defects in the refractive media of the eye or because of abnormal shortness of the eyeball. A new surgical technique for the treatment of this condition involves the insertion of a plurality of segments of transparent material, e.g. PMMA, into the cornea, to flatten the cornea and to change the refractive parameters of the eye. The technique involves making incisions in the cornea on a circle towards the outside of the cornea. The incisions are generally about 400 microns deep, i.e. about two-thirds of the thickness of the cornea, and six to eight incisions are normally made, equispaced around the cornea. Specially shaped segments of transparent material are then pushed into the incisions, from the outside of the cornea towards the optical zone. These segmental inserts have the effect of flattening the cornea and changing the refractive parameters in such a way as to bring the visual images to a focus on the retina.
SUMMARY OF THE INVENTION
[0003] It is an object of the present invention to provide a surgical instrument which will facilitate the introduction of segmental inserts into the eye by the surgeon.
[0004] It is a further object of the invention to provide an ophthalmic injector for the treatment of for example hyperopia which can be used with segmental inserts of different dimensions without the need to adjust the injector.
[0005] It is yet a further object of the invention to provide an ophthalmic injector for the treatment of for example hyperopia which enables the surgeon to perform the treatment more easily and more accurately than using forceps, which is what is currently used.
[0006] [0006]FIG. 1 of the accompanying drawings illustrates a typical segmental insert, indicated generally at 10 , as used in the treatment of hyperopia. FIGS. 1 a to 1 c show the insert in plan view, side view and cross-section respectively. The numerical ranges shown in the drawing in respect of length, width and thickness illustrate the range of dimensions which is typical for these inserts. The dimensions are given in inches. The corresponding metric values are as follows:
Length: 1.50-2.16 mm Width: 0.48-0.79 mm Thickness: 0.28-0.51 mm
[0007] The surgeon will choose segments of appropriate dimensions to meet the needs of individual patients. For any given eye, each of the segments which is inserted will be of the same dimensions.
[0008] In accordance with the invention there is provided an ophthalmic injector comprising a barrel, a plunger displaceable longitudinally within the barrel, a nose tip forwardly of the barrel, and a segment holder arranged to hold a plurality of segments to be inserted into incisions in the eye, the segment holder being displaceable stepwise and being positioned so that the segments are engageable in turn by the plunger or an extension thereof to push them from the holder through the nose tip.
[0009] The segment holder may be a rotatable carousel-type holder with segments arranged on the locus of a circle, or may alternatively be a linear holder which can be indexed through the barrel.
[0010] Preferably, the segments in the holder are retained under spring bias until pushed from the holder, to enable different sizes of segments to be accommodated in the same holder.
[0011] The barrel of the injector may be a solid element or may alternatively be of the type which can be broken open at a nose portion, in the manner of a shotgun, for the insertion of the segment holder.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In order that the invention may be more fully understood, two presently preferred embodiments of hyperopia injector will now be described by way of example and with reference to the accompanying drawings. In the drawings:
[0013] [0013]FIG. 2 is a top plan view of a first embodiment of injector in accordance with the invention, with the plunger depressed;
[0014] [0014]FIG. 3 is a side view of the injector of FIG. 2, with the plunger retracted;
[0015] [0015]FIG. 4 is a top plan view of the nose tip of the injector of FIGS. 2 and 3;
[0016] [0016]FIG. 5 is a side view of the nose tip of FIG. 4;
[0017] [0017]FIG. 6 is an end view of the nose tip of FIGS. 4 and 5;
[0018] [0018]FIG. 7 is a side view of the nose of the injector of the first embodiment;
[0019] [0019]FIG. 8 is an end view of the nose of FIG. 7, viewed from the left-hand side of FIG. 7;
[0020] [0020]FIG. 9 is an end view of the nose of FIG. 7, viewed from the right-hand side of FIG. 7;
[0021] [0021]FIG. 10 is an end view of the segment holder of the injector of FIGS. 2 and 3;
[0022] [0022]FIG. 11 Is a vertical sectional view through the centre of the segment holder shown in FIG. 10;
[0023] [0023]FIG. 12 is an end view of a segment holder spring of the injector of FIGS. 2 and 3;
[0024] [0024]FIG. 13 is a sectional view through the segment holder spring of FIG. 12;
[0025] [0025]FIG. 14 is a side view of the centre rod of the injector of FIGS. 2 and 3;
[0026] [0026]FIG. 15 is a view, on an enlarged scale, of the tip of the centre rod of FIG. 14;
[0027] [0027]FIG. 16 is a plan view of a loading plate for use with the injector of FIGS. 2 and 3;
[0028] [0028]FIG. 17 is a side view of the loading plate of FIG. 16.
[0029] [0029]FIG. 18 is a side view of a second embodiment of injector in accordance with the invention, with the plunger depressed;
[0030] [0030]FIG. 19 is an underneath plan view of the injector of FIG. 18, with the plunger retracted;
[0031] [0031]FIG. 20 shows the segment holder case used in the injector of FIGS. 18 and 19;
[0032] [0032]FIG. 21 is a cross-sectional view through the segment older case of FIG. 20;
[0033] [0033]FIG. 22 shows the spring used with the segment holder case of FIG. 20; and,
[0034] [0034]FIG. 23 is a cross-sectional view through the spring shown in FIG. 22.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] Referring first to FIGS. 2 and 3, there is shown a first embodiment of segment injector which is of the broken barrel type, i.e. the front end portion can be broken open relative to the main body of the instrument to facilitate loading of the segments to be inserted. The injector comprises a main body 11 which has a flange 12 at the rearward end. A nose 14 having a nose tip 16 is connected to the injector body 11 for pivotal movement about a pivot pin 18 . Thus, the nose 14 and nose tip 16 can be pivoted down through approximately 90° relative to the injector body. When closed, the nose 14 is held locked in place by a locking spring, screw and domed pin, indicated generally at 20 . The nose 14 houses a segment holder 22 which will be described in more detail hereinafter. As shown most clearly in FIG. 3, the segment holder projects proud of the main body of the injector so that it can be manually rotated. The segment holder is held in place in a manner which enables it to be indexed by the provision of a locking spring, screw and domed pin, indicated generally at 23 .
[0036] Within the injector body 11 there is housed a plunger 24 which has a thumb pad 26 at its outer end and which carries a pair of friction pads 28 spaced along its length for engagement with the inside of the injector body 11 . The forward end 29 of the plunger 24 is of reduced diameter and is counterbored to receive the rearward end of a centre rod 30 to which it is pinned. The purpose of the centre rod 30 is to push segments from the segment holder 22 out through the nose tip, as will be described in more detail hereinafter. Within the body 11 there is also provided a helical spring 32 which is seated at the forward end against an abutment surface within the injector body and at the rearward end against an abutment surface on the plunger 24 .
[0037] [0037]FIGS. 4, 5 and 6 show details of the nose tip 16 . In FIG. 3 the nose tip is shown with a curved configuration, whereas in FIG. 5 it is shown as linear. Whether or not the nose tip is provided with a degree of curvature, and the amount of that curvature, is a matter both of choice and of how the instrument is most easily to be used by the surgeon. Different surgical techniques may require nose tips of different configuration. As shown in FIGS. 4 and 5, the nose tip comprises a root portion 34 which is housed within the nose 14 , an intermediate portion 36 which tapers both in width and thickness, and a tip portion 38 . Along the length of the nose tip 16 there extends a guide channel 40 along which the individual segments to be inserted are pushed. The guide channel 40 has a generally trapezoidal cross-section which is wider at the surface and whose sloping side walls 42 make an angle of 90°.
[0038] FIGS. 7 to 9 shown details of the nose 14 . The rearward end of the nose 14 includes a locating lug 42 which is received in a slot in the main body 11 of the injector. The nose is pivotable about the pin 18 . The rearward face of the nose is provided with a part-circular recess 44 to receive the segment holder 22 . It will be appreciated from the location of the recess 44 , see FIG. 9 for example, that a portion of the circular segment holder 22 will extend proud of the peripheral surface of the nose 14 . Extending through the nose, from the recess 44 to the forward face of the nose, is a central passage 46 through which the segments are arranged to pass in their travel from the holder to the nose tip. The nose 14 is also provided with a generally elliptical aperture 48 which receives the root portion 34 of the nose tip 16 . Thus, the dimensions of the aperture 48 match the external dimensions of the nose tip root as shown in FIG. 6. The recess in which the spring, screw and domed pin 23 are located is indicated at 49 in FIG. 9.
[0039] [0039]FIGS. 10 and 11 shown the segment holder 22 . This is generally circular and is cup-shaped. It is provided through the base of the cup with nine equispaced holes 50 to receive the segments. Around the periphery of the segment holder is provided a series of indentations 52 by means of which the segment holder can be manually indexed on a step-by-step rotational basis. The segment holder has a central hole 53 through its base. The segment holder 22 fits within the recess 44 in the nose 14 and is engaged by the domed pin of the spring-screw-pin combination 23 to provide a ratchet-type indexing facility.
[0040] [0040]FIGS. 12 and 13 show a segment holder spring 54 which comprises a central cylindrical portion 56 and a circumferential skirt 58 which projects at an angle of some 30° to the longitudinal axis of the central cylindrical portion. The spring 54 is seated within the central aperture 53 through the segment holder 22 , with the skirt 58 extending into the chamber defined by the cup-shaped segment holder. This can be seen for example in FIG. 3. The purpose of the spring skirt 58 is to exert pressure against the segments which are loaded in the segment holder 22 . By providing this spring pressure one can accommodate different sized segments within the holes 50 in the segment holder.
[0041] [0041]FIGS. 14 and 15 show details of the centre rod 30 . The forward end of the centre rod 30 , as shown most clearly in
[0042] [0042]FIG. 15, has a stepped configuration so that the same rod can be used to propel segments of different sizes. All these tip sections of the centre rod will fit in the channel 40 of the nose tip 16 .
[0043] In use, when the carousel-style segment holder 22 has been loaded with segments of the required dimensions, with the spring 54 exerting pressure against them to hold them in place in the holes 50 , the plunger 24 is depressed to advance the centre rod 30 so that its stepped tip engages with the segment in one of the holes 50 and pushes it forward through the nose and through the nose tip, along the guide 40 into the incision in the cornea. When the segment has been inserted the surgeon will then simply rotate the segment holder 22 manually through one step, to align the next segment with the centre rod. The procedure is then repeated.
[0044] [0044]FIGS. 16 and 17 show a loading plate 60 . This is a generally rectangular plate with an annular recess 62 around a spigot 64 . The outer diameter of the circular recess 62 is equal to the external diameter of the segment holder 22 , and the diameter of the central spigot 64 is equal to the diameter of the hole 53 through the centre of the segment holder. The segment holder 22 can therefore be placed into the loading plate 60 and held there for the insertion first of the segments and then of the segment holder spring 54 . The loaded unit can then be transferred to the nose 14 .
[0045] Referring now to FIGS. 18 and 19 there is shown a second embodiment of segment injector in accordance with the invention. Components which are the same as in the first embodiment are indicated by the respective same reference numerals. In this embodiment the injector is not adapted to have the nose portion pivoted open, but instead has a solid barrel 100 . The mechanism for dispensing the individual segments is generally the same as in the first embodiment, and the description of those components of the injector will not therefore be described again. In this embodiment, the segment holder is not in the form of a carousel but is in the form of a linear case 102 which is shown most clearly in FIGS. 20 and 21. The case is fitted into the injector so as to extend transversely to the longitudinal axis of the injector. It traverses the barrel 100 through a passageway 103 (FIG. 19) through the barrel. The case is provided with a plurality of indentations 104 along its base by means of which the. case can be advanced linearly in a step-by-step manner. A screw-spring-domed pin combination 105 (FIG. 18) provides a ratchet-type mechanism. The segment holder case 102 is provided with an elongate aperture 106 therethrough. The upper portion of the case 102 is provided with a slot 108 which extends downwards at an angle of some 20° from an upper shoulder of the case down into the through aperture 106 . This angled slot 108 extends along substantially the full length of the segment holder case. This angled slot 108 is arranged to receive a segment holder spring 110 which is shown in FIGS. 22 and 23. The length of the segment holder spring 110 is equal to that of the case 102 and is provided with a plurality of nine downwardly extending teeth 112 which are thin and springy. The spring 110 is fitted into the angled slot 108 and is secured to the case by pins towards each end of the spring. The spring teeth 112 extend down into the through aperture 106 and the bottom edge of each spring tooth 112 is shaped with a concave recess so that it will contact and hold a segment between the tooth and the bottom of the aperture 106 . Again, because of the springiness of the teeth, segments of different sizes can be accommodated within the same segment holder case. Also, the configuration and shape of the spring teeth can be adapted to the configuration and shape of whatever segment is to be inserted by the injector. The number of spring teeth 112 corresponds to the number of indentations 104 in the bottom of the case, so that the case can be indexed through the injector for the serial insertion of the segments into the incisions in the cornea.
[0046] The injectors described above can be modified by being fitted with interchangeable noses and/or nose tips, to enable different segment holders to be used with the same injector.
[0047] Also, although the rotatable segment holder has been described as part of a pivotally openable injector, and the linear segment holder as part of an injector with a solid barrel, each type of segment holder can be incorporated in an injector of the other type. | An ophthalmic injector for the insertion of segments of material into the eye comprises a barrel ( 11 ), a plunger ( 24 ) displaceable within the barrel, a nose ( 14 ) and a nose tip ( 16 ). A rotatable carousel-type holder ( 22 ) for the segments is mounted in the nose for stepwise indexing movement. The segments are pushed in turn from the holder by a centre rod ( 30 ) connected to the plunger, through the nose and along a guide channel in the nose tip. The nose ( 14 ) and the nose tip ( 16 ) are pivotable through 90° relative to the barrel. Alternatively, the segment holder can be a linearly movable holder, indexable transversely across and through the barrel. The holder can carry nine segments. The injector can be used for the insertion of segments used in the treatment of hyperopia. | 0 |
APPLICATION DATA
[0001] This application claims benefit to U.S. provisional application No. 60/428,618 filed Nov. 22, 2002.
FIELD OF INVENTION
[0002] This invention relates to the synthesis of aryl intermediate compounds which are useful in the production of pharmaceutically active heteroaryl urea compounds.
BACKGROUND OF THE INVENTION
[0003] Aryl- and heteroaryl-substituted ureas have been described as inhibitors of cytokine production. These inhibitors are described as effective therapeutics in cytokine-mediated diseases, including inflammatory and autoimmune diseases.
[0004] U.S. Pat. No. 6,358,945 describes cytokine inhibiting ureas of the following formula:
[0005] An intermediate required to prepare preferred compounds described therein has a 1,4-disubstituted naphthalene as Ar 2 and is illustrated in the formula below.
[0006] The preparation of these intermediates require the coupling of the naphthyl ring with X. Preferred X include aryl and heteroaryl groups. Previously described methods, including U.S. Pat. No. 6,358,945 achieves the coupling of these aromatic residues by using a coupling reaction catalyzed by a transition metal, such as palladium, in the presence of a ligand, such as triphenyl phosphine. Coupling methods include Stille coupling, requiring the preparation of a tributylstannyl intermediate, or a Suzuki coupling, requiring the preparation of an aryl boronic acid intermediate (Scheme I).
[0007] The aryl boronic acid intermediate shown in I has previously been prepared via Br—Li exchange at −70° C. It is desirable to develop a procedure without using cryogenic condition for large-scale or industrial scale production.
[0008] Kitigawa et al. disclose a method for preparing trialkyl magnesates useful for halogen-metal exchange ( Angew. Chem. Int. Ed. 2000, 39, No. 14 2481-2483). No example in the paper implied the applicability of this method to the preparation of A, which has an acidic proton on the nitrogen.
BRIEF SUMMARY OF THE INVENTION
[0009] It is therefore an object of the invention to provide a non-cryogenic synthesis for aryl intermediate compounds such as aryl boronic acids which are useful in the production of heteroaryl urea compounds.
DETAILED DESCRIPTION OF THE INVENTION
[0010] In a broad generic aspect, there is provided a method of making a compound of the formula (A):
[0011] wherein the formula (A):
[0012] P is a nitrogen protecting group compatible with Grignard reagents, preferably P is chosen from Boc, Cbz, —CO 2 Me, —Ac, -Bn; preferably P is Boc;
[0013] Y is chosen from —B(OH) 2 , —CHR′—OH, —CR′ 2 —OH, alkyl, alkene and acyl;
[0014] E is an electrophile as defined herein below;
[0015] the phenyl ring in (A) is optionally benzo-fused to form naphthyl wherein substituents Y or NH—P can be independently at any position on each of the one or two rings, where the phenyl is not benzo-fused substitution can be para, meta or ortho, preferably para; preferably formula (A) is
[0016] said method comprising, in a one pot reaction:
[0017] reacting a compound of the formula (B) with 2 equivalents of R 3 MgLi, wherein and R is C 1-5 alkyl, preferably n-butyl, in an aprotic solvent at a temperature between −40° C. to 40° C., preferably −20° C. to 0° C., more preferably 0° C., the aprotic solvent is, for example, dioxane, diethoxymethane, methylTHF, THF, diisopropylether, hydrocarbons including hexanes, heptane, isooctane, cyclohexane, xylenes, Toluene, dichloromethane, DME, MTBE, or mixtures thereof, preferably the aprotic solvent is THF;
[0018] (B) wherein X is bromine or iodine, preferably bromine, subsequently adding an electrophile E, such as, for example, B(OCH 3 ) 3 , aldehydes such as CH 3 CHO, ArylCHO, ketones such as CH 3 COCH 3 , ArylCOCH 3 , halide such as CH 2 ═CHCH 2 Br, CH 3 I, or esters such as CH 3 CO 2 Et, preferably E is B(OCH 3 ) 3 , further non-limiting examples of E are set forth in the table below;
[0019] to produce a compound of the formula (A)
[0020] All terms as used herein in this specification, unless otherwise stated, shall be understood in their ordinary meaning as known in the art.
[0021] RT or rt—room temperature;
[0022] n-BuLi—n-Butyllithium
[0023] DME—1,2-Dimethoxyethane
[0024] THF—Tetrahydrofuran.
[0025] Boc—tert-Butoxycarbonyl.
[0026] Cbz—Benzyloxycarbonyl.
[0027] Ac—Acetyl.
[0028] Bn—Benzyl.
[0029] MeLi—methyllithium.
[0030] Unless otherwise noted, alkyl shall be understood to mean C 1-10 alkyl chain, preferably C 1-5 alkyl, branched or unbranched. An alkene is a partially unsaturated alkyl.
[0031] Ester, acyl, ketone, aldehyde and alkene shall be understood to mean an alkyl chain as herein above defined, with the respective functional group.
[0032] The term “aryl” as used herein shall be understood to mean aromatic carbocycle or heteroaryl as defined herein. Preferred carbocycles include phenyl and naphthyl. Each aryl or heteroaryl unless otherwise specified includes it's partially or fully hydrogenated derivative. For example, naphthyl may include it's hydrogenated derivatives such as tetrahydranaphthyl. Other partially or fully hydrogenated derivatives of the aryl and heteroaryl compounds described herein will be apparent to one of ordinary skill in the art.
[0033] It shall be understood, that the definitions E and Y have the following corresponding relationship as seen in the table and scheme below:
E Y B(O—C 1-5 alkyl) 3 —B(OH) 2 R′HC═O —CHR′—OH R′ 2 C(═O) —CR′2—OH R′X —R′ R′CO 2 R′ R′ 3 SnX SnR′ 3 R′ 3 SiX R′ 3 Si R′ 2 (OR′)SiX or SiR′ 2(OR′) (R′ 2 SiO) 3
[0034] Wherein R′ can be alkyl or aryl as defined herein, X is halogen and for B(O—C 1-5 alkyl) 3 the C 1-5 alkyl includes all C 1-5 alkyl, preferably methyl, ethyl, propyl and butyl, more preferably methyl.
[0035] The compounds of the invention are only those which are contemplated to be ‘chemically stable’ as will be appreciated by those skilled in the art. For example, a compound which would have a ‘dangling valency’, or a ‘carbanion’ are not compounds contemplated by the invention.
[0036] In order that this invention be more fully understood, the following examples are set forth in the overall reaction scheme below. These examples are for the purpose of illustrating preferred embodiments of this invention, and are not to be construed as limiting the scope of the invention in any way.
EXAMPLE
Synthesis of N-Boc-4-amino-1-naphthalene boronic acid
[0037] [0037]
[0038] In a dry flask under Argon was added butylmagnesium chloride (2.0 M in THF, 2.0 mL, 4.0 mmol) and anhydrous THF (10 mL). The solution was cooled to −5° C. and butyllithium (1.6 M in hexane, 5.0 mL, 8.0 mmol) was added dropwise while the temperature was kept below 0° C. After the resulting solution was stirred at 0° C. for 0.5 h, the temperature was lowered to −5° C. N-Boc-4-bromo-1-aminonaphthalene (0.64 g, 2.0 mmol) was dissolved in anhydrous THF(10 mL) and added dropwise while the temperature was kept below 0° C. The solution was stirred at 0° C. for 0.5 h. HPLC of a sample taken from the solution and quenched with MeOH indicated that no starting material was left. The temperature was lowered to −5° C. and trimethyl borate(2.5 mL, 22.0 mmol) was added slowly. After the mixture was stirred at 0° C. for 2 h, ammonium chloride solution (saturated, 20 mL) was added and the mixture was stirred at 21° C. for 0.5 h. The pH of the mixture was adjusted to 7 with sodium bicarbonate and the mixture was stirred at 21° C. for 18 h. Ethyl acetate (10 mL) was added and the mixture was stirred for 0.5 h. The organic layer was separated and dried with magnesium sulfate. The solvent was removed under vacuum and then hexane (60 mL) was added and the resulting slurry was stirred for 0.5 h. Filtration and hexane (10 mL) wash gave the title compound as a white solid (0.46 g, 80.5% pure, 65% yield). | Disclosed are methods of making aryl intermediate compounds of the formula (A) which are useful in the production of heteroaryl ureas,
(A) Y and P are defined herein below. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to an in-line sealed electrical connector apparatus having a connector apparatus position assurance device, and a locking method thereof. More particularly, this invention is directed to the connector apparatus position assurance device having contiguous parts for ensuring the engagement of the male and female connector assemblies of the in-line sealed electrical connector apparatus, and a locking method thereof.
2. Discussion of the Relevant Art
U.S. Pat. No. 7,465,192 is directed to an inline electrical connector apparatus that has a female connector assembly, the female connector assembly having a female housing, a female wire seal, and a female cover. The in-line sealed electrical connector of U.S. Pat. No. 7,465,192 further has a male connector assembly, the male connector assembly having a male housing, a retention clip, a male housing seal defining a male housing seal opening, a male wire seal, and a male cover. The female connector assembly is inserted within the male connector assembly, the female connector assembly being latched into the male connector assembly.
When the in-line electrical connector apparatus is in use, a first wire assembly is connected to the female connector assembly, while a second wire assembly is connected to the male connector assembly.
However, in the in-line electrical connector apparatus of U.S. Pat. No. 7,465,192, there is no assurance that the male housing assembly and the female housing assembly remain engaged and locked.
SUMMARY OF THE INVENTION
To ensure that the male housing assembly and the female housing assembly of the in-line sealed electrical connector apparatus of the present invention remain engaged and locked, a connector apparatus position assurance device is employed. The connector apparatus position assurance device has contiguous parts that engage various parts of the retention clip of the male connector assembly at different levels of insertion of the connector apparatus position assurance device into the male connector assembly. The insertion of the connector apparatus position assurance device is also accomplished at various stages (e.g., from pre-lock position to final lock position) dependent on the insertion level of the female connector assembly into the male connector assembly. For example, the effect of the level of insertion of the female connector assembly on various parts of the retention clip in turn affect the insertion of the connector apparatus position assurance device into the male connector assembly (i.e., from pre-lock position to final lock position). Also, if, e.g., the connector apparatus position assurance device happens to be fully inserted and in the final lock position, without the female connector assembly having been fully mated with the male connector assembly, the female connector assembly cannot be inserted into the male connector assembly.
Once fully inserted, the connector apparatus position assurance device ensures the locking engagement of the male and female connector assemblies of the in-line sealed electrical connector apparatus of the present invention. This is accomplished by the connector apparatus position assurance device of this invention ensuring that the retention clip of the male connector assembly fully locks therein the female connector assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of the in-line sealed electrical apparatus having a connector apparatus position assurance device of the present invention.
FIG. 2A is side elevation view showing a first side of the connector apparatus position assurance device of the present invention; FIG. 2B is a side elevation view showing a second side, opposite the first side, of the connector apparatus position assurance device of the present invention; and FIG. 2C is an elevation view showing an end side of the connector apparatus position assurance device of the present invention.
FIG. 3 is a perspective view of a retention clip of the male connector assembly showing the different parts thereof, which affect the insertion of the connector apparatus position assurance device of the present invention.
FIG. 4 illustrates a perspective view of the connector apparatus position assurance device, in a pre-lock position, in which a lowered inner retention clip finger and a raised outer retention clip finger Hock the connector apparatus position assurance device from being inserted.
FIG. 5 illustrates a perspective view of the connector apparatus position assurance device, still in a pre-lock position, in which the inner retention clip finger is raised, but the raised outer retention clip finger continues to block the connector apparatus position assurance device from being inserted.
FIG. 6 illustrates a perspective view of the connector apparatus position assurance device in which the inner retention clip finger is raised, while the outer retention clip finger is lowered for allowing the connector apparatus position assurance device to be finally unblocked and ready to be inserted.
FIG. 7 illustrates a perspective view of the connector apparatus position assurance device a fully inserted position and in a final lock position.
FIG. 8 is a perspective view of the connector apparatus position assurance device, in a full insertion position and final lock position, for completing the locking of the male and female connector assemblies of the in-line sealed electrical connector apparatus of this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is an exploded view showing the in-line sealed electrical connector apparatus of the present invention, generally referred to as reference number 1 . The in-line electrical connector apparatus 1 includes a male connector assembly 3 and a female connector assembly 5 . Mounted within the male connector assembly 3 is a retention clip 7 for receiving therein the female connector assembly 5 . Shown in FIG. 1 is a connector apparatus position assurance device 8 insertable into the male connector assembly 3 and the retention clip 7 . The male connector assembly 3 has, at an end portion thereof; a cover 10 . A wire assembly (not shown) can be inserted into the male connector assembly 3 through openings (not shown) passing through the cover 10 ; and another wire assembly (not shown) can similarly be inserted into the female connector assembly 5 through openings (not shown) at a free end 6 thereof.
The male connector assembly 3 has slots 12 , 14 passing therethrough for accommodating therein protrusions 20 , 22 extending from an upper side of the retention clip 7 . Slots 16 , 18 , opposed to the slots 12 , 14 , are for accommodating therein protrusions (not shown) extending from a lower side of the retention clip 7 , the lower side of the retention clip 7 being opposed to the upper side of the retention clip 7 .
The cover 10 of the male connector assembly 3 has an upper slot 25 passing through an upper side of the cover 10 and a lower slot 27 passing through a lower side of the cover 10 . The upper slot 25 is for accommodating therein a protrusion 30 extending from an upper side of the male connector assembly 3 . While the lower slot 27 is for accommodating therein a protrusion (not shown) extending from a lower side of the male connector assembly 3 . The cover 10 includes an elongated slot 28 extending along an inner surface thereof for accommodating therein an elongated protruding member 29 extending along a side portion of the male connector assembly 3 , the elongated slot 28 being used to slidably guide the elongated protruding member 29 when the cover 10 is slidably mounted on an end portion of the male connector assembly 3 .
As also illustrated in FIG. 1 , the male connector assembly 3 has a lever arm 50 with a fixed end 51 and a free end 52 . The free end 52 of the lever arm 50 includes an inner protruding member 54 , the inner protruding member 54 having an upper substantially inclined surface 55 and a lower substantially flat surface 56 . The fixed end 51 of the lever arm 50 is connected to the lower side of the male connector assembly 3 via a member 53 (generally, an L-shaped member). See, also, FIG. 8 .
The retention clip 7 includes a lower side 32 and an upper side 34 . An inside portion of the lower side 32 of the retention clip 7 includes an elongated slot 30 which accommodates therein an elongated protrusion (not shown) extending from a lower side of the female connector assembly 5 , the elongated slot 30 guiding the elongated protrusion of the female connector assembly 5 when the female connector assembly 5 is inserted into the retention clip 7 once the retention clip 7 is mounted inside the male connector assembly 3 . See, also, FIG. 3 .
Further, as also illustrated in FIG. 1 , the upper side 34 the retention clip 7 includes a pair of flexible fingers 36 , 38 ; namely an inner finger 36 and an outer finger 38 , the outer finger 38 having the protrusion 20 thereon (discussed earlier).
As later discussed, when the retention clip 7 is fully inserted and mounted within the male connector assembly 3 , the inner protruding member 54 of the free end 52 of the lever arm 50 is placed within a space 60 between end portions of the lower side 32 and the outer finger 38 of the retention clip 7 , the inner protruding member 54 of the lever arm 50 being wedged within the space 60 to prevent the outer finger 38 from moving downward (and the protrusions 20 , 22 from being dislodged from the slots 12 , 14 ) and to keep the retention clip 7 fully mounted and locked within the male connector assembly 3 . Also, the lever arm 50 is kept from moving (and therefore the inner protruding member 54 of the lever arm 50 from moving away from the slot 60 ) by a bar 62 connected at a side of the male connector assembly 3 .
As further shown in FIG. 1 , the female connector assembly 5 includes, on an upper surface thereof an elongated slot 40 for accommodating therein the outer finger 38 of the retention clip 7 when the female connector assembly 5 is fully inserted within the retention clip 7 , as more fully discussed later.
The connector apparatus position assurance device 8 has leading end members 70 , 72 ; namely, a first leading end member 70 and a second leading end member 72 , the first leading end member 70 extending longer from the base end 75 of the connector apparatus position assurance device 8 than the second leading end member 72 . As better shown in FIG. 2B and FIG. 2C , the axis of elongation of the second leading end member 72 is positioned below and to the side relative to the axis of elongation of the first leading end member 70 .
As further illustrated in FIG. 1 , the connector apparatus position assurance device 8 also has an elongated aperture 77 passing through a lower portion thereof, a pair of protrusions 79 extending downward from a bottom elongated member 81 thereof (see, FIG. 2A ), and an elongated protrusion 80 extending from a side thereof. When the apparatus position assurance device 8 is inserted into the male connector assembly 3 , the elongated protrusion 80 is slidably accommodated and partially guided within a corresponding elongated slot (not shown) within an inner surface of the male connector assembly 3 (more particularly, the inner surface of the lever arm 50 of the male connector assembly 3 ).
Also, the bottom elongated member 81 , below the elongated aperture 77 , acts as a flexible cantilever, and flexes when the pair of protrusions 79 slide over the generally L-shaped member 53 when the apparatus position assurance device 8 is inserted into the male connector assembly 3 . The pair of protrusions 79 , along with the generally L-shaped member 53 , act as additional assurance for ensuring that the apparatus position assurance device 8 is securely in place, in final lock position, when fully inserted into the male connector assembly 3 .
FIGS. 2A , 2 B, and 2 C illustrate the connector apparatus position assurance device 8 of the invention, in more detail, with FIG. 2A being a side elevation view showing a first side of the connector apparatus position assurance device 8 , FIG. 2B being a side elevation view showing a second side, opposite the first side, of the connector apparatus position assurance device 8 , and FIG. 2C being an elevation view showing an end side of the connector apparatus position assurance device 8 . Shown in FIG. 2B is the second leading end member 72 having the axis of elongation being positioned below and to the side relative to the axis of elongation of the first leading end member 70 resulting in a ledge-like surface 90 on an upper surface of the second leading end member 72 (see, FIG. 2B ).
Further illustrated in FIG. 2B is a slot 92 formed on a side surface of the base end 75 of the connector apparatus position assurance device 8 . The slot 92 (see, also, FIG. 2C ), which accommodates therein the elongated protruding member 29 extending along a side portion of the male connector assembly 3 , the slot 92 being used to slidably guide the connector apparatus position assurance device 8 when the connector position assurance device 8 is slidably inserted into the male connector assembly 3 .
FIG. 3 illustrates the retention clip 7 having the inner finger 36 and the outer finger 38 , both fingers 26 , 28 being flexible. When the retention clip 7 is mounted and locked within the male connector assembly 3 , the protrusions 20 , 22 of the retention clip 7 are accommodated within slots 12 , 14 , respectively, of the male connector assembly 3 , while opposing slots 16 , 18 of the male connector assembly 3 accommodate therein protrusions (not shown) extending from a lower side of the retention clip 7 , the inner protruding member 54 of the lever arm 50 of the male connector assembly 3 being wedged within the space 60 to prevent the flexible outer finger 38 from moving downward for securing the retainer clip 7 within the male connector assembly 3 by ensuring that the protrusions 20 , 22 remain within the slots 12 , 14 , respectively. The end portion of the lower side 32 has a substantially flat raised portion 93 , while the end portion of the outer finger 38 has a sloping portion 95 , the substantially flat raised portion 93 and the sloping portion 95 abutting and contacting the lower substantially flat surface 56 and the substantially inclined surface 55 , respectively, of the inner protruding member 54 of the free end 52 of the lever arm 50 , when the retention clip 7 is mounted and locked within the male connector assembly 3 .
The free end portion of the inner finger 36 has a ledge-like member 95 , while the free end portion of the outer finger 38 has a ledge-like member 98 .
During assembly of the in-line sealed electrical connector apparatus 1 , FIGS. 4-7 illustrate the mating of the female connector assembly 5 , the retention clip 7 , and the connector apparatus position assurance device 8 , with the presumption that the retention clip 7 has been mounted within the male connector assembly 3 . For clarification, in FIGS. 4-7 , the retainer clip 7 is not shown already mounted within the male connector assembly 3 so as to better explain the insertion and locking steps when the female connector assembly 5 , the retention clip 7 , and the connector apparatus position assurance device 8 achieve full mating and in final lock position. That is, to better understand the mating and locking steps of the female connector assembly 5 , the retention clip 7 and the connector apparatus assurance device 8 , the illustration of the male connector assembly 3 has been omitted from FIGS. 4-7 . In this invention, the retention clip 7 has been pre-mounted and locked, in the manner described above, within the male connector assembly 3 before the female connector assembly 5 is inserted into the retention clip 7 and before the connector apparatus position assurance device 8 is inserted into the male connector assembly 3 .
During initial insertion of the connector apparatus position assurance device 8 , in the pre-lock position, as shown in FIG. 4 , the insertion of the female connector assembly 5 into the retention clip 7 raises the outer finger 38 . The raising of the outer finger 38 results in the first leading end member 70 of the connector apparatus position assurance device 8 to be blocked by the end portion of the outer finger 38 . Further, the inner finger 36 remains in its lowered position; consequently,the second leading end member 72 of the connector apparatus position assurance device 8 is blocked by the end portion of the inner finger 36 . Thus, at initial insertion shown in FIG. 4 , the connector apparatus position assurance device 8 remains at a pre-lock position and cannot yet be inserted.
As shown in FIG. 5 , when the female connector assembly 5 is further inserted but not yet fully inserted) into the retention clip 7 , the leading end portion of the female connector assembly 5 reaches the inner finger 36 and raises the inner finger 36 . Consequently, the second leading end member 72 of the connector apparatus position assurance device 8 becomes unblocked. However, because the outer finger 38 remains in a raised position, the first leading end portion 70 of the connector apparatus position assurance device 8 remains blocked. Thus, the connector apparatus position assurance device 8 remains at a pre-lock position and cannot yet be inserted.
In FIG. 6 , the female connector assembly 5 has been fully inserted into the retention clip 7 . Consequently, the outer finger 38 has dropped into the elongated slot 40 of the female connector assembly 5 , thereby lowering the outer finger 38 . With the lowered outer finger 38 and with the raised inner finger 36 , the first leading end portion 70 and the second leading end portion 72 , respectively, of the connector apparatus position assurance device 8 become unblocked, and the connector apparatus position assurance device 8 is set and ready to be inserted.
With the female connector assembly 5 fully inserted into the retention clip 7 , as shown in FIG. 7 , the outer finger 38 is lowered when it drops into the elongated slot 40 of the female connector assembly 5 and the inner finger 36 remains raised, thereby unblocking the first and second leading end portions 70 , 72 , and allowing the connector apparatus position assurance device 8 to be fully inserted to complete the lock position and be at final lock position.
FIG. 8 shows the in-line sealed electrical connector apparatus of this invention in which the connector apparatus position assurance device 8 is in final lock position, ready to receive a wire assembly (not shown) to be inserted into the openings (not shown) passing through the cover 10 of the male connector assembly 3 and another wire assembly (not shown) to be inserted into the female connector assembly 5 through openings (not shown) at a free end 6 thereof. As shown in FIG. 8 and as discussed earlier, the retention clip 7 is mounted and kept locked within the male connector assembly 3 with the protrusions 20 , 22 of the retention clip 7 being respectively accommodated within the slots 12 , 14 of the male connector assembly 3 . (Protrusions (not shown) extending from the lower side of the retention clip 7 are similarly accommodated within respective slots 16 , 18 (see, FIG. 1 ) of the male connector assembly
In order to more clearly illustrate the connector apparatus position assurance device 8 in its fully inserted position and in complete or final lock position, the illustration of the side portion of the male connector assembly 3 containing the lever arm 50 and the bar 62 of the male connector assembly 3 is omitted in FIG. 8 . (Only a cross-section of the inner protruding member 54 of the lever arm 50 , discussed earlier, is shown in FIG. 8 , positioned within the space 60 between the end portions of the lower side 32 and the outer finger 38 of the retention clip 7 .) The connector apparatus position assurance device 8 , with its bottom elongated member 81 being seated on the generally L-shaped member 53 extending from the lower side of the male connector assembly 3 , is prevented from sliding out by the protrusions 79 and further prevented from moving laterally by its base end 75 being seated via the slot 92 thereof onto the elongated protruding member 29 extending along the side portion of the male connector assembly 3 . The first leading end member 70 is seated onto the ledge-like member 98 of the free end portion of the outer finger 38 , while the second leading end member 72 abuts a side portion of the free end portion of the outer finger 38 . The cover 10 is slidably mounted onto the male connector assembly 3 and locked thereto with the upper protrusion 30 and the lower protrusion (not shown) of the male connecter assembly 3 being respectively accommodated within the upper slot 25 and the lower slot 27 of the cover 10 .
As discussed above, the connector apparatus position assurance device 8 of this invention cannot be inserted past the pre-lock position until the female connector assembly 5 has been fully inserted and mated with the male connector assembly 3 .
Also, with the in-line sealed electrical connector apparatus 1 of this invention, if the connector apparatus position assurance device 8 happens to be fully inserted and in the final lock position before the female connector assembly 5 is inserted, the first leading end portion 70 of the connector apparatus position assurance device 8 is positioned on the ledge-like member 98 of the free end portion of the outer finger 38 of the retention clip 7 . Consequently, the outer finger 38 is at a lowered position, and is prevented from being raised by the first leading end portion 70 . Thus, the outer finger 38 blocks the female connector assembly 5 from entering the retention clip 7 . In other words, the female connector assembly 5 will detect its inability to be inserted by the inability of the outer finger 38 to be raised upward, for allowing the female connector assembly 5 to be inserted into the retention clip 7 , when the connector apparatus position assurance device 8 is in the final lock position.
Moreover, the female connector assembly 5 can only fully mate or inserted into the male connector assembly 3 when the connector apparatus position assurance device 8 is in the above-discussed pre-set position. If for example, a partial or improper mating is achieved (i.e., if the female connector assembly 5 is partially or improperly inserted into the male connector assembly 3 , as shown in FIG. 4 or FIG. 5 ), the connector apparatus position assurance device 8 cannot move forward or inserted because either the inner finger 36 has not been raised for allowing the second leading end member 72 of the retention clip 7 to be unblocked or the outer finger 38 has not been lowered for allowing the first leading end member 70 to be unblocked. Only when the female connector assembly 5 has fully mated or inserted into the male connector assembly 3 has occurred will the connector apparatus position assurance device 8 be allowed to be fully moved forward or inserted because the inner finger 36 has been raised for unblocking the second leading end member 72 of the retention clip 7 and the outer finger 38 has been lowered for unblocking the first leading end member 70 of the retention clip 7 , as shown in FIGS. 6 , 7 and 8 ), thereby having the connector apparatus position assurance device 8 to be in final lock position.
The present invention is not limited to the above-described embodiments; and various modifications in design, structural arrangement or the like may be used without departing from the scope or equivalents of the present invention. | A connector apparatus position assurance device ensures that a male connector assembly and a female connector assembly of an in-line sealed electrical connector apparatus of the present invention remain engaged. The connector apparatus position assurance device has contiguous parts that engage various parts of a retention clip of the male connector assembly at different levels of insertion of the connector apparatus position assurance device into the male connector assembly. The insertion of the connector apparatus position assurance device is also accomplished at various stages (i.e., from pre-lock position to final lock position) depending on the insertion level of the female connector assembly into the male connector assembly. Consequently, the effect of the level of insertion of the female connector assembly ensures that the male and female connector assemblies remain engaged. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the priority of Swiss Application No. 00 979/93-4, filed Mar. 30, 1994, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to an apparatus for attaching working elements, in particular a fixed carding element to a rotating, fibre-opening roller of a preparatory machine in a spinning mill.
2. Discussion of the Background of the Invention and Material Information
It is known, in spinning mill preparatory machines, particularly in carding machines, to attach working elements, such as separation knives, fixed carding elements, and the like, directly on the machine frame and that they are then set to the correct radial and/or pivot distance, relative to the rotating roller, by means of setting means such as eccentrically held discs, slots, spacers, or the like.
These settings require a considerable amount of effort and have to be carried out regularly in several partial steps, as the adjustment of the setting means and a subsequent fixation, via a screw, again causes a slight displacement of the setting, i.e. the distance, to be made. For such settings it is necessary to precisely adhere to the required tolerance ranges, which are constantly becoming increasingly narrower, by means of sheet calibers, screw pitch gages and the like.
Therefore, it an the object of this invention to achieve similarly precise distances, within a narrow tolerance range, in a more simple manner than in the previously-described methods.
SUMMARY OF THE INVENTION
This object is achieved via an apparatus for attaching a working element to a rotating fiber-opening roller, the roller being rotatably journalled in spaced axle retainers, wherein the working element is attached on the axle retainers via respective end caps, with the end caps at least partially encompassing the axle retainers.
The end caps are connected either to the axle retainers or with the working element, with each of the end caps preferably being provided with a plane surface in the zone of the working elements or the axle retainers.
In one embodiment of the present invention, each of the end caps is at least partially prismatically formed.
In another embodiment of the present invention, each of the end caps is provided with a recess, with the recess including means for guiding, which preferably consists of angular grooves.
In a further embodiment of this invention, each of the end caps is of unitary or one piece construction either with the axle retainer or the working element.
Previously, it was always the custom that fiber-opening rollers were held directly in a machine frame and that the pertinent working elements, such as separation knives and fixedly arranged carding elements, were also attached to the machine frame. Owing to the production tolerances it was thus necessary to set the required working distances by means of setting means such as spacers, slots, screws, etc. only during the installations thereof. However, since the production of fiber-opening rollers, such as pin rollers, clothing rollers provided with saw teeth, or needle rollers, with ever increasing precision, the outer circumferences become nearly ideally cylindrical and the diametral tolerances are kept minimal.
This trend or realization caused us to seek new means to allow the working elements to be arranged more precisely with respect to the roller. An accurately fitting attachment of the working element on the axle box or bearing retainer of the rotating roller gives, in addition to the advantage that less components are required, among other things, the added enormous advantage that a textile machine can be produced with less effort related to work the involved, i.e., with considerably less adjustment work.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings, there have generally been used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 is a schematic partial view of a fiber-opening roller including a cross section through a fixed carding element;
FIG. 2 is a sectional view, taken along line A--A of FIG. 1, through the axle box and the working element showing the end cap as an integral part of the axle box.
FIG. 3 is a sectional view, similar to that of FIG. 2, showing the end cap as a separate part, interposed between the axle boxes and the working element;
FIG. 4 is a sectional view, similar to that of FIG. 2, showing the end cap as an integral part of the working element; and
FIG. 5 is a sectional view, similar to that of FIG. 2, but taken along line B--B of FIG. 1, showing the engaging surface of the combing element situated in precisely the same plane as the engaging surface of the carrier on the axle boxes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With respect to the drawings it is to be understood that only enough of the construction of the invention and the surrounding environment in which the invention is employed have been depicted therein, in order to simplify the illustrations, as needed for those skilled in the art to readily understand the underlying principles and concepts of the invention.
FIG. 1 shows a fiber-opening roller 1, which here preferably takes the form of a licker-in, wherein the needles, tips or saw-tooth clothings thereof are not shown. Roller 1, is retained, via its axles or shafts 2, in axle boxes or axle retainers 4. The right portion of shaft 2 is shown with a broken end section, as it is connected with a non-illustrated drive unit of any desired type. The axle or longitudinal axis of roller 1 is denominated with reference numeral 3. A rolling contact bearing 5, shown purely schematically, resides within axle box 4, with rolling contact bearing preferably taking the form of a roller or needle bearing. Axle boxes 4 include end caps 6 having attached thereto working elements 7, which, in this embodiment, take the form of a fixed carding element. Fixed carding element 7 consists of a carrier 8 and one or more combing inserts 9, with carrier 8 being attached to cap 6 by means of non-illustrated screws.
FIG. 2 shows the same elements as FIG. 1 and utilizes same reference numerals. As can readily be seen in the drawing, end cap 6 is arranged prismatically in the zone adjacent to carding element 7, i.e., the connecting surfaces or areas of cap 6 abutting with carrier 8 are consistent with or correspond to the surfaces or areas of a prism having n corners. Carrier 8 consists of a drawn aluminum profile having hollow chambers 10 so as to both ensure stability and to allow adequate dissipation of the heat arising during operation. On the left side of carrier 8, a separator blade 11 is fixedly attached thereto with, for example, two hexagon socket screws 12. Non-illustrated slots in separator blade 11 permit the precise positioning of the blade tip thereof with respect to the saw-tooth clothing of roller 1.
As shown in FIG. 2, carrier 8 is also, at least in the zone adjacent to end cap 6, prismatically arranged, via which the precise positioning of the carrier 8, with respect to end cap 6, occurs automatically. As visible in FIG. 2, end cap 6 is a unitary part of axle box 4, which is generally made of cast iron. However, end cap 6 may also be a separate part which is fixedly attached, such as by screws, to axle box 4. This latter embodiment, however, has the disadvantage that in this manner a less precise control of the distance of the working elements, with respect to the rollers, is achieved, since the attached connection also adds further tolerances.
The preciseness required, without the need for adjustment, can be achieved in the illustrated embodiment because the engaging surface of the comb inserts or combing elements 9 is situated in precisely the same plane or in a plane precisely parallel thereto as the engaging surface of carrier 8 on axle boxes 4. For such preciseness it is not absolutely necessary that the surfaces of the cap 6 are at least partly prismatically arranged, but recesses could also be provided in carrier 8. These recesses could, for example, be angular grooves or flutes, for which purpose congruent mating elements would be provided on cap 6. The previously-described prismatic arrangement, however, is preferred owing to the simplicity of its solution. In another embodiment, end caps 6 could also be parts or portions of carrier 8 and respective countersink areas could be provided on axle bearing 4 so as to satisfy the previously-mentioned requirement of preciseness.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims and the reasonably equivalent structures thereto. Further, the invention illustratively disclosed herein may be practiced in the absence of any element which is not specifically disclosed herein. | An apparatus for attaching working elements, such as carding elements, to a rotating fiber-opening roller, such as a licker-in, wherein the working element is attached on the axle boxes or retainers of the roller by means of an end cap at least partially encompassing the axle boxes or axle retainers. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to dispensers, and more particularly, to dispensers for discharging material under pressure.
In the prior art, basically three different types of dispensers for discharging material are provided. These include: aerosol devices utilizing chemical propellants to pressurize and discharge the material; trigger operated mechanical discharge means wherein a pivoted trigger or lever is connected with a piston or plunger to obtain intermittent discharge or squirts of material; and finger operated pumps wherein a plunger is depressed with the finger to obtain intermittent discharges or squirts of the material.
All of these devices have one or more more disadvantages. For example, aerosol devices utilizing chemical propellants are being banned because of their potential harm to the environment. Moreover, these devices require specially constructed containers built to withstand high internal pressure, and the chemical propellants are not compatible with many materials desired to be dispensed. Additionally, there is considerable danger in handling and disposing of aerosol devices utilizing chemical propellants because of the pressures and explosive materials involved, and special precautions must be observed when filling aerosol containers utilizing chemical propellants.
The trigger operated dispensers and finger operated pump dispensers both eliminate the dangers inherent with chemical propellants, but are relatively difficult to operate and only a single short burst or discharge of the material is obtained with each manipulation of the actuator. The action required to operate such devices, and particularly the pump or plunger type devices, results in spray inaccuracy and finger fatigue.
SUMMARY OF THE INVENTION
The present invention represents a significant improvement over the prior art devices described above and is a specific improvement over the invention disclosed in Ser. No. 889,904, filed Mar. 24, 1978, which is, in turn, a divisional application of Ser. No. 729,830, filed Oct. 5, 1976, now Pat. No. 4,167,941.
More particularly, the present invention relates to a mechanically operated dispensing device which does not rely upon chemical propellants to obtain a pressurized discharge of the material and wherein the device may be easily operated with only one hand. Moreover, the device of the invention has several different modes of operation, including: a continuous and substantially constant discharge of material after an initial accumulating or charging operation, and requiring minimal force to operate a discharge member or button for release of material pressurized during the accumulating or charging operation; a continuous spray or discharge of the material during the time a pressurizing or charging member is being operated; and intermittent spurts or discharges of material coinciding with operation of a charging or pressurizing member.
Even more specifically, the present invention relates to a trigger operated dispensing device wherein a pivoted trigger is connected with a first expansible chamber means or pressurizing chamber for drawing material from a container and pressurizing it for discharge under pressure. A second expansible chamber means or accumulating chamber is connected with the first expansible chamber means for receiving pressurized material therefrom and accumulating a quantity of the material for subsequent discharge under pressure. A discharge valve includes flow control means connected between the expansible chambers and a discharge nozzle for operation between a plurality of positions, including a first position for precluding flow from either of the expansible chambers to the nozzle, and a second position establishing fluid communication between the expansible chambers and the nozzle. When the valve is in its first position, the trigger may be operated to draw material from the container, pressurize it and charge it into the accumulating chamber for storage of a quantity of the material under pressure in the accumulating chamber. Subsequent operation of the valve means to its open position releases the accumulated pressurized material from the accumulating chamber through the nozzle.
Alternatively, the valve means may be left in an open position and the trigger operated, whereupon the material will be drawn from the container to the first expansible chamber means, under pressure, and thence discharged in a substantially continuous flow through the valve means and nozzle.
If the first operation of the dispenser of the invention is accomplished with the valve in the open position, the material will be drawn into the first expansible chamber, pressurized therein and discharged through the nozzle in intermittent bursts or spurts, concomitant with operation of the trigger. On the other hand, if the first operation of the dispenser of the invention is accomplished with the valve in the closed position, operation of the trigger will cause material to be drawn from the container into the first expansible chamber, pressurized therein and discharged into the second expansible chamber means for accumulation of the material therein by repeated operations of the trigger. Subsequently, when the valve is opened, the accumulated, pressurized material in the second expansible chamber means will be discharged through the nozzle with a continuous, long duration, relatively constant pressure spray or stream, as desired, Thereafter, if the valve is left in the open position and the trigger operated, material will be drawn from the container into the first expansible chamber means, pressurized therein and discharged through the nozzle. However, a portion of the material will enter the second expansible chamber means and accumulate therein under pressure, whereby when the trigger is released for return of the first expansible chamber means to draw an additional charge of material thereinto, the previously accumulated material in the second expansible chamber means will be discharged through the nozzle, such that a substantially continuous discharge of material is obtained during operation of the trigger, the aforesaid being accomplished by means of controlling functional variables.
Moreover, the trigger operated dispenser of the present invention is exceptionally simple and economical in construction and is rugged and durable in operation. Further, when operating in the duration mode, the dispenser may be operated in any position, even upside down, without affecting the performance thereof. Additionally, the dispenser of the invention is refillable, if desired, and accomplishes performance goals currently achieved only with propellant based aerosols in explosion-proof cans. The present invention also allows optimum product formulation rather than requiring compromise due to chemical incompatibility between the product to be dispensed and a chemical propellant.
Still further, the present invention may be used to dispense a wide variety of products. Additionally, the dispenser includes means which permits unused pressurized product to leak back into the container, thereby providing a child safety feature. Means is also provided for relieving excess pressure, thereby preventing overpressurization of the second expansible chamber means.
Even further, a unique, unitary, integrally molded piston-trigger unit is provided in accordance with the invention, which is more economical and is easier to assemble than prior art devices; and a unique, integrally molded trigger return spring is provided in the shroud of the dispenser of the invention.
OBJECTS OF THE INVENTION
It is an object of this invention to provide a means for discharging material under pressure, without using chemical propellants and wherein the means is selectively operable to obtain either a duration discharge or an intermittent discharge of the material.
Another object of the invention is to provide a mechanically operated means for obtaining a long duration discharge of material, and wherein the means may be easily operated with only one hand.
A further object of the invention is to provide a mechanically operated means for discharging material under pressure wherein the means may be operated with one hand, and is selectively operable to obtain either a duration discharge or an intermittent discharge of the material, and wherein the means is exceptionally simple and economical in construction and is rugged and durable in use.
A still further object of the invention is to provide a trigger operated dispensing device for discharging material under pressure, wherein the device includes means for obtaining either a substantially constant pressure, long duration spray or discharge of the material, or an intermittent discharge of the material as desired.
A still further object of the invention is to provide a dispensing device which is capable of operating in three different modes for obtaining either a long duration constant discharge of material, or continuous discharge of material during operation of the pressurizing means, or intermittent discharge of the material concomitant with operation of the pressurizing means.
A more specific object of the invention is to provide a trigger operated spray dispenser which includes a first expansible chamber means connected with a pivoted trigger whereby operation of the trigger alternately draws material from a container into the first expansible chamber means and then pressurizes the material and transfers it under pressure to a second expansible chamber means for accumulation under pressure of the material, and a valve means is connected with the second expansible chamber means for releasing the pressurized material therefrom, as desired.
Another object of the invention is to provide a mechanically operated dispensing device for obtaining pressurized discharge of material, wherein a valve member is provided and has an off position precluding flow from the device and an on position enabling flow in either of two different modes.
A further object of the invention is to provide a trigger operated spray dispenser which has an accumulating chamber therein for accumulating a quantity of material under pressure and wherein a leak-back passage is provided for leaking unused material from the accumulating chamber to thereby provide a child safety feature.
Yet another object of the invention is to provide a means for discharging material under pressure wherein an accumulating chamber is provided for accumulating a quantity of material under pressure for subsequent discharge, and overpressure relief means is provided in communication with the accumulating chamber means for relieving excess pressure from the accumulating chamber means.
An even further object of the invention is to provide a trigger operated spray dispenser which is capable of obtaining a duration spray and which may be attached to conventional containers.
Yet a further object of the invention is to provide a trigger operated spray dispenser which may be attached to conventional containers and which may be assembled on conventional filling and capping lines and yet which includes means for obtaining a duration spray.
A further object of the invention is to provide a unique, integrally molded piston and trigger unit, which is economical and easy to assemble.
A still further object of the invention is to provide a unitary piston and trigger unit, integrally molded from high density polyethylene, and thus facilitate assembly of the unit to the dispenser manifold.
An even further object of the invention is to provide a unique, unitary, integrally molded shroud and trigger return spring unit, which eliminates the need for a separate trigger return spring, thus making the device of the invention more economical than some prior art devices, and facilitating assembly thereof.
Yet another object of the invention is to provide a positive acting vent for the container, which is opened to vent the container whenever the accumulating chamber means is expanded for discharge of material.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a container having a trigger operated dispenser of the invention assembled thereto.
FIG. 2 is an exploded perspective view of the dispenser of the invention.
FIG. 2a is a perspective view of the unitary, integrally molded piston and trigger unit of the invention, showing the piston in the as-molded orientation.
FIG. 3 is a view in side elevation of the dispenser of the invention showing the parts of FIG. 2 assembled together, except for the piston/trigger, discharge valve means, shroud and nozzle, which are removed from this figure for the purposes of clarity.
FIG. 4 is an enlarged, longitudinal vertical sectional view of the dispenser of the invention.
FIG. 5 is a view in section taken along line 5--5 in FIG. 4.
FIG. 6 is a front elevational view of the device of FIG. 4 with portions broken away, and the shroud in section.
FIG. 7 is a bottom view of the dispenser of FIG. 4.
FIG. 8 is an enlarged front view in elevation of the trigger/piston of the device of the invention.
FIG. 9 is an enlarged, fragmentary view in section, with portions removed, showing the leak-back and overpressure relief channel.
FIG. 9a is a fragmentary view in section of the blow-by and leak-back features of the invention of FIG. 9.
FIG. 9b is a view in section taken along line 9b--9b in FIG. 9a.
FIG. 9c is a view in section taken along line 9c--9c in FIG. 9b.
FIG. 9d is a view in section taken along line 9d--9d in FIG. 9b.
FIG. 9e is a view in section taken along line 9e--9e in FIG. 9a.
FIG. 10 is an exploded perspective view, with parts shown in section, of the nozzle and spud used in the device of the invention.
FIG. 11 is an enlarged, fragmentary sectional view of the discharge valve showing the valve in its depressed or open position for obtaining discharge of material.
FIG. 12 is a view similar to FIG. 11 but with the discharge valve rotated 90° about its longitudinal axis to lock the valve in its depressed or open position for continuous discharge of material from the device.
FIG. 13 is an enlarged fragmentary sectional view showing a modified discharge valve wherein positive opening of the valve from the bladder is provided and showing the discharge valve in the open position.
FIG. 14 is a view similar to FIG. 13, showing the valve in its closed position.
FIG. 15 is a front view of the modified trigger.
DETAILED DESCRIPTION OF THE INVENTION
In the drawings, wherein like reference numerals indicate like parts throughout the several views, a container C having a trigger operated dispensing device D thereon in accordance with the invention is represented generally at 10 in FIG. 1. The container C may be made of any suitable material such as metal, glass or plastic amd may be produced in any desired configuration or design for functional or aesthetic reasons.
The components of the dispensing device D are seen best in FIGS. 2 through 7 and comprise a closure member 11, which in one form of the invention comprises a cylindrical, internally threaded skirt 12 having a top wall 13 with a central opening 14 formed therethrough. A vent adapter 15 has a cylindrical side wall 16 extended through the opening 14 in the closure 11 and an outwardly directed annular flange 17 on the lower end thereof engaged beneath the end wall 13 of the closure 11. The vent adapter 15 has a concave, substantially frustoconically shaped end wall 18 with a central opening 19 therethrough and an upstanding post or vent actuator 20 integrally formed thereon. A plurality of outwardly formed rings or ribs 21 are on the outer surface of the cylindrical body 16 of the vent adapter 15 for a purpose described below.
A one-piece molded bladder retainer 22 includes a depending cylindrical skirt 23 having a plurality of ribs or channels 24 formed on the inner surface thereof for secure snap-fitting engagement with the ribs 21 on the vent adapter 15, as seen in FIG. 4. Thus, when the vent adapter, bladder retainer and closure are assembled together, as in FIG. 4, they are securely held in the assembled relationship by engagement of the outwardly turned flange 17 of the vent adapter beneath the wall 13 of closure 11 and the engagement of cylindrical wall 23 of bladder retainer 22 against the top of wall 13. A generally rectangularly shaped upstanding configuration 25 is formed on the top of cylindrical skirt 23 at one side thereof, and defines a rectangularly shaped channel therein in which the upstanding post 20 is slidably received when the parts are in assembled relationship. The configuration 25 thus defines a guide or support member for the vent actuator 20 and the guide or support member extends substantially from the outer circumference of skirt 23 to the center thereof. An elongate, axially extending tubular member 26 is formed at the center of the bladder retainer coaxially with the axis of skirt 23, and a plurality of axially extending flutes or channels 27 are formed in the outer surface thereof at the lower end for cooperation with the opening 19 through the frustoconical wall 18 of the vent. Thus, with the parts in their normal assembled position, as seen in FIG. 4, the flutes or channels 27 terminate short of the point of engagement of wall 18 with the outer surface of tubular member 26, whereby the opening 19 through the wall 18 is closed. However, when the wall 18 is moved downwardly, the opening 19 comes into registry with the flutes or channels 27 thereby establishing communication from above the wall to below the wall.
An upstanding, substantially circular superstructure 28 is formed at the upper end of the tubular member 26 and has an opening 29 formed therethrough with its axis extending perpendicularly to the axis of the skirt 23. A second, smaller opening 30 is also formed through the circular superstructure 28 and extends from the front face 31 thereof rearwardly into registry with the upper end of the bore through tubular member 26. A radially outwardly projecting locking rib 32 is formed on the outer periphery of the superstructure 28 and an axially forwardly projecting annular wall or retaining flange 33 is formed on the inner surface of the superstructure 28 in surrounding relation to opening 29.
An expansible chamber means or accumulating chamber 34 comprises a resilient bladder 35 having an elongate hollow body with a radially outwardly projecting flange 36 on one end thereof, having an annular rearwardly directed wall or retaining lip 37 received in the cavity formed behind retaining lip or flange 33 of the bladder retainer 22. The bladder 35 also has a relatively thin, flexible, forwardly projecting, cylindrical valving wall 38 formed on the forward wall surface thereof, and an annular, radially inwardly directed, flexible valving ring or member 39 is formed substantially coplanar with the forward end wall surface of the bladder and defines a central opening 40 opening into the hollow interior of the bladder.
A one-piece molded manifold member or body 41 includes a cylindrical wall 42 having a detent rib or ring 43 formed on the inner surface thereof and which cooperate with the locking rib 32 on the bladder retainer 22 to hold the manifold 41 to the bladder retainer as seen in FIG. 4. An annular, rearwardly facing wall 44 is formed in the manifold, radially inwardly of the skirt or wall 42, and the annular wall 44 engages an outer marginal edge portion of the flange 36 on bladder 35 to securely hold the bladder in position between the bladder retainer and manifold. The end wall 44 is countersunk at 45, defining a recess or chamber in which the cylindrical valving wall 38 of the bladder is received. The diameter of the chamber 45 is approximately the same as the outer diameter of the wall 38, whereby the wall 38 engages snugly against the wall of chamber 45, and cooperates therewith to form a valve preventing flow from the bladder into a radially extending port or passage 46 formed in the manifold 41 and which communicates at its radially outer end with the forward end of passage 30 in bladder retainer 22. The central portion of the manifold 411 projects rearwardly at 47 into engagement with the annular valving member 39 on the bladder whereby flow from the hollow interior of the bladder into the chamber 45 is prevented by seating of the valving member 39 against the projection 47 of the manifold. A chamber 48 is formed at one side of the bladder in communiction with the central opening 40 for free flow of material from within the bladder, through the chamber 48 and into elongate passage or port 49 extending forwardly through a tubular discharge portion 50 of the manifold.
The manifold 41 also includes a cylindrical wall 51 projecting forwardly from the cylindrical wall 42 at substantially one diametral half portion thereof, and having an open forward end 52, and an opening 53 through the rearward end opening into the chamber 45.
A novel piston-trigger combination includes a piston 54 reciprocable in the cylinder 51 and defining with the cylinder, and expansible chamber means or charging chamber, which is operable when the piston is moved forwardly in cylinder 51 to draw material from a container C upwardly through dip tube T and through passage 30 into passage 46, urging the annular cylindrical valving wall 38 to an open position from the end of passage 46, and into the cylinder 51. When the piston 54 is moved rearwardly in the cylinder, the material therein is pressurized and caused to flow through the opening 53 and against valving member 39, moving it away from the projection 47, and thence into the bladder 35 and also through chamber 48 and into passage 49.
The piston 54 is formed integrally with a trigger-type actuator 55 having a generally flat lower end 56 and a bifurcated upper end 57 defining a pair of spaced apart legs 58 and 59 having inturned pivot pins or stub shafts 60 and 61 at their upper ends, respectively. The piston 54 and trigger 55 are preferably molded from a high density polyethylene, which enables assembly of the piston-trigger to the manifold, and ensures long life of the unit, and does not require initial flexing of the piston relative to the trigger when the molded assembly is first removed from the mold, as do prior art structures molded from polypropylene wherein it is necessary to flex the unit immediately upon its removal from the mold and while still warm in order to obtain appropriate molecular orientation such as to define a hinge. Thus, the steps of assembling the unit of the invention are more simple and economical than with the prior art devices, and to applicant's knowledge, the present invention is the only unitary, integrally molded piston-trigger unit. Moreover, while only one piston is shown, more than one piston could be connected with the trigger, if desired, for cooperation with a corresponding number of cylinders in order to obtain desired or required displacement volume in the device, while maintaining satisfactory force requirements.
The manifold 41 further includes an upstanding tubular post member 62 having a discharge passage 63 extending axially therethrough and opening through the upper end thereof, and terminating at its lower end in communication with the forward end of passage 49 in tubular discharge member 50.
A forwardly extending nozzle tube 64 is formed at the upper end of the post 62 and projects in a direction parallel with the tubular discharge member 50. The nozzle tube 64 has a coaxially extending nozzle spud 65 formed therein and projecting axially outwardly beyond the end of the nozzle tube. The spud 65 is spaced inwardly from the inner wall surface of nozzle tube 64 and has a pair of longitudinally extending feed grooves or channels 66 and 67 therein. A port 68 extends from the annular chamber defined between spud 65 and tube 64 and communicates with passage 63 in post 62. A radially outwardly projecting flange or rib 69 is formed on the outer end of nozzle tube 64 and locks behind a cooperating rib 70 formed in the inner surface of the skirt 71 of nozzle 72. A tubular sleeve 73 is formed within the nozzle 72 and projects rearwardly into the annular chamber defined between the spud and nozzle tube and seals the annular chamber against flow outwardly past the nozzle, except for flow through the feed grooves or channels 66 and 67 to the nozle opening.
As seen best in FIG. 10, a pair of diametrically opposed channels or slots 74 and 75 are formed on the inner face of the nozzle end wall and communicate at their inner ends with a relatively small circular swirl chamber 76. A second pair of substantially radially extending, diametrically opposed channels or slots 77 and 78 are also formed in the nozzle end wall and extend substantially perpendicular to the axis of the slots 74 and 75. The slots 77 and 78 communicate tangentially at their inner ends with the swirl chamber 76. The bead or rib 70 formed on the inner surface of the nozzle skirt 71 includes a pair of detents spaced 180° apart for cooperation with the flange or rib 69 on the nozzle tube 64 whereby the nozzle 72 may be turned or rotated to either of two positions disposed 180° apart, and whereat either the pair of slots 74 and 75 will be aligned with the feed grooves 66 and 67, or the slots 77 and 78 will be aligned with the feed grooves or slots 66 and 67. If the slots 74 and 75 are aligned with the feed grooves, a stream of fluid is emitted from the nozzle, whereas if the slots 77 and 78 are aligned with the feed grooves 66 and 67, a spray of fluid is emitted from the nozzle.
The discharge tube 50 projects at 79 beyond the post 62, and the bore 49 in the discharge tube extends outwardly through the extended end portion 79 and opens outwardly through the outer end thereof. A discharge valve 80 is received in the passage 49 in the extended end portion 79 and includes a tubular valving shaft 81 snugly received in the passage 49 and having a passage 82 formed therein at the inner end thereof communicating in axially aligned relationship with the passage 49 and terminating at its inner end in a wall 83. A plurality of radially extending ports 84 and 85 are formed through the wall of the shaft 81 at the inner end of the passage 82, and a head member 86 is formed on the outer end of the shaft outwardly of the extended end portion 79 of discharge tube 50. The head member or button 86 has a flexible annular skirt 87 thereon which engages against the outer end portion of the extended end 79 and serves to resiliently urge the discharge valve 80 outwardly of the extended end 79, or to the right as viewed in FIG. 4. A circumferentially extending annular seal and stop 88 is formed on the outer surface of the shaft 81 between the open inner end thereof and the radial ports 84 and 85, and when the discharge valve is urged outwardly by the skirt 87, and the annular seal and stop 88 engages against an adjacent wall surface of the passage 63 in post 62 to prevent further outward movement thereof. In this position the ports 84 and 85 are sealingly closed to flow therethrough and no material can flow through the passage 63 to the nozzle. However, the head or button 86 may be engaged with the finger and pressed inwardly of the extended end portion 79 against the flexing, resilient action of the skirt 87 to align the radial ports 84 and 85 with the vertical passage 63 in post 62, whereupon any pressurized fluid in passage 49 will escape through passage 82 and ports 84 and 85, and thence upwardly through vertical passage 63 and through port 68 to the annular chamber between the nozzle spud 65 and nozzle tube 64 and thence through the feed grooves or slots 66 and 67 to one or the other of the pairs of radially extending slots or channels in the nozzle end wall.
A pair of radially outwardly projecting latching means or tabs 89 and 90 are formed on the head or button 86 whereby the button may be moved inwardly to open the discharge valve 80 and rotated 90° in either direction to bring one or the other of the latching tabs 89 and 90 into registry behind the skirt 71 of nozzle 72, thereby latching the button and discharge valve in the inwardly depressed, open position. See FIG. 12.
A pair of stirrups or U-shaped pivot supports 91 and 92 are formed on opposite sides of the nozzle tube 64, and the inwardly projecting pivot pins or tabs 60 and 61 on the trigger are received therein.
A safety feature is provided in association with the bladder 35 for relieving or returning to the container excess pressure which might be developed by excessive operation of the trigger without an intervening discharge of material. Additionally, a slow leak-back is provided whereby the dispensing device of the invention is not capable of being left with an undischarged pressurized supply of material in the bladder for any extended period of time. This safety feature is seen best in FIGS. 4, 6, 9 and 9a-9e, and as seen in these figures, the flexible, cylindrical valving skirt or wall 38 terminates short of the end surfaces of the chamber 45 in which it is received, and a relatively short, rearwardly projecting tab 93 is integrally formed in the chamber at the end wall thereof and projects rearwardly into contiguous relationship with the forward edge of the valving skirt or wall 38. A channel or roughened surface configuration or the like may be provided to enable the slow leak-back to be accomplished. An axially extending blow-by passage or port 94 is formed in the side wall of chamber 45 and extends rearwardly from tab 93 to the surface or shoulder 44 in the bladder retainer and thence downwardly at 95a and laterally at 95b into registry with the port 46. In normal usage, the valving skirt or wall 38 does not effect a perfectly fluid-tight seal relative to the surface of the chamber 45, and particularly at the location of the tab 93. Accordingly, if the bladder 35 is inflated or filled with material to be dispensed and the discharge valve is not opened to dispense or discharge the material from the bladder, the material will nonetheless slowly leak back through the ports or passages 94 and 95 to passage 46 and from there back into the container. Similarly, if excessive pressure is generated within the bladder 35 by overfilling it, the flexible valving skirt or wall 38 will flex away from the tab 93, opening relatively free communication with passage 94, thereby dumping or by-passing the excessive pressure back into the container.
A one-piece, molded shroud 96 is disposed in covering relationship to the dispenser assembly and includes a pair of spaced apart opposite side walls 97 and 98, extending downwardly closely on opposite sides of the manifold 41. If desired, the opposite side portions of the manifold at 42a and 42b may be flattened to engage the inner surface of the sides 97 and 98 of the shroud relative to the manifold. Additionally, a downwardly projecting, rectangularly shaped web or plate 99 is engaged at its bottom and end edges in a complemental channel 100 formed on the top of the discharge tube member 50 and the rear surface of the post 62, respectively. A pin 101 projects downwardly from the underside of the top wall 102 of the shroud and is engaged in the upper end of passage 63 in the post 62 closing the passage and also accurately aligning the shroud relative to the manifold and assisting in retaining the parts in assembled relationship. A pair of integrally molded, downwardly projecting, spaced aparts leaf spring members 103 and 104 depend from the top wall 102 of the shroud into aligned registry with the legs 58 and 59 of the trigger 55, and normally urge the trigger forwardly or outwardly, as seen in FIG. 4. When the trigger is pressed rearwardly, the leaf spring members 103 and 104 flex rearwardly with the trigger and the natural resiliency or memory thereof urges the trigger forwardly to its normal, at rest position.
A pair of inverted, generally U-shaped bracket members 105 and 106 are formed integrally with the shroud on the inner surface of the top wall 102 thereof, and extend downwardly over the pivot pins 60 and 61 of the trigger, retaining them in the stirrups 91 and 92.
MODIFICATION
A modification of the dispensing device of the invention is indicated generally at D' in FIGS. 13 through 15 and as with the previous form of the invention, includes a shroud 96 which is disposed in covering relationship to a modified manifold member 41' having a first cylinder 51 defined thereon and in which a piston 54 is reciprocably received for operation by a trigger 55 to alternately draw material from a container, up through dip tube T, into the cylinder 51, past valve 38 defined on the bladder 34', and thence past valve 39'a into the bladder for accumulation under pressure.
A slightly modified discharge tube 50' has an elongate passage 49' extended therethrough and positioned such that the valve ring 39'b normally closes the inner or rearward end of the passage 49'. An elongate valve actuator rod l07 extends through the passage 49' from adjacent the valve 39'b to adjacent the outer or forward end of the passage 49'. The outer end 108 of rod 107 is snap-fitted, or otherwise suitably secured, to a shank portion 109 of a modified discharge valve member 80' which comprises head 86' having the shank or shaft 109 integral therewith. The head 86' has a skirt 87 thereon as in the previous form of the invention and also has a pair of laterally outwardly projecting latching tabs 89 and 90. Additionally, the discharge valve member 80' has a finger engaging structure or trigger configuration 110 formed integrally therewith to facilitate manipulation thereof with the finger of the user.
The dispensing device D' is rendered tamper-proof by means of a thin frangible web 11 which integrally joins the head 86' of discharge valve 80' and the nozzle 72' prior to use of the device. However, when the discharge valve 80' is depressed to open the valve 39'b, as seen in FIG. 13, the web 111 is fractured, thus providing an indication that the device has been actuated.
The dispensing device D' is shown prior to being actuated in FIG. 14 wherein the frangible web 111 is shown intact and the discharge valve 80' in its forward biased condition with the valve 39'b closed, thereby precluding flow from the bladder 34' and through the passage 49' to the nozzle 72'.
Therefore, except for the modifications relative to the discharge tube 50' and discharge valve 80' and its association with the valve 39'b of bladder 34', this form of the invention is substantially the same as that previously described.
It should be noted that shank portion 109 of the modified discharge valve 80' effects a fluid tight seal with the outer end of passage 49'.
Thus, the present invention provides a unique dispensing device which is capable of operating in several different modes, including duration, relatively constant spray, and continuous spray during operation of an actuator.
With the unique structure of the present invention, substantially all of the components thereof may be snapped together for assembly of the device and a minimum number of parts, for example 10, may be used in its construction. Further, the device may be easily and economically molded. Therefore, a simple three plate molding operation with the maximum number of cavities may be used in making the present invention.
The unique discharge valve used with the dispensing device of the invention serves as an automatic off feature thereby adding to the safety of the dispensing device and rendering it suitable for use around small children. In other words, a child would be unlikely to manipulate both the trigger and the discharge valve in order to obtain discharge of the material from the device of the invention.
Assembly of the device of the invention is quite easy, and orientation of the bladder, for example, is not required to obtain proper valving action. The snap together, modular assembly of the device of the invention makes it easy to pre-test various subassemblies for determining the operation of various phases of the device. Further, these same features make it relatively easy to interchange different material for the bladder and other elements or components of the invention for desired purposes.
The materials used in the device may be selected for any desired effect and in this connection the bladder is not normally submerged in product during shipment or storage. Further, there are no metal parts used in the device of the invention with the possible exception of the actuator rod 107 which may be metal if desired.
The combination of orifice sizes, bladder wall thickness, blow-by pressure and the like permits a wide range of pressures to be used or obtained, suitable for dispensing a wide variety of products, and the device of the invention is easily adaptable to existing container configurations without regard to any specific structural requirements as to strength or adaptability to conventional containers.
In addition to all of the other advantages of the invention, it is less expensive than conventional spray systems and since the subassemblies may be made and assembled as noted above, high quality control can be obtained with a low reject rate.
Further, the unique, positive acting vent of the invention insures that proper venting of the container will be obtained. In operation of this vent, when the trigger is actuated to accumulate material in the bladder, the bladder expands and engages the post or vent actuator 20, to move the wall 18 downwardly and bring the opening 19 into registry with the fluted end portion 27 of stem 26, thus venting atmospheric air to the interior of the container. This positive vent, and the simplicity of construction and ability to use any desired materials, results in an economical, effective, and easy to use spray dispenser which does not rely upon chemical propellants, and yet which is capable of obtaining duration or continuous discharge of material.
As this invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, the present embodiment is, therefore, illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description preceeding them, and all changes fall within the metes and bounds of the claims or that form their functional as well as conjointly cooperative equivalents are, therefore, intended to be embraced by those claims. | A multi-function dispenser may be adjusted to obtain a spray or stream of the material dispensed, either as a long duration discharge of the material or as intermittent discharges corresponding to actuation of a trigger actuator, or as a continuous discharge during actuations of the trigger, depending upon functional design variables. Structure is provided for storing an accumulated amount of material upon repeated operations of the trigger, for subsequent prolonged discharge of the material, or the accumulating structure may be bypassed for intermittent discharges of the material as the trigger is operated, or the accumulating structure may function as a holding chamber whereby a continuous discharge of the material may be obtained while the trigger is being operated. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to a device which secures an object such as a bicycle for transport and repair, and more particularly, to a combination bicycle car rack and work stand especially adapted for attachment to a motor vehicle.
BACKGROUND ART
[0002] A bicycle car rack is a common means of transporting bicycles on a vehicle. Typically, such racks utilize the vehicle's existing trailer hitch receiver as an attachment point. When the bicycle rack is not in use, the rack is simply disconnected from the receiver. A-well known device to secure a bicycle during repair is a portable repair stand. Typically, the portable repair stand includes a clamp which secures the bicycle at a desired location and orientation, and a base which supports the suspended bicycle.
[0003] A number of prior art references disclose both hitch racks and repair stands. One example of a reference which discloses a repair stand which mounts to a motor vehicle includes the U.S. Pat. No. 5,385,280. In this reference, a base member is adapted to connect to the receiver hitch of the vehicle. A riser member adjustably connects to the base member. A clamp support member projects horizontally from the riser member. The clamp support member includes a clamp which may secure the bicycle frame, or other components of the bicycle.
[0004] One example of a bicycle rack which is mounted to a vehicle includes the U.S. Pat. No. 4,676,413. This reference discloses a pair of frame mounting brackets secured to the frame of the vehicle. A rack assembly is supported by the frame mounting brackets. Bicycle hangar rods are secured to the top end of the rack assembly. One or more bicycles may be mounted on the rack assembly and secured by the hangar rods.
[0005] U.S. Pat. No. 3,981,491 is an example of a portable work stand. The work stand includes a pair of relatively movable jaws between which a tubular member of a bicycle may be securely clamped.
[0006] U.S. Pat. No. 5,277,346 discloses a clamping device especially adapted for securing bicycles thereto. The clamping device attaches to the trailer hitch of the vehicle. The clamping device includes cooperating clamping jaws which, once closed, are automatically locked in the closed position about the tubing of the bicycle.
[0007] Other examples of bicycle racks adapted for mounting to a vehicle include U.S. Pat. Nos. 5,277,346; 5,803,330; 4,676,414; 5,845,831; and 6,000,593. The purpose common to each of these references is a device which rigidly mounts one or more bicycles to a vehicle; however, no means is provided to orient a bicycle in a multitude of positions in accordance with functional attributes of a work stand. Thus, while the foregoing body of prior art indicates that it is known to support bicycles on vehicles for transporting the bicycles, or to mount a work stand to a vehicle for repair of a single bicycle, it is not contemplated to provide in a single device a combination work stand which enables one to exactly position a bicycle in a desired orientation, and simultaneously provide a bike carrier or bike rack to secure and transport additional bicycles on the same device.
SUMMARY OF THE INVENTION
[0008] The present invention, in broad terms, includes capabilities as both a work stand for repair and maintenance of a bicycle, and a bicycle car rack for securing and transporting one or more bicycles to a vehicle. Structurally, the bicycle car rack and work stand of the invention includes a support assembly characterized by an insert tube which is received in the receiver tube of the trailer hitch assembly, a vertical frame tube connected to the protruding end of the insert tube, and a horizontal frame tube connected to the upper end of the vertical frame tube. A clamp assembly is mounted on the horizontal frame tube and may be used to secure and precisely position a bicycle for maintenance or repair. One or more bike carrier members are provided to secure additional bicycles to the car rack and work stand. Optionally, the clamp assembly may be removed and replaced with a bike transport assembly which allows a number of additional bicycles to be secured to the device of this invention. The clamp assembly is adjustable to receive various sizes of bike tubing frames, or other components of a bicycle which must be secure for maintenance or repair.
[0009] The vertical frame tube pivotally connects to the receiver tube. A tilt lock pin is provided which allows the vertical frame tube to be secured in a vertical upright position or rotated downward to a more horizontal position. Additional structural support is provided in the form of an anti-sway plate which more rigidly secures the insert tube to the receiver tube of the trailer hitch assembly. A gusset may be provided to further support the vertical frame tube and the gusset, if used, acts as a cable pass-through.
[0010] The clamp assembly may be rotated to any desired position. A securing handle is used to engage or disengage a pair of clutch plates, and a user may then rotate the clamp assembly to the desired orientation while the clutch plates are disengaged.
[0011] The clamp assembly includes a clamp handle which manipulates an upper jaw of a pair of opposing jaw channels which secure the bicycle component therebetween. A lower jaw channel is fixed to a clamp support tube of the clamp assembly. The upper jaw channel moves with respect to the lower jaw channel, and can be locked into place by pushing down on the clamp handle tube. The gap between the upper and lower jaw channels may be adjustable by a barrel nut which provides linkage between the clamp handle and the clamp support tube. Accordingly, the clamp assembly is able to receive various sized bicycle components.
[0012] If there is no need for conducting repair or maintenance on a bicycle, the clamp assembly may be removed and replaced with a bike transport assembly which has a plurality of bike carrier channels. For each of the bike carrier channels, a tubular member of the bicycle rests in the channel, and then a strap may be used to secure the bicycle component to the particular channel.
[0013] Although this invention is adapted for attachment to a vehicle, the invention may also be disconnected from a vehicle and mounted to a stationary pedestal receiver.
[0014] The foregoing discussed advantages along with others will become apparent from a review of the description which follows in conjunction with the corresponding figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] [0015]FIG. 1 is a fragmentary perspective view of the bicycle car rack and work stand of this invention illustrating the clamp assembly attached, and the bicycle transport assembly detached;
[0016] [0016]FIG. 2 is a reduced perspective view of the device of this invention illustrating the invention mounted to the trailer hitch assembly of a vehicle, and also illustrating a bicycle secured by the clamp assembly;
[0017] [0017]FIG. 3 is a fragmentary exploded perspective view of the device of this invention illustrating both the clamp assembly and bike transport assembly detached from the support assembly;
[0018] [0018]FIG. 4 is a vertical section, taken along line 4 - 4 of FIG. 3, illustrating the device of the invention assembled and with the clamp assembly illustrated in the open position;
[0019] [0019]FIG. 5 is another vertical section, taken along line 4 - 4 of FIG. 3, illustrating the clamp assembly in the closed position for securing a component of a bicycle;
[0020] [0020]FIG. 6 is a fragmentary perspective view illustrating the rotational capability of the clamp assembly;
[0021] [0021]FIG. 7 is a another fragmentary perspective view illustrating the bike transport assembly attached, and further showing a component of a bicycle mounted to one of the bike carrier channels as by a strap assembly;
[0022] [0022]FIG. 8 is a perspective view of a pedestal assembly which is integral with the device of this invention;
[0023] [0023]FIG. 9 is a perspective view of a pedestal receiver which may be used when the device is removed from its mounted position on a vehicle;
[0024] [0024]FIG. 10 is a fragmentary perspective view showing the receiver of FIG. 9 in use; and
[0025] [0025]FIG. 11 is an exploded perspective view of FIG. 10.
DETAILED DESCRIPTION
[0026] [0026]FIG. 1 illustrates the car rack and work stand 10 of this invention. The device includes three major assemblies, namely, a clamp assembly 12 , a support assembly 14 , and a bike transport assembly 110 . As shown in FIG. 2, the support assembly 14 includes a horizontally extending insert tube 16 which is inserted in the receiver tube T of the trailer hitch assembly of a vehicle V. The support assembly 14 further includes a vertical frame tube 18 which rotatably connects to insert tube 16 as by tilt swivel pin 38 . The upper end of frame tube 18 connects to horizontal frame tube 20 as by a welded connection along seam 22 . The insert tube 16 includes one or more mounting pin holes 24 drilled transversely through the tube 16 . Mounting pin P may then secure the insert tube 16 by inserting the pin P through the hole in receiver tube T and the aligned mounting pin hole 24 . FIG. 2 shows but one means by which the device of this invention may be attached to the trailer hitch assembly of a vehicle. The arrangement shown in FIG. 2 is one of the more common trailer hitch assemblies found on many modern vehicles. As well understood by those of skill in the art, insert tube 16 could be modified or adapted for connection to other types of trailer hitch assemblies.
[0027] In order to enhance the structural integrity and stability of the device, an anti-sway plate 26 is provided, along with tensioner 28 . As shown in FIG. 2, anti-sway plate 26 overlaps the interface between receiver tube T and insert tube 16 . Tensioner 28 is tightened which then stabilizes the connection between receiver tube T and insert tube 16 . Further structural support is provided by angled gusset plate 30 which is welded to the vertical frame tube 18 . A pair of securing plates 34 which are provided for extra structural support receive both the tilt swivel pin 38 and tilt lock pin 36 . As shown in FIG. 3, the tilt lock pin 36 may be removed which allows vertical frame tube 18 to rotate. Tilt swivel pin 38 remains attached. It may be necessary to rotate vertical frame tube 18 if the device of this invention is mounted to the trailer hitch assembly of a pick-up truck, or other recreational vehicle which has a tailgate. Rotation of frame tube 18 to the more horizontal position would allow the tailgate to be opened.
[0028] The horizontal frame tube 20 has mounted thereto one or more bicycle carrier channels 42 . FIG. 1 illustrates just one bike carrier channel 42 ; however, it is well within the scope of this invention to have additional bike carrier channels 42 , depending upon the length of frame tube 20 . Bike carrier channel 42 includes a lower support member 42 , and a rubber or resilient covering 46 overlying the support member 44 . As best seen in FIG. 4, the bike carrier channel is a v-shaped member which is simply welded to the upper surface of frame tube 20 .
[0029] Now referring to FIGS. 1, 3, 4 , 5 and 6 , the clamp assembly 12 will now be explained in more, detail. The clamp assembly 12 includes a clamp handle tube 48 which is grasped by the user and is positioned either in the open position as shown in FIG. 3, or in the closed position as shown in FIG. 1. The clamp handle tube 48 connects to clamp handle square 50 . A pair of clamp side plates 52 and 53 serves as the primary linkage members. As shown, handle pivot pin 54 is inserted between the plates 52 and 53 and thus rotatably connects handle square 50 to plates 52 and 53 . A pair of jaw pivot mounts 66 and 67 attached to the upper surface of clamp support tube 64 . Jaw pivot pin 56 is inserted between pivot mounts 66 and 67 , and thus rotatably attaches side plates 52 and 53 to the mounts 66 and 67 . A clip may be used to secure pins 54 and 56 as necessary, and which allows more easy disassembly of this clamp assembly. Upper jaw channel 60 attaches to the forward or distal ends of side plates 52 and 53 , as best seen in FIG. 4. Lower jaw channel 62 is mounted to the most forward or distal end of clamp support tube 64 . An upper handle pivot mount 68 is mounted to the lower or under side edge of clamp handle square 50 . A pair of lower handle pivot mounts 72 and 73 as best seen in FIG. 3 are mounted to the clamp support tube 64 proximally of the jaw pivot mounts 66 and 67 . Threaded rod 76 extends from mount 68 and is secured by pivot mount pin 70 . A barrel nut 78 is screwed over the free end of threaded rod 76 . As shown in FIG. 4, the lower end of barrel nut 78 attaches to extension 75 which is rotatably secured between mounts 72 and 73 by pin 74 . The barrel nut can be screwed or unscrewed along the threaded rod 76 to change the effective length of the linkage between upper pivot mount 68 and lower pivot mounts 72 and 73 .
[0030] When the clamp handle tube 48 is lifted to the more vertical orientation, jaw 60 is separated from jaw 62 . When the tube 48 is pushed down to the more horizontal orientation, upper jaw of channel 60 moves towards lower jaw channel 62 . As best seen in FIG. 6, a stop tab 80 mounts horizontally between side plates 52 and 53 , and serves as a stop to limit the downward travel of clamp handle tube 48 by contact with the lower edge of upper pivot mount 68 . As best seen in FIG. 5, a portion of the frame F of a bicycle is locked between jaws 60 and 62 . The gap G between jaws 60 and 62 can be changed to accommodate-the particular sized frame member which is secured between the jaws by screwing or unscrewing the barrel nut 78 over threaded rod 76 .
[0031] As shown in FIG. 6, the clamp assembly 12 may be rotated to any desired position. This capability is achieved by clutch plates 82 and 86 which may be engaged or disengaged by securing handle 100 . More specifically, clutch plate 82 is secured to the proximal end of clamp support tube 64 . Clutch plate 86 is secured to the distal or forward end of horizontal frame tube 20 . A clutch plate bushing 84 is positioned between the clutch plates 82 and 86 . The securing handle 100 includes an elongate threaded bolt 104 which is inserted through an opening on the upper end of vertical frame tube 18 , and extends internally through frame tube 20 . The threaded bolt 104 further extends through an opening 88 in clutch plate 86 , opening 90 in bushing 84 , and through a central opening in clutch plate 82 . A grip 102 attaches to the proximal end of threaded bolt 104 . As shown in FIG. 4, an internal securing nut 106 is rigidly mounted within the interior of support tube 64 , and the distal end of the threaded bolt 104 also extends through the securing nut 106 . If it is desired to rotate the clamp assembly, grip 102 is unscrewed thus loosening clutch plates 82 and 86 . The clamp assembly is rotated to the desired orientation, and then grip 102 is tightened thus forcing clutch plates 82 and 86 back against one another. Washer 103 may be mounted over threaded bolt 104 to help prevent damage against the exterior surface of tube 18 due to contact with the grip 102 .
[0032] Hasp openings 92 and 94 may be drilled through clutch plates 86 and 82 , which allows a lock 98 having a hasp 96 to pass therethrough, as shown in FIG. 4. Thus, the clamp assembly can be locked to prevent theft.
[0033] Now referring to FIG. 7, the bike transport system 110 is shown mounted to support assembly 14 . The bike transport assembly includes a plurality of bike carrier channels 112 , mounted to the support tube 114 . As with the clamp assembly, the bike transport assembly 110 also includes its own clutch plate 116 which mounts against clutch plate 86 . Thus, the bike transport assembly 110 may also be rotated to the desired orientation. However, the most common and efficient orientation of the bike transport assembly is when the carrier channels 112 are maintained in a horizontal orientation. The bike carrier channels 112 are constructed in the same manner as carrier channel 42 , and are simply welded to the support tube 114 . In order to lock the bike transport assembly to the support assembly, bike transport assembly also includes a hasp opening 118 which may be aligned with hasp opening 92 to receive the hasp 96 of lock 98 . Although a bike transport assembly 110 has been illustrated, it shall be understood that the device of this invention can also be used in conjunction with other types of securing assemblies such as an assembly for securing skis or other objects. Thus, the ski rack would simply have to include some means for connection to the clutch plate 86 , preferably a clutch plate like clutch plate 116 of the bike transport assembly 110 . Those skilled in the art can envision other specific objects which might be transported by the device of this invention.
[0034] A strap assembly 120 as of the type shown in FIG. 7 may be used to secure the bicycles to the bike carrier channels. One particularly effective strap assembly 120 includes a loop 122 , a strap portion 124 , and hook and pile material 126 . The strap assembly 120 can simply be wrapped around the frame F of the particular bicycle, and around the corresponding bike carrier channel. Those skilled in the art can envision other types of strap assemblies which may be used to secure the frame or other components of a bicycle to the bike carrier channels.
[0035] [0035]FIG. 8 shows an alternative embodiment wherein the device of the invention is not mounted to a vehicle, but rather is permanently mounted to a stationary pedestal. As shown, this stationary embodiment pedestal assembly 130 simply comprises the vertical tube 18 attached to a base 132 . The base 132 is of sufficient weight and size to stabilize the upper components of the device, or the base 132 can be of a smaller size and bolted to the floor for support.
[0036] FIGS. 9 - 11 illustrate yet another alternative embodiment of the invention which allows the invention to be adapted for mounting to another type of stationary base or pedestal. As shown in FIG. 9, this base 134 includes a vertical support member 136 having a lower end attached to base support member 138 . The upper end of vertical support member 136 attaches to horizontal receiving member 140 . Once the device is removed from a vehicle, the free end of insert tube 16 is inserted within the opening 141 of Horizontal receiving member 140 . One of the holes in insert tube 16 is aligned with hole 146 and a pin 144 may be used to secure the connection of insert tube 16 and receiving member 140 . A small flange 142 may be welded to horizontal receiving member 140 . This flange 142 helps to assure that anti-sway plate 26 sets flush against securing plate 34 and against the flange 142 .
[0037] While various embodiments of the present invention have been described in detail, it is apparent that further modifications and adaptations of the invention will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention. | A combination bicycle car rack and work stand is provided. The device has one or more bicycle carrier channels to secure one or more bicycles, and a clamp assembly which can be oriented in a desired position in order to perform maintenance or repair on another mounted bicycle. The invention may be mounted to a vehicle, or may be mounted to a stationary base. If the clamp assembly is not in use, additional bicycles may be transported by removing the clamp assembly, and attaching a bike transport assembly which includes additional bike carrier channels. Enhanced structural support is provided on the support assembly of the device to ensure a strong and rigid connection with the hitch assembly of a vehicle. The clamp assembly is adapted to receive various sized components of a bicycle, and can be rotatably oriented with ease. | 8 |
[0001] This application is a continuation of U.S. application Ser. No. 13/010,457, filed Jan. 20, 2011, which application is a continuation of U.S. application Ser. No. 11/470,658, filed Sep. 7, 2006, which claims the benefit of Provisional application 60/734,728, filed on Nov. 8, 2005, all of which are incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to laundry appliances and in particular to laundry washing machines for household use.
BACKGROUND TO THE INVENTION
[0003] U.S. Pat. No. 6,212,722 proposes an improved laundry washing machine for domestic use. This machine is of the top loading type having an outer bowl, a wash basket within the outer bowl and access to the wash basket through a top opening. A motor is provided to drive rotation of the wash basket within the outer bowl. A wash plate is provided in the lower portion of the wash basket to be rotated by the motor with the wash basket or independently of the wash basket. The patent proposes a combination of water level control, wash plate design, wash basket design and movement pattern for the wash plate which leads to an inverse toroidal movement of the laundry load during a wash phase. The sodden wash load is dragged by friction radially inward on the upper surface of the wash plate and progresses upward in the region of the centre. The sodden wash load then progresses radially outward to the wall of the wash basket and downward to the base of the wash basket. This has been found to provide an effective wash action with low water consumption.
[0004] The patent indicates that this is only achieved at water levels within a determinable band. With too much water the inverse toroidal rollover motion is not achieved because the clothes lose frictional contact with the wash plate.
[0005] The present inventors have ascertained a desire to include an effective wash mode that sacrifices a degree of water efficiency in favour of dilution of the wash solution. The inventors consider this to be particularly desirable in the case of heavily soiled laundry items or laundry items having insoluble soiling, such as muddy, sandy or grass covered sports clothes, and in the case of laundry subject to dye leakage.
[0006] The inventors consider that the laundry machine described in U.S. Pat. No. 6,212,722 is only partially effective in this regard. At higher water levels in which the machine cannot perform the inverse toroidal rollover pattern the inventors consider the machine is likely to provide a less effective wash action. The effect of inverse toroidal wash action by dragging is only available at low water levels, and there is a middle water level at which no rollover occurs. Where the laundry load does not rollover wash action of clothing against the wash plate is limited to a small fraction of the load and wash performance suffers.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide a laundry machine which goes some way toward overcoming the above disadvantages or which will at least provide the public with a useful choice.
[0008] In a first aspect, the invention may broadly be said to consist in a laundry machine comprising a cabinet, a wash tub supported within the cabinet, a motor suspended beneath the wash tub, a wash basket rotatably supported within the wash tub and drivingly connected to the motor, and a wash plate disposed in the bottom of the wash basket and defining an outer periphery. The wash plate comprises a central hub encircled by the outer periphery, a plurality of vanes extending substantially radially from the central hub toward the outer periphery. The vanes comprise a continuously increasing width as they extend radially away from the hub, a pair of sidewalls diverging as they extend away from the hub, an outer portion terminating at the outer periphery, a shoulder extending from the hub and transitioning into the outer portion, wherein the shoulder is located above the outer portion and both the outer portion and shoulder have a convex cross section. Further, the wash plate is rotatably supported in the wash basket and drivingly connected to the motor to oscillate the wash plate such that the cloth items directly above the wash plate are frictionally dragged in an oscillatory manner and the cloth items rollover within the wash basket along an inverse toroidal rollover path.
[0009] This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more of said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a cutaway perspective view of a laundry machine according to a preferred embodiment of the present invention.
[0011] FIG. 2 is a block diagram of a control system for a laundry washing machine.
[0012] FIG. 3 is a perspective view of the wash basket base moulding according to the machine of FIG. 1 .
[0013] FIG. 3 b is a perspective view of another embodiment of a wash basket base moulding according to the present invention.
[0014] FIG. 4 is a perspective view from above of the wash plate according to a preferred embodiment of the present invention.
[0015] FIG. 4 b is a perspective view from above of the wash plate according to present invention as shown in 3 b.
[0016] FIG. 5 is a cross-sectional side elevation of the wash plate of FIG. 4 .
[0017] FIG. 6 is a plan view of the wash plate of FIG. 4 .
[0018] FIG. 7 is a plan view of a section of wash plate including arcuate apertures.
[0019] FIG. 8 is a graph of rotational speed versus time, illustrating elements of a wash plate drive profile for exciting toroidal rollover.
DETAILED DESCRIPTION
[0020] The present invention relates to improvements and adaptations on the wash system described in U.S. Pat. No. 6,212,722. The contents of that patent are incorporated herein by reference.
[0021] A laundry machine incorporating improvements and adaptations of the present application is illustrated in FIG. 1 . The laundry machine includes a cabinet 100 with a lid 102 and a user console 104 . A controller 106 is located within the body of the user console. The controller 106 includes a power supply and a programmed microcontroller. The power supply receives power from the mains supply and supplies power to the microcontroller, to a power supply bridge for the electric motor and to ancillary devices within the machine such as a pump and valves. Delivery of power to the motor 114 and the ancillary devices is at the control of microcontroller. The microcontroller receives inputs from a user interface on console 104 .
[0022] A tub 120 is supported within the cabinet. The tub is preferably suspended from the upper edge of the cabinet. The tub may alternatively be supported from below or from the sides of the cabinet. A wash or drain pump is fitted to the lower portion of the tub. The pump is preferably located at a sump portion of the tub.
[0023] A wash basket 122 is supported for rotation within the tub. Opening the lid 102 provides user access to an upper open end of the wash basket.
[0024] A wash plate 124 is mounted in the lower portion of the wash basket.
[0025] The improvements and adaptations of the present invention are preferably implemented in a laundry machine of a direct drive type. However other drive systems involving for example gearbox or belts may alternatively be used.
[0026] A motor 114 below the tub directly drives a shaft 128 . The shaft 128 extends through the lower face of the tub, where it is supported in a pair of bearings 130 . Seals prevent water escaping the tub at the interface between the tub and shaft.
[0027] The wash basket 122 is mounted on the shaft within the tub. The wash basket may typically comprise a base 132 and a perforated cylindrical skin 134 . The perforated cylindrical skin extends up from the base to define an open ended drum. The wash basket may include a balance ring at the upper edge of the cylindrical skin.
[0028] The wash plate 124 is also fitted to the shaft, within the wash basket 122 .
[0029] An arrangement is provided to enable the motor 114 to selectively drive either the wash plate 124 independently of the wash basket 122 , or drive the wash basket 122 . In driving the wash basket the motor may also drive the wash plate. Various mechanisms have been proposed to accomplish this selective drive. A number of variations including twin concentric shafts and a selectable clutch to connect the motor with either or both shafts are noted in the prior art and may be applied.
[0030] Alternatively a floating clutch of a type previously described in U.S. Pat. No. 5,353,613 may be used. The machine illustrated in FIG. 1 makes use of such a floating clutch. The wash basket 122 is slidably mounted on the drive shaft 128 . The wash plate 124 is fixed to rotate with the upper end of the drive shaft. The wash basket 122 includes float chambers 140 on the underside of the wash basket base member. The wash basket is allowed to rotate on the shaft. A vertically inter-engaging clutch 142 is provided between the wash basket 122 and wash plate 144 or between the wash basket 122 and shaft 128 . A first clutch member having upwardly facing engagements may be provided in conjunction with the wash plate or a spline on the shaft. An downwardly facing clutch member is provided in conjunction with the wash basket. With the wash basket in an upper or raised position the upwardly facing and downwardly facing clutch members are not engaged and the wash basket is free to rotate on the shaft. With the wash basket in a lower position the members are not engaged. In use the wash basket will be disengaged from the shaft when sufficient water has been added to the tub for the wash basket to float to its raised position. The amount of water required before the wash basket floats depends on the weight of laundry in the wash basket. In the floated condition the shaft will drive the wash plate but will not directly drive the wash basket. In the lower condition the shaft will drive the wash plate and wash basket together.
[0031] The controller is part of a control system for coordinating the operations of the laundry machine. The control system is illustrated in the block diagram of FIG. 2 . The controller includes a microcontroller 800 . The microcontroller may include a micro computer and ancillary logic circuits and interfaces. The micro controller receives user input commands on user interface 802 . The user interface may include, for example, a plurality of touch controls such as switches or buttons, or may include a touch screen, or may include rotary or linear selection devices. The micro controller may include a display device 804 to provide feedback to a user. The display device may comprise a plurality of indicators, such as lights or LEDs, or may include a screen display. The display device 804 and the user interface 802 may be mounted to a single module incorporating the micro controller.
[0032] The micro controller receives power from a power supply 806 . The micro controller also controls power switches 808 applying power from supply 806 to drive motor 810 . The micro controller controls further power switches 812 applying power from supply 806 to a pump 814 . The micro controller also controls a power switch 830 applying power to a cold water inlet valve 832 and a power switch 834 applying power to hot water inlet valve 836 .
[0033] The micro controller preferably receives feedback from position sensors 816 associated with the motor. These sensors may for example be a set of digital Hall sensors, sensing changes in rotor position, or may be any suitable encoder. Alternatively rotor position and movement may be sensed from motor drive current or EMF induced in unenergised motor windings.
[0034] The micro controller also preferably receives input from a water level sensor 818 , which detects the level of water in the tub of the machine, and from a temperature sensor 820 which detects the temperature of water being supplied to the wash tub.
[0035] The present application presents several adaptations that enhance the operation of a wash system attempting to induce inverse toroidal rollover by frictional dragging or by fluid mechanics. These adaptations enhance the ability to generate inverse toroidal rollover wash pattern at low water levels and help extend the water levels at which this wash pattern can be maintained. A number of these adaptations involve the shape and configuration of elements of the wash plate. In particular they involve the form of the upper surface of the wash plate, including the presence and location of apertures through the wash plate. Other adaptations involve the shape and size of buffers arrayed on the base of the spin tub around the periphery of the wash plate. An additional aspect involves control methods for helping establish and maintain the inverse toroidal rollover pattern and for beneficially extending the range of operation of the inverse toroidal rollover to higher water levels.
[0036] Exemplary wash plates are illustrated in FIGS. 4 to 6 . FIGS. 3-5 illustrate one exemplary wash plate and FIGS. 3B and 4B illustrate a second exemplary wash plate. As shown in FIGS. 4 and 4B , the wash plate rises from a generally circular periphery 400 to a raised central hub 402 . The upper surface of the wash plate is broadly divided into alternating sectors. The alternating sectors comprise raised sectors 404 , or vanes, and intermediate lower sectors 406 . The lower sectors 406 are in the general form of a shallow cone with increasing gradient toward the hub 402 , so as to be outwardly concave in radial cross-section. This can generally be seen in FIG. 5 . In the outer region of the wash plate the low sectors 406 have a generally shallow gradient. In the region closest to the hub 402 the low sectors 406 of the wash plate have a higher gradient.
[0037] Each vane 404 has a form devised to enhance initiation and maintenance of inverse toroidal rollover by encouraging the inward dragging of laundry items by friction that are in contact with the upper surface of the wash plate. This enhanced form includes three major features. It is believed that each of these features independently offers an improvement over prior forms. The cumulative improvement offered by these features enables the appliance to maintain inverse toroidal rollover at higher water levels.
[0038] Each vane includes a divergent form wherein the width of the vane increases moving from the hub to the periphery of the wash plate. Further, each vane includes steep side walls 410 adjacent the neighbouring low sectors of the wash plate.
[0039] The upper face of an outer portion 412 of each vane is generally flat and the vane slopes down towards its outer periphery 414 to the level of the circular periphery 400 of the wash plate.
[0040] Each steep side surface 410 of each vane is outwardly concave. That is, the side surfaces of each vane diverge more rapidly as the vane extends toward the outer periphery 400 of the wash plate. Furthermore the opposing side surfaces 410 of adjacent vanes, facing toward one another across the low sector 406 between them, are each concave relative to the other and relative to a radius extending from the centre of the wash plate. The outermost portion of each sidewall hooks toward the adjacent vane so as to be inclined in advance of a radial plane of the wash plate. The inventors have found that such side surfaces 410 aid in dragging the cloth items inward to the centre of the wash plate.
[0041] Rapid oscillation of the wash plate provides a centrifugal pumping action inducing radially outward water flow. Such radial flow above the wash plate may inhibit inward movement of the laundry items and is detrimental to establishing the inverse toroidal rollover pattern. The shape of the side surfaces 410 also counteract the centrifugal pumping action of the wash plate as it is oscillated. The inventors have found that the side surfaces 410 aid in achieving inverse toroidal roll-over at all water levels.
[0042] In the region of the vane 404 nearer the hub 402 a ridge or shoulder 420 rises from the general outer portion 412 of each vane. The ridge or shoulder 420 has side faces 422 rising to a ridge. The side faces of the shoulder 420 are less steep than the steep side faces 410 . When the wash plate is oscillated the angled side faces 422 of the shoulder 420 push on the laundry items near the hub 402 so as to impart a vertical component of force on them. Laundry items near the centre of the wash plate are then thrust upward, which aids inverse toroidal motion.
[0043] Preferably there are a plurality of such vanes 404 , for example 3, 4, 5 or 6 such vanes. Most preferably there are 3 or 4 such vanes.
[0044] Preferably the relative proportion of vane to plan area of the wash plate, is between 0.33 and 0.66.
[0045] The shape and size of the washplate, including shoulder area, along with basket capacity, and drive profiles used by the controller, can impact motor temperatures. Accordingly these factors need to be balanced according to the overall machine requirements.
[0046] The inventors have found that by providing apertures 430 through the wash plate, radial outward water flow is induced below the wash plate by the shape of the underside of the vanes 404 , and that this reduces or compensates for induced outward flow above the wash plate. To enhance outward flow under the wash plate the underside of the wash plate may include a plurality of spaced radial ribs 432 .
[0047] The base of the wash basket preferably includes an annular series of flow channels extending from the upper side of the base through to the lower side of the base. These channels 304 can be seen in FIG. 3 . Fluid may flow from apertures 430 and through these flow channels to the region below the wash basket, between the wash basket and outer tub. This fluid may flow from there out to the wall of the outer tub, upward between the wall of the outer tub and the cylindrical wall of the wash basket and then inward through the perforations of the wash basket. The water flow carries lint into the space between the wash basket and the tub. This lint becomes caught up on the outside of the spin basket and tends not to reenter the spin basket. The lint is then removed in the drain operation subsequent to the wash cycle or is extracted by a lint filter in a recirculation system.
[0048] Furthermore, the apertures 430 through the wash plate are preferably provided adjacent each steep side wall 410 of each vane as shown is FIG. 4 , or between each steep side wall 410 as shown in FIG. 4B . It is believed that the suction effect generated by the pumping action under the wash plate draws laundry items against the upper surface of the wash plate in these regions directly adjacent the side walls 410 of the vanes. This enhances contact of the laundry items with the side walls 410 . It is believed that this contact promotes the inverse toroidal rollover wash pattern. The inventors consider that this effect is useful in promoting maintenance of the inverse toroidal rollover wash pattern with higher water levels, where laundry items otherwise tend to float out of contact with the wash plate.
[0049] The apertures 430 may comprise small groupings or arrays of circular or shaped holes adjacent the side walls of the vane, or alternatively may comprise one or more elongate slots through the wash plate in the region adjacent the vane. FIG. 7 illustrates an example wash plate including arrays of short curved slots 700 , or arcuate holes, in place of circular holes. Sufficient apertures may be provided in the regions of the low sectors adjacent the sidewalls, and may therefore be excluded from regions of the low sectors that are not close to the sidewalls of the vane.
[0050] To enhance the dragging effect of the laundry over the surface of the oscillating wash plate the inventors consider it advantageous for the spin basket to resist movement relative to laundry in the lower portion of the spin basket. For this purpose a series of tall buffers was proposed in U.S. Pat. No. 6,212,722. The present inventors now believe that smaller buffers that do not interact with laundry that is well above the level of the wash plate are preferable. A spin basket base member 300 including an annular series of buffers 302 of preferred form is illustrated in FIGS. 3 and 3B . The base member includes a hub portion 308 and a periphery 306 . With the wash plate in place the periphery 306 of the base member 300 encloses the space between the outer edge of the wash plate and the cylindrical wall of the wash basket. As seen in FIG. 3 the preferred buffers have a very low profile. Each buffer extends radially inward from the side wall of the spin basket. Each buffer preferably has a height of less than 3 cm, relative to the surrounding surface of the base member. Each buffer has a flattened shape, being several times wider that its height. Each buffer tapers as it extends in toward the wash plate.
[0051] The washer is capable of washing in two modes, a high efficiency mode and a traditional deep fill mode. In high efficiency mode the water to clothes ratio is typically less than 10 litres/kg. The traditional deep fill wash typically uses over 15 litres/kg. The two modes each have their benefits. The high efficiency mode uses less water and the more concentrated detergent solution gives excellent soil removal results for soluble soils. The traditional mode uses more water but is better at removing insoluble soils, such as sand and grass.
[0052] Wash performance in both modes requires achieving sufficient turnover of the clothes. In the high efficiency mode, higher contact with the wash plate due to lower water level means a marriage between plate shape and plate movement can readily create the inverse toroidal motion.
[0053] The preferred controller applies an initial wash plate drive profile to initiate the inverse toroidal motion. The initial drive profile is characterised by higher angular velocity and longer stroke length to start the clothes movement. This movement is subsequently maintained by a maintenance drive profile with lower angular velocity and stroke length. Many drive systems are possible for controlling wash plate drive profiles. One example is described in U.S. Pat. No. 5,398,298.
[0054] The initial drive profile is varied according to load size. The profile is more vigorous for larger load sizes. The load size is determined from the amount of water required to float the wash basket. The controller chooses the profile from the bowl float level.
[0055] Preferably the maintenance drive profile is also varied according to load size. Again the profile is more vigorous for larger load sizes.
[0056] By way of example in the preferred embodiment of the present invention the preferred controller can adaptively adjust the drive profile from stroke to stroke to try and maintain a drive profile of certain measured characteristics. An example drive profile is illustrated in FIG. 8 . The idealised profile is represented by the solid line. The profile achieved using the control methods described in U.S. Pat. No. 5,398,298 is illustrated by the dot-dash line. The profile includes a ramp where the wash plate speed increases approximately linearly. This ramp is followed by a plateau period. After the plateau period, the wash plate and motor coast to a stop. The stroke is then repeated in the reverse direction. The measured characteristics are plateau speed (ω), ramp time and plateau time. A more vigorous profile is characterised by greater energy input. In the measured characteristics this may be indicated by higher target plateau speed and reduced target ramp time while maintaining an overall stroke duration or angular stroke length.
[0057] For example in a test machine the inventors have found the following values for the measured characteristics to provide acceptable results:
Small Loads
[0058]
[0000]
Initial Profile
Maintenance Profile
Load
Ramp
Plateau
Ramp
Plateau
Size
Speed
Time
Time
Speed
Time
Time
1 kg
85
332
500
77
321
400
2 kg
89
299
500
80
299
400
3 kg
95
255
500
86
270
400
Medium Loads
[0059]
[0000]
Initial Profile
Maintenance Profile
Load
Ramp
Plateau
Ramp
Plateau
Size
Speed
Time
Time
Speed
Time
Time
3 kg
91
270
375
87
294
275
3.7 kg
96
255
400
91
284
300
5.0 kg
105
248
412
99
277
325
Large Loads
[0060]
[0000]
Initial Profile
Maintenance Profile
Load
Ramp
Plateau
Ramp
Plateau
Size
Speed
Time
Time
Speed
Time
Time
5.5 kg
120
228
462
108
262
362
6.5 kg
128
216
488
113
257
375
7.0 kg
130
208
500
116
252
387
[0061] The preferred controller operates an adaptive control where the rate of increase in an applied motor voltage, a point of cutting off this rate of increase, and a period of subsequent steady voltage, are each varied from stroke to stroke based on feedback of the resulting measured characteristics of previous strokes. These adjustments may be made in accordance with the methods set out in U.S. Pat. No. 5,398,298.
[0062] Acceptable wash performance is considered a compromise between achieving regular inverse toroidal turnover of a wash load within the spin basket and wear and tear associated with wash profiles that are too vigorous (and speeds that are too high) or entanglement (angular strokes that are too long).
[0063] In the preferred implementation each of the target measured characteristics for the initial profile is set according to the size of the wash load. The target measured characteristics are also set for the maintenance profile according to the load size. The size of the wash load may be measured in a number of ways known to persons skilled in the art. In the implementation preferred by the inventors the size of the wash load is determined from the level of water in the tub, measured by a water level sensor of any known type, at the water level when the spin basket floats and becomes disconnected from the motor drive shaft. This disconnection may be ascertained by monitoring changes in motor performance which indicate that the motor is no longer directly driving rotation of the spin basket.
[0064] The inventors have ascertained that these target characteristics of their preferred initial drive profiles and maintenance drive profiles can each be modelled as a curve or series of curves. Accordingly, preferred values for use by the microcontroller may be read from lookup tables or derived from appropriate formulae.
[0065] In the traditional deep fill mode there is less contact with the plate. The inverse toroidal laundry movement is started at a low water level preferably the same level as the high efficiency mode using the initial drive profile. However, rather than backing off into the maintenance profile once the inverse toroidal motion is established, for the traditional wash, the controller continues the vigorous profile while continuing to add water.
[0066] To initiate inverse toroidal motion the initial drive profile is preferably applied for from one to three minutes. The maintenance profile is generally sufficient to maintain the inverse toroidal motion once the motion has been established. This reduced vigour profile is more suitable for general wash action on the laundry load without excessive wear.
[0067] However the inverse toroidal motion may be lost, for example due to unusual load distribution or entanglement of laundry items. Accordingly, in the preferred embodiment of the invention the initial, or a similar vigorous profile, is applied for short periods intermittently in the wash cycle.
[0068] The preferred laundry washing machine implementing the present invention includes the capacity to circulate wash liquor from the lower portion of the wash tub to pour or spray the wash liquor onto the laundry load from a location above the laundry load. For example a conduit may lead from the lower portion of the tub to a spray nozzle overhanging the wash basket at the upper edge of the tub. A lower end of the conduit may be supplied with wash liquor from the lower portion of the tub by a pump. The pump may be a separate recirculating pump, or may be the drain pump, with a diverter valve selectively supplying wash liquor to a drain hose, or to the recirculation conduit.
[0069] In the case of this preferred laundry device it is preferred that the inverse toroidal rollover wash pattern is established after an initial period of circulating wash liquor without agitation.
[0070] This period may include the period prior to there being sufficient wash liquid to establish inverse toroidal rollover. For example, in the most preferred machine including floating disconnection between the spin basket and drive shaft, circulation can occur in the period before disconnection. The period of circulation without agitation may go on beyond this initial float period.
[0071] According to a further aspect of the present invention, in a preferred machine with recirculation of wash liquor, the recirculation may be activated during the inverse toroidal rollover wash pattern. The recirculation may be active during establishment of rollover or during maintenance of rollover. In some circumstances the inventors prefer to intermittently activate recirculation during maintenance of toroidal rollover. They consider that this draws water from generally below the wash load and applies this wash liquor to generally above the wash load. This encourages contact between the laundry items and the wash plate. This may be particularly effective in conjunction with the apertures through the wash plate, as this circulation liquid is drawn from wash liquid beneath the spin basket, and this liquid has generally passed through the apertures of the wash plate. The inventors further consider that this may be particularly beneficial in the case of increased water levels, where transfer of wash liquid from below to above the laundry will discourage or counteract floating.
[0072] The curving steep side walls and raised shoulders of the wash plate vanes create enough inward and then upward movement to keep the inverse toroidal motion going even when there is reduced contact between the clothes and the wash plate.
[0073] In summary, wash plate and drive profile design have created a wash system that means both high efficiency and traditional washing modes are possible in the one machine. | A laundry machine configured to supply a first amount of water to the wash tub wherein a wash plate can be oscillated such that clothes items directly above and in contact with the impeller are frictionally dragged in a oscillatory manner with the wash chamber while continuing to oscillate said wash plate, an additional supply of water is added to said wash tub such that as cloth items lost frictional engagement with the wash plate, the cloth items continue to move along an inverse toroidal rollover path at higher water levels. | 3 |
BACKGROUND OF THE INVENTION
During the drilling of boreholes, such as occasioned in seeking oil and gas production, the driling rigs must have made available a nearby large storage pond, called a mud pit, so that drilling mud can be mixed with various different chemical additives in order to carry out a proper drilling operation. Brine is often used in tremendous quantities in drilling operations and the handling of thousands of gallons of salt water is costly and must be carefully contained in order to avoid waste and contamination of the immediate area. It is especially important that the brine be contained within a reliable storage pond or tank in order to prevent damage to the underlying aquifer as may occur by the salts and chemicals escaping through the tank bottom and soaking into the fresh water zone. Moreover, vegetation, livestock, and wild animal life must be protected from runoff and spillage of the various chemicals employed in drilling a borehole.
Heretofore, the importance of lining earthen tanks has been ignored, or else the tanks have been inadequately lined by cementing together the edges of several polyethylene sheets. This is difficult to properly carry out in the field because the wind blows the light weight polyethylene about, making it difficult to effect a proper bond at the seams; and, furthermore, dirt and debris is blown onto the glue, causing the seam to subsequently part. The polyethylene liner is easily damaged by rocks and other sharp objects. Moreover, air entrapped under the plastic liner tends to float the entire liner to the surface, and therefore, it is not unusual for the workmen to attempt to overcome this drawback by throwing weights, rocks and other debris into the tank. Of course, this action contributes to the danger of injuring the liner as well as contaminating the contents of the tank.
Therefore, it is desirable to have a tank liner in the form of a unitary membrane which is impervious to drilling mud, chemical additives, and salt water. It would be desirable that the membrane be efficiently fabricated insitu to form a monocoque liner which overcomes the above drawbacks and which is not easily damaged.
SUMMARY OF THE INVENTION
This invention relates to tank liners and specifically to a method of lining an earthen tank with a unitary plastic impregnated fiberglass membrane by bonding fiberglass and paper together with a polyester resin to form a panel. The panel is rolled up into a convenient cylindrical roll and transported to the tank site.
The tank is formed by an excavation made into the ground and the panels are unrolled and placed within the tank adjacent to one another with the marginal edges thereof overlapping one another. The overlapped edges are bonded to one another by utilizing polyester resin and fiberglass cloth to thereby effect a unitary membrane which completely covers the entire bottom of the tank.
The marginal peripheral edges of the membrane preferably extends horizontally away from the tank and an overburden of earth is placed thereon to protect the marginal edges of the liner from livestock and equipment.
A primary object of the present invention is the provision of a unitary tank liner fabricated insitu and made of individual fiberglass panels having the edges thereof bonded to one another.
Another object of the invention is to provide a resin impregnated unitary fiberglass membrane for lining an earthen tank.
A further object of this invention is to disclose and provide a tank liner fabricated insitu by special fiberglass panels joined together to provide a unitary membrane which is impervious to salt water and drilling mud.
A still further object of this invention is to provide a polyester impregnated fiberglass tank liner made by field joining a multiplicity of panels together to provide a unitary membrane for containing liquids within an earthen tank.
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.
These and various other objects and advantages of the invention will become readily apparent to these skilled in the art upon reading the following detailed description and claims and by referring to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view taken along line 1--1; of FIG. 2 and discloses a tank having a liner made in accordance with the present invention;
FIG. 2 is a plan view of a tank having a liner made in accordance with the present invention;
FIG. 3 is an enlarged, broken, top plan view which discloses the tank of FIGS. 1 and 2 under construction;
FIG. 4 is a cross-sectional view taken along line 4--4 of FIG. 3;
FIG. 5 is a top plan view of part of the tank liner apparatus disclosed in FIGS. 1-3.
FIG. 6A is a cross-sectional view taken along line 6--6 of FIG. 5 and FIG. 6B is a modification thereof;
FIG. 7 is an end view disclosing the material of FIG. 5 in a rolled up configuration;
FIG. 8A is a cross-sectional side view of the tank lines of the present invention and FIG. 8B is a modification thereof.
FIG. 9 is a cross-sectional view taken along line 9--9 of FIG. 8; and,
FIG. 10 is a cross-sectional view of another embodiment of this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 discloses a tank 10 formed into the earth and adapted to hold salt water, crude oil, alkali solution, drilling mud, or various other chemical products. The area 12 surrounding the tank generally slopes downwardly therefrom with an embankment 14 usually being formed about the outer periphery of a tank liner 16 made in accordance with the present invention. Numeral 18 indicates the liquid level of the tank. The outer marginal peripheral edge portion 20 of the tank liner lies horizontally and preferably is covered with earth in the indicated manner of FIGS. 1 and 2.
The tank liner 16 is a unitary membrane and comprises a multiplicity of parallel panels 22 made in accordance with the present invention. The corners 24 of the tank may be at an abrupt angle as illustrated, or alternatively may be smoothly contoured into a long sweeping curve, as may be desired.
FIG. 3 discloses the method of fabricating the tank liner 16. As illustrated, the elongated, parallel, adjacent panel members 22 are arranged with their adjacent edges 25 and 26 slightly overlapping one another, as for example 2 or 3 inches of overlap for a panel of material 10 or 20 feet in width.
Numeral 27 indicates the step of placing a panel of material 22' adjacent to panels of material 22 already formed into the tank liner. The material of sheet 22' is laid down by unrolling the rolled up cylinder of material 122.
Numeral 28 indicates a reinforced lap-joint made insitu in accordance with the present invention. The lap-joint is formed by sand blasting the overlap area in the indicated manner of numeral 30 by employment of sandblasting equipment 32 having an outlet nozzle 34 of conventional design. Numeral 36 indicates plastic resin which has been applied to the sandblasting area.
As seen in FIGS. 3 and 4, the roll of material 122 is unrolled and panel 22' properly overlapped respective to the last laid panel, whereupon the adjacent panels are attached to one another by staples 38. Numeral 40 indicates a six inch width of reinforcement fiberglass matt bonded to the margins of two adjacent panels to reinforce the seam 28. Numeral 42 shows the fiberglass resin which is applied to complete the seam 28.
In FIGS. 5 and 6, numerals 44 and 46 indicate two sheets of material which are joined together to form a panel. Numeral 48 indicates a joint where reinforced material is placed at the longitudinal interseam 50 for effectively bonding the individual sheets of material together during the manufacture thereof.
Each sheet of the panel of material comprises a lower layer 52 of craft paper, a layer of fiberglass matt 54, which preferably is 11/2 ounces per square foot, and is available from Fiberglass Inc., Garland, Texas, with polyester resin 56 and 58 forming the outer surface. The polyester resin is a special blend comprised of iso and artho polyesters which impart flexibility into the panels and is available from Cook Paint and Varnish Company. Kansas City, Kas.
The outer surface adjacent the interface 58 is not sand blasted for the reason that the fiberglass reinforcing strip 60 is affixed to the outer surface of the panel with fiberglass resin 62 before the polyester resin 56 has completely cured.
The panels preferably are comprised of two 100 feet lengths of 5 feet wide fiberglass sheets which results in a, 100' × 10' panel. The panel can be rolled into a cylinder 122 is illustrated in FIGS. 3 and 7.
FIGS. 8 and 9 set forth in the constructional details of the completed tank liner. As seen in FIGS. 8A and 9, the factory splice 48 joins a plurality of sheets together to provide s multiplicity of panels which are joined together by a field splice 28 so that the tank liner comprises a membrane fabricated insitu in accordance with the method of the present invention.
FIGS. 6B and 8B illustrates another embodiment of the invention wherein the individual panels are fabricated from sheets having the marginal adjacent edges thereof overlapped and bonded together. The papers 52, 53 are overlapped and bonded to the overlapped fiberglass sheets 54, 55. Polyester 44 and 46 forms the outer surface and completes the panel. Numeral 148 broadly indicates the factory lap seam.
As particularly seen in FIG. 8B, the panels 22' are joined together at 28 in the same manner described above in conjunction with FIG. 8A. The field seams 28 join the panels 22' together to form the tank liner or continuous membrane.
FIG. 10 illustrates a large storage tank 68 having a bottom 70 therein which has been aged at 72 whereupon it will no longer hold liquid and the entire bottom heretofore usually must be replaced. A roof 74 is supported by the tank sidewalls 76 in the usual manner.
The bottom of the tank is repaired in the manner indicated by numeral 78 by providing a monolithic new plastic floor therewith in accordance with the present invention. The new floor is comprised of spraying foam plastic material 80 to a depth of 2-4 inches into the bottom of the tank with the foam bottom being carefully applied so as to achieve a smooth level floor. Inlet and outlet holes are marked so that they can be opened later on. A layer of rubber, like material 66 of about 1/8-1/4 inch in thickness is next applied over the entire surface of the floor. The rubber-like material is made of Urethane plastics which air dries to provide a resilient, impervious, continuous tank bottom. The rubber-like material can also be catalyst cured as is known to those skilled in the art.
In carrying out the method of the first embodiment of the present invention, a plurality of sheets of craft paper are laid in side by side abutting relationship and extended in width and length in an amount slightly greater than the panel being fabricated. The paper preferably comprises two parallel sheets six feet in width thereby providing ample overage which can be trimmed from the final panel.
Two adjacent abutting sheets of fiberglass matt five feet in width and one hundred feet in length are laid out in superimposed relationship on the paper with the adjacent edge portions of the fiberglass matt abutting one another. Polyester resin is next sprayed onto the matt and the narrow strip of material 60 is next applied before the polyester resin has set up. Additional polyester resin is applied to the strip 60 by using special paint rollers having a nap cover thereon made especially for the fiber glass industry.
As soon as the fiberglass resin has cured to hardness, which normally is about one hour, the excess paper is trimmed from the edges and the panels are stacked for final cure which requires 1-3 days, depending upon the temperature, humidity and ventilation. The finally cured panels are each rolled into a cylinder 122 and stored until needed to fabricate the tank.
In the second embodiment of the invention disclosed in FIGS. 6B and 8B, the craft paper is laid out on the floor in the before described manner but with the adjacent longitudinal edge portions thereof being overlapped as seen in FIG. 6B at numeral 148. When the sheets of matt are superimposed upon the craft paper, care is taken to overlap the adjacent edges thereof aproximately two inches, thereby eliminating the need for the strip of reinforcing matt 60 illustrated in FIG. 6A. The panels are cured and rolled in cylinders as in the before described manner.
The tank site is prepared by excavating a suitable area and using the excavated material to build up the sides thereof. Padding material, such as chip base or sand, is added as needed to made absolutely certain that a suitable bed is presented for receiving the unitary membrane. The rolls of material are next unrolled in the illustrated manner of FIG. 3 and the overlapping edges 25, 26 thereof stapled using a commercial air stable gun, as seen at 38 in FIGS. 3 and 4. In order to properly bond each of the panels to one another, it is essential that the area 30 be sandblasted so as to remove objectional films of material therefrom and furthur to roughen up an area which is to receive the fiberglass resin, thereby enhancing the bond. The resin and strip 40 is applied at the interface by utilizing the beforementioned roller.
After the membrane has been fabricated insitu a portion of the excavating material is back filled at 14 thereby covering the marginal peripheral edge portion of the membrane to prevent future damage thereto.
The present invention provides a unitized membrane which lines an earthen tank in an improved and unusual manner and thereby prevents leakage of objectionable chemicals into the surrounding area. | A unitary liner for an earthen tank fabricated in insitu from a multiplicity of fiberglass panels bonded together to form a unitized membrane which is impervious to brine, crude and drilling mud. The fiberglass panels are prefabricated and rolled into cylinders for delivery to the tank site where field fabrication of the membrane is completed by attaching overlapping edges of the panels to one another to form a seam. The edges are subsequently bonded together by fiberglass cloth and polyester resin. The fiberglass panels are made up of a plurality of sheets of paper and fiberglass cloth bonded together by fiberglass resin. The cylinder is of a configuration which enables it to be easily handled by workmen. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a new and improved apparatus for the determination of the thermal efficiency of a chemical reaction. In the context of this disclosure the term "thermal efficiency", or equivalent expressions, generally refer to the quantity of heat consumed or liberated in a chemical reaction.
When carrying out chemical reactions on a large scale basis as accurate as possible knowledge of their kinetic behavior is necessary. Since practically every chemical reaction is associated with a more or less large conversion of energy and the transformed quantity of heat is in a certain relationship to the reaction rate and the concentration of the reaction product it has been found that thermal analysis constitutes a practical and good expedient for obtaining information concerning the reaction kinetics of the most different reactions.
The invention of this development concerns an apparatus, generally designated as a thermal flow calorimeter, for determining the thermal efficiency of a chemical reaction, and which apparatus is of the type incorporating a reaction vessel equipped with a stirrer mechanism, a heat exchanger for influencing the temperature of the reaction mixture, the heat exchanger being located in the circulation system of a heat transfer fluid medium e.g. heat transfer liquid. Further, there are provided means for circulating the heat transfer fluid medium, measurement feelers for the temperature of the reaction mixture and the heat transfer fluid medium, and a regulation system cooperating with the measurement feelers for controlling the temperature of the reaction mixture. The regulation system embodies a reference value transmitter for the temperature of the reaction mixture and a temperature regulator which opposingly changes the temperature of the heat exchange fluid medium entering the heat exchanger for deviating the temperature of the reaction mixture by a multiple of the value of such reference value deviation.
A state-of-the-art heat flux calorimeter or thermal flow calorimeter of this type has been disclosed, by way of example, in Swiss Pat. No. 455,325. With this prior art calorimeter the heat exchanger is constructed as a pipe coil arranged within the reaction vessel. The pipe coil forms part of a circulation system in which there is circulated a suitable heat transfer medium. In the circulation system there is provided a cooling device which cools the medium down to a constant temperatuure throughout the entire reaction time. After the cooling device there is connected a heating device which heats the medium to the momentarily required temperature. By means of the heating device a regulator controls the temperature of the medium which flows into the pipe coil in such a manner that by means of the pipe coil there is always delivered or withdrawn, as the case may be, just so much heat from the reaction mixture and corresponding to the thermal efficiency that the temperature of the reaction mixture follows a preprogrammed time function. Under these conditions the quantity of heat which is consumed or liberated respectively, by the medium per unit of time through the agency of the pipe coil constitutes a measure for the thermal efficiency of the reaction. In order to determine this quantity of heat there is continually recorded the difference of the temperature of the heat transfer medium which prevails at the input and at the output of the pipe coil. Under the precondition that there prevails a constant rate of flow through the pipe coil this temperature is proportional to the quantity of heat which has been consumed or liberated, as the case may be, between the measurement points.
One of the drawbacks of this prior art thermal flow calorimeter resides in the presence of a pipe coil internally of the reaction vessel. Due to the arrangement of such pipe coil within the reaction vessel the elimination of the reaction residues which is required after each measurement is rendered extremely difficult. Although it might appear to be obvious to simply replace the reaction vessel which is equipped with the internally arranged pipe coil by means of a double-wall reaction vessel such is not possible by virtue of the specially employed measurement principle, since in the case of a double-wall reaction vessel completely different heat flow conditions prevail which cannot be so simply monitored, and which for such special measuring principle falsify the measurement results and thus render such less reliable for reaching conclusions regarding the thermal efficiency of the chemical reaction.
One of the most decisive drawbacks of the heretofore known thermal flow calorimeters resides in the stark dependency of the measuring accuracy upon the constant flow rate per unit of time of the quantity of heat transfer medium flowing through the pipe coil. It is particularly difficult with high throughput and especially in the case of non-isothermic reactions to maintain a constant throughflow rate since the viscosity characteristics of the heat transfer fluid medium markedly vary.
A further drawback of the prior art thermal flow calorimeter resides in the nature of the regulation system for the temperature of the heat transfer medium. This system functions in accordance with the throughflow principle and is much too sluggish for higher throughflow rates. Additionally, it is relatively uneconomical since owing to the series arranged cooling and heating devices it is necessary to initially cool the entire circulating medium to a constant temperature which is below the temperature which is just required and then such must be again heated to the required value.
The above-discussed drawbacks and limitations have resulted in the recognition that the heretofore known thermal flow calorimeter is not satisfactory in practice.
SUMMARY OF THE INVENTION
Accordingly it will be recognized from what has been discussed above that this particular field of technology is still in need of apparatus for determining the thermal efficiency of a chemcial reaction in a manner not associated with the aforementioned drawbacks and limitations of the prior art proposals. It is therefore a primary objective of the present invention to satisfy this need which exists in the art.
Another and more specific object of the present invention aims at the provision of an apparatus which is relatively simple in construction and extremely reliable in operation by means of which it is possible to determine the thermal efficiency of chemical reactions of random nature and under random reaction conditions, especially also larger reaction volumes, with the greatest possible resolution and accuracy.
The present invention relates to an apparatus of the previously mentioned type which is manifested by the features that the reaction vessel is equipped with a double-wall jacket or shell which forms the heat exchanger, that the heat transfer fluid medium can be circulated so rapidly that the difference of its temperature at the input and at the output of the shell throughout the entire duration of the reaction, with the exception of possibly occurring momentary irregularities in the reaction kinetics, does not exceed 1°C, that the temperature regulator is constructed as a mixture regulator and encompasses a respective container for heat transfer fluids which are hotter and colder with respect to the temperature of the heat transfer fluid which is circulated in the circulation system and each such container is operatively connected with the circulation system as a function of the reference value deviation of the temperature of the reaction mixture, and further, that there is provided an apparatus for the continuous determination of the difference between the temperatures of the reaction mixture and the heat transfer fluid or fluid medium at a randomly selected location of the heat exchanger.
The apparatus of the invention functions according to a new measurement principle. In contrast to the heretofore known apparatus the small temperature differential between the input and the output of the heat exchanger is not employed as a measurement for the thermal efficiency of the reaction, rather by sufficiently rapidly circulating the fluid medium of the circulation system such temperature differential is intentionally reduced as much as possible and therefore the difference between the temperature of the heat transfer fluid medium which is approximately equal in this way throughout the entire heat exchanger and the temperature of the reaction mixture is evaluated as a measure for the thermal efficiency of the reaction. This novel measuring principle is considerably more accurate and reliable than that employed with the previously described apparatus of the prior art. However, it cannot be realized with the heretofore known means of such apparatus, namely a pipe coil and a relatively inertia-prone temperature regulating system which functions according to the throughflow principle. The requisite precondition for such measuring principle is that there be provided a reaction vessel with a douoble-wall shell or jacket, a very rapid temperature regulation system for the heat transfer fluid medium and appropriately dimensioned circulation means in order to insure for a sufficiently rapid circulation of the fluid medium. On the other hand, the throughflow rate of the heat transfer fluid medium through the heat exchanger need not be constant.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a schematic illustration of the entire arrangement of exemplary embodiment of inventive apparatus;
FIG. 2 graphically illustrates an example of a heat flux or thermal flow curve of a temperature-programmed course of reaction determined with such apparatus;
FIG. 3 is a graph illustrating an example for the thermal flow curve of an isothermic reaction; and
FIG. 4 illustrates in detail a variant embodiment of the apparatus depicted in FIG. 1, and partially shown in cross-sectional view.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, in the exemplary embodiment of apparatus depicted in FIG. 1 reference numeral 1 designates a reactor or reaction vessel formed of glass and having a capacity of about 2.5 liters, this reactor being equipped with a double-wall shell of jacket. The reactor is sealed by means of any suitable cover and dimensioned such that it can withstand pressures up to about 4 atmospheres absolute (excess) pressure. A motor driven stirrer or agitator 2 extends into the interior of the reactor 1, the purpose of the stirrer 2 is to continuously mix the reaction mixture 3 which is located within the reactor so that there prevails therein an approximately homogeneous temperature distribution.
The hollow compartment or space 4 in the reactor shell, conveniently designated by reference character 1a, and formed by both of the shell walls 1b, is connected through the agency of an inlet 1c and an outlet 1d with a circulation system 100 for a heat transfer fluid medium, typically a liquid, for instance a low-viscosity silicone oil. Instead of using a liquid it is to be specifically understood that it is also however possible to use any other suitable medium. This circulation system 100 embodies the shell compartment 4, a circulation pump 5, a throttle element 6 and not particularly designated conduits or lines which operatively interconnect such components.
The circulation pump 5 possesses such a great delivery capacity that the heat transfer liquid during its passage through the hollow shell compartment 4 is neither heated or cooled, as the case may be, by more than 1°C owing to the heat exchange action with the reaction mixture. Preferably the temperature difference between the inlet 1c and the outlet 1d of the hollow shell compartment 4 should be in the order of several tenths of a degree. Such conditions are applicable for the entire course of the reaction. During sudden initiation of a reaction or during the switching-on and switching-off of the calibrated heating arrangement which is still to be described it is, however, possible that the indicated boundaries are momentarily exceeded. Such sudden briefly lasting changes of the thermal efficiency are conveniently referred to hereinafter as unstable or irregular points of the reaction kinetics irrespective of their cause. Generally, it is possible to maintain the indicated boundaries for the temperature differential in that there is circulated per minute a quantity of heat transfer liquid which corresponds approximately to three-fold to sixty-fold the volume of the shell compartment. In this way there is insured for a sufficiently rapid heat exchange with the reaction mixture in the reactor 1.
Continuing, it will be observed that connected in parallel to the throttle element 6 are a respective container or vessel 7 and 8 through the agency of a valve 9 and 10 respectively, at the circulation system 100. In relation to the quantity of liquid circulated in the circulation system 100 the container 7 contains a larger quantity of relatively cooler heat transfer fluid medium e.g. liquid, whereas the container 8 contains a relatively warmer liquid. Within the container 7 there is arranged a heat exchanger 30 through which flows any suitable coolant, for instance brine, and serving to cool the liquid flowing through the circulation system. The temperature of the liquid in the container 7 is determined by a measurement or measuring feeler 31 and delivered to a regulator 32 which controls a valve 33 arranged in the infeed conduit for the cooling liquid or coolant. In the circulation system for the heat transfer liquid there is further provided an additional measuring or measurement feeler 34 which determines the temperature prevailing at the circulation system and likewise delivers such determined temperature value to the regulator 32. Such regulator 32 actuates the valve 33 in such a manner that the difference between the temperature of the heat transfer liquid in the circulation system 100 and its temperature in the container 7 maintains an adjustable constant value. Depending upon the nature of the reaction which is to be examined the container temperature can amount to about -50°C to +180°C.
Within the container 8 there is arranged a suitable, for instance electrical heating device 35, by means of which the heat transfer liquid can be heated to a temperature in the range of about +20°C to +250°C. A temperature feeler 36 determines the container temperature and delivers such to a regulator 37 in a similar manner as for the container 7, this regulator is simultaneously also operatively connected with the temperature feeler 34 in the circulation system 100. The regulator 37 controls a switch 38 in the current circuit of the heating device 35 in analogous manner as the regulator 32.
Supposing now that, for instance, the temperature of the liquid in the circulation system should be reduced, then the valve 9 is opened and cold liquid flows out of the container 7 in a special manner still to be described into the circulation system until at that location the desired temperature has adjusted. On the other hand, for the purpose of increasing the temperature hot or warmer liquid is delivered to the circulation system from the container 8 by opening the valve 10. Owing to the relatively high delivery capacity or output of the pump 5 and the large containers for the respectively hot and cold liquid it is possible to bring the temperature of the heat transfer liquid which is located in the circulation system 100 and therefore flows through the hollow shell compartment 4 to the desired value practically without any delay in time and within a sufficiently small time span (with time-constants of about 30 seconds).
A regulation or regulator system 11 serves to control the temperature of the heat transfer liquid in the circulation system. This regulation system 11 cooperates with two temperature feelers 12 and 13 arranged within the reactor and in the circulation system or in the hollow shell compartment as well as with a program transmitter 14. This program transmitter 14 delivers the desired time course of the temperature of the reaction mixture in the reactor as a reference value. In the case of isothermic reactions this reference value of course is constant as a function of time.
This regulation system or regulator 11 is constituted by a so-called cascade regulator. It encompasses a master regulator or controller 15, a follower regulator or controller 16 and a pulse generator 17. The master regulator 15 which can possess proportional characteristics, proportional-integral characteristics or proportional-integral-differential characteristics, forms an error signal from the deviation of the actual value of the reaction temperature from its reference value. From this error signal there is formed together with the reference value of the reactor temperature the reference value for the temperature in the circulation sytem and compared with the actual value of the temperature of the circulation system. The follower regulator 16 forms an output signal from the reference value deviation of the circulation system temperature, the magnitude of this output signal determining the rate of change of the temperature of the circulation system. The follower regulator can have two point- or three point- characteristics, preferably however possesses proportional- or proportional-differential characteristics. The output signal is transformed at the pulse generator 17 into heating- or cooling control pulses which periodically open and close the valve 9 or the valve 10 respectively, depending upon whether it is desired to reduce or increase the temperature in the reactor below or above the momentary reference value. The duration and amplitude of the pulses are essentially constant. The pulse intervals between each two successive pulses are not constant, rather depend upon the magnitude of the reference value deviation of the reaction temperature and the magnitude of the output signal formed by the follower regulator. This pulse-like control of the circulation system temperature permits of the use of relatively inexpensive regulation valves, since such need only possess an open-close characteristic or function, and do not have to operate on a proportional basis.
The master regulator 15 and the follower regulator 16 are adjusted such that with a predetermined deviation of the reactor temperature from the reference value the reference temperature of the circulation system deviates by a multiple of such deviation from the momentary actual value of the circulation system temperature. A typical factor which has proven itself in practice by experience amounts to about 10; i.e. with a reference value deviation of the reactor temperature of 1°C the circulation system reference temperature is changed by 10°C. With suitable adjustment of this gain or amplification factor and the proportional band of the follower regulator it is possible to achieve the result that with thermal transformations in the reactor the temperature of the heat-transfer circulation system liquid assumes a value, within a very short period of time and practically without any overshooting, at which the thermal flow between the reactor and the circulation system is equal to the thermal efficiency in the reactor.
For determining this thermal flow or heat flux between the internal space of the reactor and the hollow shell compartment or space there are provided two further temperature feelers 18 and 19 arranged in each one of both spaces and an apparatus 20 for recording the values detected by such measurement feelers. The recording apparatus 20 plots the time-course of the difference between the reactor temperature and the circulation system temperature upon a paper strip or other suitable recording medium. At the same time there is also recorded the temperature in the reactor. The temperature difference between the reaction mixture and the circulation system liquid constitutes a measure for the thermal flow and thus for the thermal efficiency of the reaction.
For calibrating the apparatus there is provided in the internal space of the reactor an electrical heating element which has not been particularly shown. By means of this calibration heater there is delivered to the reactor during a predetermined time-span an exactly defined quantity of heat and thus there is plotted the associated heat flux or thermal flow curve which will be more fully explained hereinafter on the basis of the following example. The integral over such heat flux curve then provides a calibration factor for the apparatus.
In FIG. 1 there is additionally schematically illustrated a further advantageous auxiliary apparatus for the previously described apparatus. Such auxiliary apparatus constitutes an automatic dosing apparatus 40 by means of which solid, liquid or gaseous substances can be introduced into the reaction mixture at an exactly defined period of time or continuously in an exactly defined quantity. The dosing device or apparatus 40 encompasses a delivery or infeed line 41 which opens into the reactor, the other end of this delivery line or conduit leading to a not particularly illustrated supply container for the substance which is to be dosed. A throughflow regulator 42 is located in the delivery conduit or line 41 and such regulator is controlled by an electronic control device 43. At this control device 43 there can be conveniently adjusted the point in time and the quantity of the substance which should be supplied into the reactor.
Of course, a number of dosing devices could be provided.
Now in FIG. 4 there has been illustrated a particularly advantageous exemplary embodiment of the construction of a temperature regulating system for the heat transfer liquid. In this exemplary embodiment both of the containers for the heat transfer liquid and the circulation pump have been assembled together into a compact unit.
Both of the containers 51 and 52 for the heat transfer liquid are arranged in superimposed fashion, as shown, and intermediate thereof there is located the circulation pump which is shown, for instance, as a centrifugal pump 53. This pump 53 is connected through the agency of a respective suction-side connection 53a and pressure-side connection 53b with the circulation system of the heat transfer liquid.
Both of the containers 51 and 52 are of the same general construction. In the embodiment under discussion they possess a substantially cylindrical configuration with vertically extending lengthwise axes, but of course could have a different configuration, such as also a polygonal cross-sectional configuration. The housing 53c of the pump 53 is also constructed at its outer surface so as to be likewise substantially cylindrical and in this case has the same outer diamter as both of the containers 51 and 52. At the upper and lower end faces of the pump housing 53c there are suitably formed a respective annular or ring-shaped groove 53' in which there are seated the associated marginal edges of the bottomless top container 52 and the coverless lower container 51. Stated in another way both of the containers 51 and 52 are open at one respective end, but in the arrangement under discussion the end surfaces or faces of the pump housing 53c form the floor and cover of the upper container 52 and the lower container 51. The edges of the containers 51 and 52 which are seated in the annular or ring-shaped grooves 53' are equipped with a respective radially outwardly protruding flange 51a and 52a respectively. By means of these flanges both of the containers 51 and 52 are clamped together through the agency of screws 54 or equivalent fastening expedients. In this way the pump 53 is also fixedly held between both of the containers 51 and 52. Owing to the essentially equal diameter of these three superimposed and interconnected components such form a compact structural unit. To avoid any thermal losses and heat exchange between the containers via the pump the pump housing 53c is advantageously formed of a thermally insulating substance, for instance glass-fiber reinforced polytetrafluoroethylene. Additionally, this entire structural unit is enclosed by means of a not particularly illustrated envelope or shell formed of insulating material.
The pump impeller 53d of the centrifugal pump 53 is seated upon a vertical pump drive shaft 55 which is rotatably mounted at the upper and lower portion of the pump housing 53c by means of a respective radial bearing 55b and 55a. The pump shaft 55 depends downwardly into the lower container 51 and at that location carries a repulsion element, which in the illustrated embodiment comprises a propeller 55c which, during rotation of the pump shaft 55, generates an axial flow within the container 51. In similar manner the pump shaft 55 also extends upwardly and into the upper or top container 55. In this case, however, the pump shaft 55 extends through the cover 52' of such container 52 and is operatively connected with the drive shaft of a suitable drive motor 56 arranged upon such container cover 52'. An axial bearing 55d which is secured to the cover 52' secures the pump shaft 55 against axial displacement. Upon the section of the pump shaft which is located within the upper container 52 there is likewise arranged a propeller 55 e or the like, and this propeller produces an axial flow at the heat transfer liquid located within the container. Owing to such flows which are produced in the containers there is obtained within such containers as uniform as possible temperature distribution. For this purpose there is also arranged in each container 51 and 52 a respective substantially cylindrical flow guide surface 57a and 57b coaxially arranged with respect to the pump shaft 55 and serving to further intensify the circulation effect.
Now in order to bring and maintain the temperature of the heat transfer medium in the upper container to the value which is required in each case for the function of the entire apparatus the container 52 is equipped with an electrical heating element 58. Furthermore, the lower container 51 is equipped with a cooling coil 59 which can be connected with any suitable and therefore not particularly illustrated source of a cooling medium or coolant. A respective regulating device 60 and 61 controls the temperature of the heat transfer liquid in the upper container 52 and the lower container 51 respectively, by actuating the electrical switch 58a and opening and closing the valve 59a respectively.
The mounting of the pump drive shaft 55 in the pump housing 53c occurs without any packing gland, in other words is not carried out so as to provide a tight seal. Therefore the internal space or compartment of the pump is continuously flow connected via the bores 66 and 67 in the pump housing, through which the pump shaft is guided, and both of the radial bearings 55a and 55b, with the lower and upper containers. The throughflow cross-sections of such connections are dimensioned such that between the inner space of the pump and the upper and lower containers there does not occur any liquid exchange brought about by convection. This can be accomplished, for instance, by carrying out an appropriately narrow dimensioning of the bores 66 and 67 or also by providing an appropriately narrow opening in the covers of the radial bearings 55a and 55b.
The pressure side of the pump 53, in other words the radially outwardly located region of the inner space of the pump, is connected via a bore in the pump housing 53c with a connection 53e at which there are connected through the agency of a branch element two conduits or lines 62 and 63, each of which is equipped with a respective shutoff or closure element 62a and 63a respectively. The conduit 62 opens into the lower portion of the lower container 51 and the conduit 63 opens into the upper portion of the upper container 52, as shown. Together with the associated container, the pump and the connection 53e, these conduits form two auxiliary or branch circulation systems for the working circulation system for the heat transfer liquid.
The mode of operation of the regulation system is as follows: During the normal condition of the system both of the valves 62a and 63a are closed. The pump 53 then circulates the heat transfer liquid only through the working circulation system. Now when the temperature in the working circulation system should increase, then, the valve 63a at the upper auxiliary or branch circulation system is opened. Consequently, a portion of the liquid which circulates in the working circulation system is branched-off through the connection or conduit 53e into the associated auxiliary or branch circulation system. This however brings about that owing to the new prevailing excess pressure in the upper container a corresponding quantity of relatively warmer liquid flows out of the upper container 52 through the radial bearing 55b into the pump 53 where at that location it admixes with the cooler circulation system liquid and finally brings about an increase of the temperature of the working circulation system.
In analogous manner for the purpose of reducing the temperature in the working circulation system the valve 62a is opened and closed. By suitably selecting the temperature differential between the liquids in the containers and in the working circulation system and by appropriately dimensioning the flow resistance in the auxiliary circulation systems it is possible to obtain an extremely rapidly reacting temperature control.
Both of the regulators 60 and 61 cooperate with a respective temperature feeler 60a and 61a in the containers 51 and 52 respectively, and a further temperature feeler 60b in the working circulation system, preferably arranged at the pump inlet, and maintain constant the difference between the temperatures of the heat exchange liquid in the working circulation system and in the containers.
Here also both of the valves 62a and 63a are controlled by means of a regulation system or regulator system, in the same manner as for the exemplary illustrated embodiment of FIG. 1, and which regulator cooperates with a respective temperature feeler 64a and 64b as well as a program transmitter 65. The temperature feeler 64a is arranged at the output-side pump connection 53b and the temperature feeler 64b is arranged in the inner space of the reactor. The regulation system 64 corresponds in its construction and in its mode of operation to the regulation system 11 of the embodiment of FIG. 1.
The temperature control unit for the heat transfer liquid as illustrated in FIG. 4 is extremely simple in construction and therefore relatively inexpensive. In particular it requires only a single drive motor for the circulation pump and both of the propellers in the containers. The individual components including the pipe conduits can be limited to a minimum and the pipe conduits also can be designed of extremely short construction. The apparatus is very compact and constitutes a space-saving unit owing to the direct connection of both containers with the pump into a unitary assembly. Due to the unique arrangement of the pump between both of the containers it is possible to save at least two pipe conduits and in particular to avoid having to use a relatively inexpensive sealed mounting arrangement for the pump shaft in the pump housing. The arrangement of the containers above one another and the pump drive motor upon the upper container also renders possible a glandless and therefore inexpensive mounting of the pump shaft at the cover of such container.
There will now be described hereinafter the functioning of the equipment illustrated in FIG. 1 on the basis of the examination of the isomerism of trimethylphosphite by way of example. The reaction proceeds according to the equation: ##EQU1##
If such reactions run out of control then the reaction mixture heats up very intensely and thus attains high vapor pressures. The pressure increase occurs so rapidly that there cannot be realized a stabilizing boiling, rather than a foaming of the reaction mass which can even bring about bursting of an open reactor or reaction vessel.
Elementary analysis of such reactions have shown that they are increasingly more dangerous the quicker that they proceed. However, for production reasons there is an interest to have these reactions occur with as great as possible reaction rates. In order to clarify the question what reaction rate is permissible within the prevailing safety regulations and under what reaction conditions such rate can be realized there is required a model of the reaction kinetics. To this end there is provided a mathematical model with a number of variable parameters and such parameters are varied by means of a computer in such a manner until the mathematical model coincides with the experimental data.
FIG. 2 illustrates the results of a temperature-programmed thermal flow experiment, and FIG. 3 that of an isothermal flow experiment.
For the practical performance of the temperature-programmed thermal flow experiment the reaction constituents are admixed with one another in a cold condition. Thereafter the reaction mixture is carefully heated in that the program transmitter 14 is set to a linear temperature increase of about 8°C per hour. The increase of the temperature in the reactor is illustrated at the lower portion of the diagram of FIG. 2. The regulator 11 then controls the circulation system temperature such that the temperature in the reaction vessel assumes the course prescribed by the program transmitter.
As readily recognized from the showing of FIG. 2 the heat flux or thermal flow curve at the start of the temperature increase has a sudden negative drop or jump. This is caused by the fact that the temperature of the heat transfer liquid in the circulation system must be greater by a certain amount than the temperature of the reaction mixture if this temperature should follow the desired program. From the magnitude of this temperature jump towards the negative it is possible to determine the specific heat of the reaction mixture.
Owing to the increasing temperature in the reactor the reaction gradually begins to start and thus releases heat which brings about that the reaction temperature tends to increase beyond the reference temperataure prescribed by the program transmitter. This attempt on the part of the reaction temperature to exceed the prescribed reference temperature is immediately counteracted by the regulator in that it reduces by an appropriate value the temperature of the heat transfer liquid. The difference between the reactor temperature and the circulation system temperature results in the heat flux curve illustrated in FIG. 2. The ordinate of such diagram has already been calculated in Kcal per Mol.
As recognized by referring to FIG. 2 the reaction rate, which is a measure of the heat flux, at the start increases relatively slowly and then very rapidly to a maximum value and finally again drops back to null owing to the increasing throughput. From this point in time any further heating-up of the reaction mixture is no longer sensible because now the reactor temperature is maintained constant. In so doing the thermal flow curve of course again makes an upward jump at the value null and then extends horizontally, as shown.
The thin horizontal full-line b shown in the drawing of FIG. 2 is designated as the base line. The momentary thermal efficiency of the reaction can be ascertained from the vertical spacing of the corresponding point along the thermal flow curve from such base line. The surface which the thermal flow curve encloses together with the base line corresponds to the total heat transformation of the reaction.
In order to carry out the isothermal experiment (FIG. 3) initially the mixture, without any catalyst, is brought to the reaction temperature, then at the point in time designated by reference character O there is added the catalyst (CH 3 J). The full line illustrates the undisturbed isothermal reaction course. The broken line curve illustrates the reaction course after the addition of an inhibiter. The inhibiter (triethylamine) reacts in an exothermal very rapid reaction with the catalyst and thus brings the reaction to standstill.
The last experiment particularly accentuates the advantages and possibilities of the previously described exemplary embodiments of equipment. It shows that with the inventive equipment it is possible to better and more clearly detect the special particular dangers which inherently reside in the kinetics of the isomerism of trimethylphosphite than with the classical techniques. On the other hand, it clearly demonstrates in a particularly impressive manner the important significance of the possibility of being able to undertake manipulations at the reaction mixture during the measurements.
Of course, with the previously described exemplary embodiments of equipment one is not bound to initiating the reaction by heating or by a single or one-shot addition of a catalyst. For instance, it is possible to continuously introduce into the reactor by means of the automatic dosing devices a reaction component during the isothermal or temperature-programmed reaction course.
The recording device of course is not limited to a paper strip-plotting device, rather there can be used any suitable device by means of which it is possible to record or retain the temperature values determined by the measurement feelers. For instance the recording device can be a storage from which the stored information is delivered to a computer which, on the basis of this information, directly calculates an appropriate theoretical kinetic model of the reaction.
With the previously described equipment, among other things, the following advantages are particularly worthy of comment.
a. The possibility of examining technical, concentrated exothermic and endothermic reaction systems under the conditions which approximate those prevailing during production;
b. Close actual surface-volume conditions of the examined reaction mixture;
c. The possibility of carrying out isothermal, temperature-programmed and if necessary also adiabatic experiments;
d. The possibility of interceding in the course of the reaction by dosing-in gaseous, solid and liquid reagents according to adjustable dosing programs;
e. The possibility of determining the theoretical kinetics through a number of few isothermal and temperature-programmed experiments;
f. When using glass reactors there is the possibility of visually observing the reaction course (phase-, modification-, color- and viscosity changes of the reaction mixture); and
g. When using appropriately constructed metallic reactors there is the possibility of examining high-pressure reactions with the same basic equipment (heat exchanger system, regulator system).
While there is shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously emobided and practiced within the scope of the following claims. ACCORDINGLY, | An apparatus for determining the thermal efficiency of a chemical reaction wherein a reaction vessel is equipped with a double-wall jacket or shell which forms a heat exchanger, a heat transfer fluid medium is circulated so rapidly that the difference of its temperature at the inlet and at the outlet of the shell throughout the entire duration of the reaction, with the exception of possibly occurring momentary irregularities in the reaction kinetics, does not exceed 1° C. A temperature regulator is provided which is constructed as a mixture regulator and encompasses a respective container for heat transfer fluids which are hotter and colder with respect to the temperature of the heat transfer fluid which is circulated in the circulation system and each such container is operatively connected with the circulation system as a function of the reference value deviation of the temperature of the reaction mixture. Further, there is provided an apparatus for the continuous determination of the difference between the temperatures of the reaction mixture and the heat transfer fluid at a randomly selected location of the heat exchanger. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional of U.S. patent application Ser. No. 10/596,412 filed on Jun. 13, 2006, which is a National Phase application of PCT/KR04/03327, which claims priority to KR10-2003-0093342 and KR10-2004-0058809, the full disclosure of each of these documents is incorporated by reference in their entirety herein.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention relates to novel derivatives of oxazolidinone, preparation methods of the same, and pharmaceutical compositions comprising the same for use in an antibiotic.
[0004] 2. Description of the Related Art
[0005] Used as orally administrable antibacterial agents, oxazolidinone compounds are not products of fermentation, but artificially synthesized ones, and various structures of their derivatives are known. For instance, 3-phenyl-2-oxazolidinone derivatives having one or two substituents are stated in U.S. Pat. Nos. 4,948,801, 4,461,773, 4,340,606, 4,476,136, 4,250,318 and 4,128,654. 3-[(Monosubstituted) phenyl]-2-oxazolidinone derivatives of Formula 2 are disclosed in EP 0312000, J. Med. Chem. 32, 1673 (1989), J. Med. Chem. 33, 2569 (1990), Tetrahedron, 45, 123 (1989), etc.
[0000]
[0006] Pharmacia & Upjohn developed oxazolidinone derivatives of Formulas 3 and 4 (WO 93/23384, WO 95/14684 and WO 95/07271). Having succeeded in gaining the approval of the Food and Drug Administration (FDA) of U.S.A., the oxazolidinone derivative of Formula 3, by the name of ‘Zyvox’, has come into the market. However, these conventional synthetic oxazolidinone compounds were found to suffer from the disadvantage of showing antibacterial activity against a narrow spectrum of bacteria, being toxic to humans, and being poor in therapeutic activity in vivo. Zyvox may be used restrictively as injection since the solubility of Zyvox against water is inadequate for use in injection, which is about 3 mg/ml.
[0000]
[0007] Further, WO 93/09103 discloses derivatives of phenyl oxazolidinone, substituted with heterocyclics such as thiazole, indole, oxazole and quinole, as well as pyridine, at position 4 of the phenyl ring. However, these derivatives of oxazolidinone are known as providing insufficient medicinal effects because the heterocyclics bear simple substituents such as alkyl or amino groups.
[0008] In WO 01/94342, synthesizing derivatives of phenyl oxazolidinone, having with pyridine or derivatives of phenyl at position 4 of the phenyl ring was described. The compounds synthesized are potent in inhibitory activity against a broad spectrum of bacteria and are also superior antibiotic to Zyvox. However, The compounds are unable to be formulated as injection because solubility of the same is under 30 μg/ml.
[0009] Accordingly, the intensive and thorough research on oxazolidinone derivatives, conducted by the present inventors aiming to overcome the above problems encountered in prior arts, resulted in the finding oxazolidinone derivatives as well as prodrugs thereof, wherein the prodrugs are prepared by reacting amino acid or phosphate with the oxazolidinone derivatives having hydroxyl group. Further, salts of the oxazolidinone derivatives prodruged were easily synthesized by using amine group of amino acid of the same to synthesize organic acid or inorganic acid and by using a hydroxyl group of phosphate and one selected from sodium and calcium. The oxazolidinone derivatives have excellent effects on antibiotic activity and the solubility of the same is greatly enhanced.
SUMMARY OF THE INVENTION
Disclosure of the Invention
Technical Problem
[0010] It is an object of the present invention to provide novel derivatives of oxazolidinone.
[0011] It is another object of the present invention to provide a method of preparing the above-mentioned derivatives.
[0012] It is still another object of the present invention to provide a pharmaceutical composition comprising the above-mentioned derivatives for use in an antibiotic.
Technical Solution
[0013] The present invention provides novel derivatives of oxazolidinone corresponding to Formula 1 defined below.
[0000]
[0014] In the Formula 1, X represents carbon or nitrogen.
[0015] R 1 and R 1 ′ respectively represent hydrogen or fluorine.
[0016] R 2 represents —NR 5 R 6 , —OR 7 , triazol, fluorine, alkylphosphate, monophosphate or a metal salt of phosphate;
[0017] R 5 and R 6 , which are the same or different, respectively represent hydrogen, C. sub. 1-4 alkyl group or acetyl; and
[0018] R 7 is hydrogen, C. sub. 1-3 alkyl group or acylated amino acid. When the R 7 is acylated amino acid, amino acid refers to alanine, glycine, proline, isoleucine, leucine, phenylalanine, β-alanine or valine.
[0019] Het, which is a heterocyclic ring or a hetero aromatic ring, refers to pyrrole, furan, piperazine, piperidine, imidazole, 1,2,4-triazol, 1,2,3-triazol, tetrazole, pyrazole, pyrrolidine, oxazole, isoxazole, oxadiazole, pyridin, pyrimidine, thiazole or pyrazine.
[0020] R 3 and R 4 , which are the same or different, respectively refer to hydrogen, C. sub. 1-4 alkyl group that is substituted or unsubstituted with cyano, —(CH 2 )m-OR 7 (m represents 0, 1, 2, 3, 4) or ketone.
[0021] The derivatives of oxazolidinone corresponding to Formula 1 may be used for a pharmaceutically acceptable salt, it is preferably an acid addition salt prepared by using pharmaceutically acceptable free acid. The free acid may be inorganic or organic. The inorganic free acid may comprise hydrochloric acid, bromic acid, sulfuric acid, phosphoric acid, etc. The organic free acid may include citric acid, acetic acid, lactic acid, maleic acid, fumaric acid, gluconic acid, methane sulfonic acid, glyconic acid, succinic acid, 4-toluenesulfonic acid, trifluoroacetic acid, galuturonic acid, embonic acid, glutamic acid, aspartic acid, etc.
[0022] Preferred compounds of the oxazolidinone derivatives according to the present invention include the following compounds and their structures are described in Table 1.
1) (S)-3-(4-(2-(2-oxo-4-glycyloxymethylpylolidin-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 2) (S)-3-(4-(2-(4-glycyloxymethyl-1,2,3-triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 3) (S)-3-(4-(2-(5-glycyloxymethylisoxazol-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 4) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,4]triazol-1-yl)methyl oxazolidin-2-on, 5) (S)-3-(4-(2-(2-oxo-3-glycyloxypyrolidine-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 6) (S)-3-(4-(2-(5-glycyloxymethyl-[1,2,4]oxadiazole-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 7) (S)-3-(4-(2-(5-glycyloxymethyl-4,5-dihydroisoxazole-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 8) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-2-yl)methyl oxazolidin-2-on, 9) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on, 10) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 11) (S)-3-(4-(4-(4,5-dimethyloxazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide, 12) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 13) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on, 14) (R)-3-(4-(2-([1,2,4]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on, 15) (S)-3-(4-(2-(4,5-dimethyloxazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl acetamide, 16) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 17) (R)-3-(4-(2-[1,2,4]triazol-1-yl pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 18) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-fluoromethyl oxazolidin-2-on, 19) (S)-3-(4-(2-(imidazole-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-aminomethyl oxazolidin-2-on hydrochloride, 20) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 21) (R)-3-(4-(4-(4,5-dimethyloxazol-2-yl)phenyl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 22) (R)-3-(4-(2-([1,2,3]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 23) (R)-3-(4-(4-(4,5-dimethyloxazol-2-yl)phenyl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 24) (R)-3-(4-(2-([1,2,3]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 25) (S)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide, 26) (S)-3-(4-(4-(4(S)-hydroxymethyl-4,5-dihydroxazole-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide, 27) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazole-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 28) (S)-3-(4-(4-(4-hydroxymethylthiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide, 29) (R)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 30) (S)-3-(4-(4-(4-glycyloxymethylthiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic acid, 31) (S)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide, 32) (R)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 33) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methoxymethyl oxazolidin-2-on, 34) (R)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 35) (R)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 36) (R)-3-(4-(4-(4-hydroxymethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on, 37) (R)-3-(4-(4-(4-glycyloxymethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on trifluoroacetic acid, 38) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3,5-difluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 39) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3,5-difluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 40) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(N,N-dimethylaminomethyl)oxazolidin-2-on, 41) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(N-methylaminomethyl)oxazolidin-2-on, 42) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 43) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride, 44) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride, 45) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride, 46) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 47) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on hydrochloride, 48) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride, 49) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 50) (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride, 51) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 52) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride, 53) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 54) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride, 55) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 56) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on hydrochloride, 57) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 58) (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride, 59) (R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate, 60) (R)-[3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate, 61) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on, 62) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic acid, 63) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride, 64) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 65) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride, 66) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 67) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride, 68) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid, 69) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride, 70) (R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate, 71) (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on, 72) mono-[(R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate, and 73) mono-[(R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate.
[0000]
TABLE 1
Compound
Structure
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
[0096] In Table 1, ‘Ac’ represents acetyl and ‘TfOH’ refers to trifluoroacetic acid.
[0097] Further, the present invention provides a method of preparing the derivatives of oxazolidinone corresponding to Formula 1, as shown in Scheme 1 is defined below.
[0000]
[0098] In the Scheme 1, Z represents C 1-4 alkyl group, X, R 1 , R 1 ′, R 2 , R 3 and R 4 are as defined in Formula 1 and Y represents halogen.
[0099] The method of preparing the derivatives of oxazolidinone according to the present invention comprises;
[0100] substituting a halogen atom for a hydrogen atom on phenyl of a derivative (II) of hydroxymethyloxazolidinone thereby to form a derivative (III) (Step 1);
[0101] substituting stannyl for a halogen atom (Y) of the derivative (III) to form a derivative (IV) (Step 2);
[0102] reacting the derivative (IV) with pyridine or phenyl derivative that is substituted to bromine or iodine to form a derivative (V) of oxazolidinone having pyridine ring or phenyl ring (Step 3); and
[0103] reacting the derivative (V) with amino acid having a protecting group and then with acid thereby to eliminate the protecting group and to form salts of the compounds corresponding to Formula 1, or subjecting the derivative (V) to react with phosphate and then with metallic salt thereby to form salts of the compounds corresponding to Formula 1 (Step 4).
[0104] In the Step 1, the derivative (II) of hydroxymethyloxazolidinone may be synthesized by conventional methods. For example, a method may comprise substituting an amino group of anilin for a benzyloxycarbonyl group and reacting a substituted compound with glycidylbutylate in a state of strong bases thereby to form the derivative (II). The state may be prepared by adding a strong base; preferably the strong base may include n-butyllitium, sec-butyllitium, tert-butyllitium, etc., more preferably n-butyllitium. Further, it is preferable to subject the method at a temperature of about −78° C. in liquid nitrogen.
[0105] The Step 1 is subjected to substitute a hydrogen atom of phenyl group of the derivative (II) for a halogen atom, preferably for an iodine atom. When the hydrogen atom is substituted for the iodine atom, the substituted reaction may be subjected preferably by adding iodine monochloride (ICI) or trifluoroacetic acid silver salt (CF 3 COOAg) and adding iodine at room temperature.
[0106] The Step 2 is subjected the derivative (III) to react with hexamethylditin, hexabutylditin or tributyltin hydride by adding a catalyst of palladium to form the derivative (IV) of which iodine atom is substituted for a trimethylstannyl group or a tributylstannyl group. The catalyst of palladium may comprise dichlorobistriphenylphosphine palladium (II), tetrakistriphenylphosphine palladium (0), etc. It is preferred to carry out the Step 2 in a solvent of 1,4-dioxan, dimethylformamide, tetrahydrofuran, 1-methyl-2-pyrolidone, etc. at a temperature of about 90 to 150° C.
[0107] The Step 3 is carried out by reacting the derivative (IV) with a compound having hetero ring on phenyl or pyridine ring thereby to form the derivative (V). A catalyst of palladium added in the Step 3 may be identical to that of palladium in Step 2. It is preferred to carry out the Step 3 in a solvent of dimethylformamide, 1-methyl-2-pyrolidone, etc. at a temperature of about 100 to 120° C.
[0108] The Step 4 is performed by reacting the derivative (V) with amino acid that is protecting an amino group with t-butyloxycarbonyl, dicyclohexylcarbodiimide and 4-dimethylaminopyridine thereby to form the derivative (I) having amino group. The amino acid may include alanine, glycine, proline, isoleucine, leucine, phenylalanine, β-alanine, valine, etc. A solvent comprises dimethylformamide, 1-methyl-2-pyrolidone, etc. Preferably, a reaction by adding the derivative (V) with amino acid is carried out by stirring for about 5 hours above at room temperature.
[0109] A mixture of the derivative (V) and amino acid reacts to a strong acid such as trifluoroacetic acid, etc. to eliminate a protecting group. The solvent is removed from the mixture and the mixture is crystallized thereby to provide a salt of the derivative of oxazolidinone corresponding to Formula 1. Preferably, a reaction by adding the derivative (V) with amino acid is carried out by stirring for about 2 hours above at room temperature.
[0110] The salt of the derivative of formula 1, prepared by using amino acid at position R 3 or R 4 , in a method known similarly to the above method, may be gained. (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material in the method is known and the method is described in WO0194342.
[0111] Further, a phosphate metallic salt of the derivative (I) may be formed by adding sodiummethoxide, sodium hydroxide, etc. to a composition in a solvent such as methanol, ethanol etc., the composition is prepared by dissolving the derivative (V) in trimethylphosphate or triethylphosphate, adding phosphorous oxy chloride and stirring for about 12 hours at room temperature. The phosphate metallic salt may be produced by reacting the derivative (V) with tetrazole and derivates of amidite at room temperature, oxidizing a reacted compound, synthesizing a derivative of alkylphosphate, eliminating alkyl group using a strong acid thereby to form a derivative of phosphate acid, and converting the derivative of phosphate acid into the phosphate metallic salt by the above-mentioned method.
[0112] Further, the present invention provides a pharmaceutical composition comprising the derivatives of oxazolidinone corresponding to Formula 1 for use in an antibiotic.
[0113] The oxazolidinone derivatives of the present invention show inhibitory activity against a broad spectrum of bacteria, against methicillin resistant Staphylococcus aureus (MRSA) and vancomycin resistant Enterococci (VRE) and have excellent relatively antibiotic activity with a relatively low concentration thereof or in vivo.
[0114] Further, the derivatives of the present invention may exert potent antibacterial activity versus various human and animal pathogens, including Gram-positive bacteria such as Staphylococi, Enterococci and Streptococi, anaerobic microorganisms such as Bacteroides and Clostridia , and acid-resistant microorganisms such as Mycobacterium tuberculosis and Mycobacterium avium.
[0115] The derivatives of oxazolidinone, having hydroxyl, are reacted with amino acid or phosphate to form prodrugs thereof. The prodrugs have superior solubility to compounds that are not formed as prodrugs: the solubility of the prodrugs represents above 28 mg/ml and the solubility of the compound 10 mg/ml (compound 10). The prodrugs stabilize in water or acidic solution and change to hydroxylmethyl compounds by being reverted using esterase and phosphatase in a blood thereby to develop easy formulation for injection or oral administration.
[0116] The composition of the present invention may comprise at least one effective ingredient having functions similar to those of the derivatives of oxazolidinone.
[0117] For formulating a pharmaceutical composition, at least one specie of the compound of formula 1 may be admixed with at least one pharmaceutically acceptable carrier. The pharmaceutical acceptable carrier may include saline solution, sterile water, Ringer's solution, buffered saline solution, dextrose solution, malto-dextrin solution, glycerol, ethanol, etc. According to the user's necessity, the pharmaceutical composition may contain conventional expedient such as antioxidizing agent, buffer, soil cleaner, etc. Also, the compositions are admixed with diluents, disintegrants, surface active agents, binders, lubricants, aqueous solution, suspension, etc. to be formed for injection, powders, capsules, granules, tablet, etc. Preferably, the formulation is prepared using proper methods described in Remington's Pharmaceutical Science (the newest edition), Mack Publishing Company, Easton Pa., etc. according to diseases or ingredients.
[0118] The compound of the present invention may be administrated orally or parenterally, such as intravenously, hypodermically, intra-abdominally, topically, etc. The dosage of the compound may vary depending upon the particular compound utilized, the mode of administration, the condition, and severity thereof, of the condition being treated, as well as the various physical factors related to the individual being treated. As used in accordance with invention, satisfactory results may be obtained when the compounds of the present invention are administered to the individual in need at a daily dosage of about 10 mg to about 25 mg per kilogram of body weight, preferably about 13 mg to about 20 mg per kilogram of body weight, more preferably administered each of divided doses to many times per day.
[0119] The Lethal Dose (LD 50 ) of the oxazolidinone derivatives shows above 1 g/kg in test of acute toxicity so that the derivatives are found stable.
(a) Advantageous Effects
[0120] The oxazolidinone derivatives of the present invention show inhibitory activity against a broad spectrum of bacteria and lower toxicity. The prodrugs, prepared by reacting the compound having hydroxyl with amino acid or phosphate, have high solubility thereof against water.
[0121] Further, the derivatives of the present invention may exert potent antibacterial activity versus various human and animal pathogens, including Gram-positive bacteria such as Staphylococi, Enterococci and Streptococi, anaerobic microorganisms such as Bacteroides and Clostridia , and acid-resistant microorganisms such as Mycobacterium tuberculosis and Mycobacterium avium.
[0122] Accordingly, the compositions comprising the derivatives of oxazolidinone are used in an antibiotic.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
(b) Best Mode For Carrying Out the Invention
[0123] The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Preparation Example 1
Preparation of N-Carbobenzyloxy-3-fluoroaniline
[0124] 3-fluoroaniline 100 g was dissolved in 1 L of tetrahydrofuran (THF) and the solution was added with 150 g (1.8 mol) of sodium bicarbonate (NaHCO 3 ). After being cooled to 0° C., the solution was slowly added with 154 ml of N-carbobenzyloxy chloride (CbzCl) for reaction. While the temperature was maintained at 0° C., the reaction mixture was let to react for 2 hours with stirring. Afterwards, the reaction was extracted with 0.5 L of ethyl acetate. The organic layer, after being separated, was washed with brine, dried over anhydrous magnesium sulfate (MgSO 4 ) and concentrated in vacuo. The residue was washed twice with n-hexane to afford the title compound as white crystal. 132 g. Yield 85%.
Preparation Example 2
Preparation of (R)-3-(3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol
[0125] 132 g of N-carbobenzyloxy-3-fluoroaniline 132 g prepared in the Preparation example 1 was dissolved in 1.3 L of tetrahydrofuran and the solution was cooled to −78° C. 370 ml of n-buthyllitium (n-BuLi, 1.6M/n-hexane) was slowly added to the solution in a nitrogen atmosphere, followed by stirring for 10 min. And 84 ml of (R)-(−)-glycidylbuthylate was slowly added to the reaction mixture, stirred at the same temperature for 2 hours and allowed to react for 24 hours at room temperature. After completion of the reaction, the solution was added with ammonium chloride (NH 4 Cl) solution and extracted with 0.5 L of ethyl acetate at room temperature. The organic layer, thus separated, was washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was dissolved in 100 ml of ethyl acetate and washed with n-hexane to give white crystals, which were purified to the title compound. 80 g. Yield 70%.
[0126] 1 H NMR (DMSO-d 6 ) δ 7.85 (t, 1H), 7.58 (dd, 1H), 7.23 (dd, 1H), 4.69 (m, 1H), 4.02 (t, 1H), 3.80 (dd, 1H), 3.60 (br dd, 2H).
Preparation Example 3
Preparation of (R)-3-(4-iodo-3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol
[0127] In 300 ml of acetonitryl was dissolved 30 g of (R)-3-(3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol prepared in the Preparation example 2, and 46 g of trifluoroacetic acid silver salt (CF 3 COOAg) and 43 g of iodide were added to the solution. After being stirred for one day at room temperature, the solution was added with water and was extracted with ethyl acetate. The organic layer, thus separated, was washed with brine and dehydrated. And then the residue was filtered, concentrated in vacuo and dried thereby to form the title compound 44 g. Yield 94%.
[0128] 1 H NMR (DMSO-d 6 ) δ 7.77 (t, 1H), 7.56 (dd, 1H), 7.20 (dd, 1H), 5.20 (m, 1H), 4.70 (m, 1H), 4.07 (t, 1H), 3.80 (m, 1H), 3.67 (m, 2H), 3.56 (m, 3H)
Preparation Example 4
Preparation of (R)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol
[0129] In 660 ml of 1,4-dioxan was dissolved 50 g of (R)-3-(4-iodo-3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol prepared in the Preparation example 3, 52 g of hexabutylditin ((Bu 3 Sn) 2 ) and 9.3 g of dichlorobistriphenylphosphinpalladium were added into the solution, and stirred for 2 hours. The solution was filtered using celite and concentrated in vacuo. The residue was purified by column chromatography and 45 g of the title compound was formed.
[0130] 1 H NMR (DMSO-d 6 ) δ 7.74 (m, 3H), 5.20 (t, 1H), 4.71 (m, 1H), 4.08 (t, 1H), 3.82 (dd, 1H), 3.68 (m, 1H), 3.52 (m, 1H), 1.48 (m, 6H), 1.24 (m, 6H), 1.06 (m, 6H), 0.83 (t, 9H)
Preparation Example 5
Preparation of 2-cyano-5-bromopyridine
[0131] In 1 L of dimethylformamide was dissolved 100 g of 2,5-dibromopyridine, 32 g of cupper cyanide and 17.8 g of sodium cyanide were added to the solution at room temperature and the solution was stirred at the temperature of 150° C. for 7 hours for reaction. After being cooled to room temperature, the reaction mixture was added with water and extracted with ethyl acetate. The organic layer was washed with brine, dehydrated, filtered and concentrated in vacuo. The title compound 54 g was obtained. Yield 70%.
[0132] 1 H NMR (CDCl 3 ) δ 8.76 (s, 1H), 7.98 (dd, 1H), 7.58 (dd, 1H)
Preparation Example 6
Preparation of 2-(tetrazol-5-yl)-5-bromopyridine
[0133] 10 g of 2-cyano-5-bromopyridine prepared in the Preparation example 5 was dissolved in 100 ml of dimethylformamide, 5.33 g of sodiumazide, and 4.4 g of ammoniumchloride were added to the solution at room temperature, and the solution was stirred at the temperature of 110° C. for 3 hours for reaction. The reaction mixture was added with water and then was extracted with ethyl acetate. The organic layer, thus separated, was washed with brine, dehydrated, filtrated and concentrated in vacuo thereby to obtain 10.5 g of the title compound. Yield 85%.
Preparation Example 7
Preparation of 2-(1-methyltetrazol-5-yl)-5-bromopyridine and 2-(2-methyltetrazol-5-yl)-5-bromopyridine
[0134] 10.5 g of 2-(tetrazol-5-yl)-5-bromopyridine prepared in the Preparation example 6 was dissolved in 100 ml of dimethylformamide. And then 6.5 g of sodiumhydroxide was added to the solution and 9.3 g of iodomethane was slowly added to the solution at the temperature of 0° C. The solution was stirred for 6 hours at room temperature, added with water, extracted with ethyl acetate. And then the organic layer was washed with brine, dehydrated, filtrated, concentrated in vacuo and purified by column chromatography to obtain 4 g of 2-(1-methyltetrazol-5-yl)-5-bromopyridine and 5 g of 2-(2-methyltetrazol-5-yl)-5-bromopyridine.
1) 2-(1-methyltetrazol-5-yl)-5-bromopyridine
[0136] 1 H NMR (CDCl 3 ) δ 8.77 (t, 1H), 8.23 (dd, 1H), 8.04 (dd, 1H), 4.46 (s, 3H)
2) 2-(2-methyltetrazol-5-yl)-5-bromopyridine
[0138] 1 H NMR (CDCl 3 ) δ 8.80 (t, 1H), 8.13 (dd, 1H), 7.98 (dd, 1H), 4.42 (s, 3H)
Preparation Example 8
Preparation of 2-(2-methyl-[1,3,4]oxadiazol-5-yl)-5-bromopyridine
[0139] In 130 ml of acetic anhydride was dissolved 8.6 g of 2-(tetrazol-5-yl)-5-bromopyridine prepared in the Preparation example 6. And then the solution was added with 15 ml of pyridine and stirred for 3 hours for reaction. The reaction mixture was added with ethyl acetate and extracted to separate organic layer. And then the organic layer was washed with water and brine. The organic layer was dehydrated, filtrated and concentrated in vacuo to give 7.3 g of the title compound. Yield 80%.
[0140] 1 H NMR (CDCl 3 ) δ 7.99 (t, 1H), 7.40 (dd, 1H), 7.27 (dd, 1H), 1.83 (s, 3H)
Preparation Example 9
Preparation of 2-([1,2,3]triazol-1-yl)-5-bromopyridine and 2-([1,2,3]triazol-2-yl)-5-bromopyridine
[0141] 20 g of 2,5-dibromopyridine was dissolved in 200 ml of 1-methyl-2-pyrrolidone. The solution was added with 35 g of potasiumcarbonate and stirred for 10 hours at the temperature of 100° C. The reaction mixture was added with ethyl acetate and the organic layer, thus obtained was washed with water and brine. The organic layer was dried, filtered and concentrated in vacuo to provide 6 g of 2-([1,2,3]triazol-1-yl)-5-bromopyridine, 4 g of 2-([1,2,3]triazol-2-yl)-5-bromopyridine.
1) 2-([1,2,3]triazol-1-yl)-5-bromopyridine
[0143] 1 H NMR (CDCl 3 ) δ 8.53 (dd, 2H), 8.10 (d, 1H), 8.03 (dd, 1H), 7.82 (s, 1H)
2) 2-([1,2,3]triazol-2-yl)-5-bromopyridine
[0145] 1 H NMR (CDCl 3 ) δ 8.60 (t, 1H), 7.97 (s, 2H), 7.87 (s, 2H)
Example 1
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 10)
[0146] In 150 ml of 1-methyl-2-pyrrolidone was dissolved 37 g of (R)-3-(4-tributhylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol. The solution was added with 19.7 g of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, 10.44 g of lithium chloride and 2.9 g of dichlorobistriphenylphospine palladium (II) at room temperature and then stirred at the temperature of 120° C. for 4 hours. The reaction mixture was added with water and then extracted with ethyl acetate. The organic layer, thus separated, was washed with brine, dehydrated, filtrated, concentrated in vacuo and purified by column chromatography to provide 8 g of the title compound. Yield 26%.
[0147] 1 H NMR (DMSO-d 6 ) δ 8.90 (s, 1H), 8.18 (m, 2H), 7.70 (m, 2H), 7.49 (dd, 1H), 5.25 (t, 1H), 4.74 (m, 1H), 4.46 (s, 3H), 4.14 (t, 1H), 3.88 (dd, 1H), 3.68 (m, 1H), 3.58 (m, 1H)
Example 2
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 16)
[0148] The title compound 6.6 g (yield 30%) was prepared in a method similar to that of Example 1, except that, 14.3 g of 2-(2-methyl-[1,3,4]oxadiazol-5-yl)-5-bromopyridine, instead of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, was used as a starting material.
[0149] 1 H NMR (DMSO-d 6 ) δ 8.93 (s, 1H), 8.21 (s, 2H), 7.71 (m, 2H), 7.50 (dd, 1H), 5.25 (t, 1H), 4.74 (m, 1H), 4.14 (t, 1H), 3.89 (dd, 1H), 3.68 (m, 1H), 3.59 (m, 1H), 2.64 (s, 3H)
Example 3
Preparation of (R)-3-(4-(2-([1,2,4]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 17)
[0150] The same procedure as in Example 1 was conducted, except for using, instead of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, 200 mg of 2-([1,2,4]triazol-1-yl)-5-bromopyridine as a starting material, to prepare the title compound 150 mg (yield 48%).
Example 4
Preparation of (R)-3-(4-(4-(4,5-dimethyloxzol-2-yl)phenyl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 21)
[0151] The same procedure as in Example 1 was conducted, except for using, instead of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, 1 g of 4-(4,5-dimethyloxazol-2-yl)bromobenzene as a starting material, to prepare the title compound 780 mg (yield 76%).
[0152] 1 H NMR (DMSO-d 6 ) δ 7.96 (s, 1H), 7.94 (s, 1H), 7.63 (m, 4H), 7.44 (dd, 1H), 5.23 (t, 1H), 4.72 (m, 1H), 4.12 (t, 1H), 3.87 (dd, 1H), 3.68 (m, 1H), 3.56 (m, 1H), 2.32 (s, 3H), 2.10 (s, 3H)
Example 5
Preparation of (R)-3-(4-(2-([1,2,3]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 24)
[0153] The same procedure as in Example 1 was conducted, except for using, instead of 2 (2-methyltetrazol-5-yl)-5-bromopyridine, 2 g of 2-([1,2,3]triazol-1-yl)-5-bromopyridine as a starting material, to prepare the title compound 1.2 g.
[0154] 1 H NMR (DMSO-d 6 ) δ 8.88 (s, 1H), 8.76 (s, 1H), 8.28 (d, 1H), 8.21 (d, 1H), 8.01 (s, 1H), 7.70 (m, 2H), 7.51 (dd, 1H), 5.26 (t, 1H), 4.75 (m, 1H), 4.14 (t, 1H), 3.90 (dd, 1H), 3.68 (m, 1H), 3.58 (m, 1H)
Example 6
Preparation of (R)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 29)
[0155] The same procedure as in Example 1 was conducted, except for using, instead of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, 1 g of 2-([1,2,3]triazol-2-yl)-5-bromopyridine as a starting material, to prepare the title compound 0.7 g.
[0156] 1 H NMR (DMSO-d 6 ) δ 8.74 (s, 1H), 8.25 (dd, 1H), 8.23 (s, 1H), 8.11 (d, 1H), 7.69 (m, 3H), 7.49 (dd, 1H), 5.24 (t, 1H), 4.75 (m, 1H), 4.14 (t, 1H), 3.89 (dd, 1H), 3.68 (m, 1H), 3.59 (m, 1H)
Example 7
Preparation of (R)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 32)
[0157] The same procedure as in Example 1 was conducted, except for using, instead of 2-(2-methyltetrazol-5-yl)-5-bromopyridine, 1 g of 4-(4-cyanomethyl thiazol-2-yl)bromobenzene as a starting material, to prepare the title compound 520 mg.
[0158] 1 H NMR (DMSO-d 6 ) δ 8.04 (s, 1H), 8.00 (s, 1H), 7.65 (m, 5H), 7.47 (dd, 1H), 5.24 (t, 1H), 4.74 (m, 1H), 4.23 (s, 2H), 4.13 (t, 1H), 3.88 (dd, 1H), 3.68 (m, 1H), 3.59 (m, 1H)
Example 8
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3,5-difluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 38)
[0159] The same procedure as in Example 1 was conducted, except for using, instead of (R)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethanol, (R)-3-(4-trimethylstannyl-3,4-difluorophenyl)-2-oxo-5-oxazolidinylmethanol as a starting material, to prepare the title compound.
[0160] 1 H NMR (DMSO-d 6 ) δ 8.81 (s, 1H), 8.25 (d, 1H), 8.10 (d, 1H), 7.54 (d, 2H), 5.25 (t, 1H), 4.77 (m, 1H), 4.47 (s, 3H), 4.13 (t, 1H), 3.89 (dd, 1H), 3.68 (m, 1H), 3.57 (m, 1H)
Example 9
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3,4-difluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 39)
[0161] The same procedure as in Example 1 was conducted by using (R)-3-(4-trimethylstannyl-3,4-difluorophenyl)-2-oxo-5-oxazolidinylmethanol and 2-(2-methyl-[1,3,4]oxadiazol-5-yl)-5-bromopyridine as a starting material, to prepare the title compound.
[0162] 1 H NMR (DMSO-d 6 ) δ 8.83 (s, 1H), 8.25 (d, 1H), 8.15 (d, 1H), 7.55 (d, 2H), 5.25 (t, 1H), 4.77 (m, 1H), 4.13 (t, 1H), 3.89 (dd, 1H), 3.68 (m, 1H), 3.59 (m, 1H), 2.63 (s, 3H)
Example 10
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 12)
[0163] In 25 ml of dimethylformamide was dissolved 4 g of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (compound 10). The solution was added 3.34 g of 1,3-dicyclohexylcarbodiimide, 2.36 g of BOC-glycine and 0.2 g of 4-dimethylaminopyridine at room temperature and then stirred for 10 hours. The reaction mixture was added with water and extracted with ethyl acetate. The organic layer, thus separated, was washed with brine, dehydrated, filtered, concentrated in vacuo and purified by column chromatography. A residue, thus resulted in concentrating in vacuo, was dissolved in 70 ml of methylenechloride, added with 30 ml of trifluoroacetic acid, and stirred for 2 hours at room temperature. The residue was washed with ethanol and ethyl ether and concentrated in vacuo to obtain the title compound 4.47 g. Yield 76%.
[0164] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.19 (s, 3H), 8.17 (m, 2H), 7.77 (t, 1H), 7.69 (dd, 1H), 7.49 (dd, 1H), 5.00 (m, 1H), 4.46 (m, 2H), 4.47 (s, 3H), 4.24 (t, 1H), 3.92 (dd, 1H), 3.90 (s, 2H)
Example 11
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 20)
[0165] The title compound was prepared in a method similar to that of Example 10 using BOC-valline, instead of BOC-glycine.
[0166] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.40 (s, 3H), 8.21 (m, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.48 (dd, 1H), 5.05 (m, 1H), 4.63 (dd, 1H), 4.47 (s, 3H), 4.43 (dd, 1H), 4.28 (t, 1H), 4.01 (d, 1H), 3.93 (dd, 1H), 2.14 (m, 1H), 0.98 (d, 3H), 0.95 (d, 3H)
Example 12
Preparation of (R)-3-(4-(2-[1,2,3]triazol-1-yl pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 22)
[0167] The title compound was prepared in a method similar to that of Example 10 using compound 24.
[0168] 1 H NMR (DMSO-d 6 ) δ 8.87 (s, 1H), 8.76 (s, 1H), 8.33 (s, 3H), 8.29 (d, 1H), 8.00 (s, 1H), 7.77 (t, 1H), 7.76 (t, 1H), 7.67 (dd, 1H), 7.47 (dd, 1H), 5.02 (m, 1H), 4.49 (m, 2H), 4.23 (t, 1H), 3.93 (m, 3H)
Example 13
Preparation of (R)-3-(4-(4-(4,5-dimethyloxazol-2-yl)phenyl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 23)
[0169] The title compound was prepared in a method similar to that of Example 10 using compound 21.
[0170] 1 H NMR (DMSO-d 6 ) δ 8.31 (s, 3H), 7.97 (d, 2H), 7.64 (m, 4H), 7.45 (dd, 1H), 5.01 (m, 1H), 4.47 (m, 2H), 4.25 (t, 1H), 3.94 (dd, 1H), 3.90 (s, 2H)
Example 14
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 27)
[0171] The title compound was prepared in a method similar to that of Example 10 using compound 16.
[0172] 1 H NMR (DMSO-d 6 ) δ 8.96 (s, 1H), 8.31 (s, 3H), 8.22 (s, 2H), 7.76 (t, 1H), 7.66 (dd, 1H), 7.50 (dd, 1H), 5.04 (m, 1H), 4.50 (m, 2H), 4.25 (t, 1H), 3.94 (dd, 1H), 3.91 (s, 2H), 2.63 (s, 3H)
Example 15
Preparation of (R)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 34)
[0173] The title compound was prepared in a method similar to that of Example 10 using compound 32.
[0174] 1 H NMR (DMSO-d 6 ) δ 8.25 (s, 3H), 8.03 (d, 2H), 7.68 (m, 5H), 7.44 (dd, 1H), 5.01 (m, 1H), 4.48 (m, 2H), 4.25 (m, 3H), 3.92 (m, 3H)
Example 16
Preparation of (R)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 35)
[0175] The title compound was prepared in a method similar to that of Example 10 using compound 29.
[0176] 1 H NMR (DMSO-d 6 ) δ 8.78 (s, 1H), 8.23 (m, 2H), 8.22 (s, 3H), 8.20 (s, 1H), 8.12 (d, 1H), 7.75 (t, 1H), 7.67 (dd, 1H), 7.48 (dd, 1H), 5.01 (m, 1H), 4.49 (m, 2H), 4.24 (t, 1H), 3.92 (dd, 1H), 3.89 (s, 2H)
Example 17
Preparation of (S)-3-(4-(2-(2-oxo-4-glycyloxymethylpyrrolidin-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 1)
[0177] 1. The Primary Step
[0178] In 14 ml of 1-methyl-2-pyrrolidon was dissolved 1.8 g of (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide. The solution was added 1.03 g of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 0.55 g of lithium chloride and 0.15 g of dichlorobistriphenylphosphine palladium (II) at room temperature and then stirred at the temperature of 110° C. for 2 hours. The reaction mixture was added with water and extracted with ethyl acetate. After being washed with brine, the organic layer, thus separated, was dehydrated, filtered, concentrated in vacuo and purified by column chromatography thereby to obtain (S)-3-(4-(2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide 410 mg. Yield 21%.
[0179] 2. The Secondary Step
[0180] In dimethylformamide 2.3 ml was dissolved 50 mg of the compound prepared in the primary step. The solution was added with 35 mg of 1,3-dicyclohexylcarbodiamide, 25 mg of BOC-glycine and 2.1 mg of 4-dimethylaminopyridin at room temperature and then stirred for 10 hours. The reaction mixture was added with water and extracted with ethyl acetate. After being washed with brine, the organic layer, thus separated, was dehydrated, filtrated, concentrated in vacuo and purified by column chromatography. A residue, provided by concentrating, was dissolved in 2 ml of methylenechloride, added with 1 ml of trifluoroacetic acid and then stirred for 2 hours at room temperature. The residue was washed with ethanol and ethyl ether, evaporated in vacuo to obtain the title compound 140 mg.
[0181] 1 H NMR (DMSO-d 6 ) δ 8.60 (s, 1H), 8.40 (d, 1H), 8.28 (s, 3H), 8.25 (m, 1H), 8.08 (dd, 1H), 7.63 (m, 2H), 7.42 (dd, 1H), 4.76 (m, 1H), 4.27 (s, 2H), 4.16 (q, 2H), 3.87 (s, 2H), 3.80 (m, 2H), 3.42 (m, 2H), 2.62 (m, 1H), 2.11 (m, 1H), 1.83 (s, 3H)
Example 18
Preparation of (S)-3-(4-(2-(4-glycyloxymethyl-[1,2,3]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 2)
[0182] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 2-(4-hydroxymethyl-[1,2,3]triazol-1-yl)-5-bromopyridine as a starting material, to prepare the title compound.
[0183] 1 H NMR (DMSO-d 6 ) δ 8.96 (s, 1H), 8.89 (s, 1H), 8.22 (m, 6H), 7.74 (t, 1H), 7.68 (dd, 1H), 7.48 (dd, 1H), 5.42 (s, 2H), 4.78 (m, 1H), 4.19 (t, 1H), 3.91 (s, 2H), 3.79 (dd, 1H), 3.43 (m, 2H), 1.83 (s, 3H)
Example 19
Preparation of (S)-3-(4-(2-(5-glycyloxymethylisoxazol-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 3)
[0184] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 2-(5-hydroxymethylisoxazol)-5-bromopyridine as a starting material, to prepare the title compound.
[0185] 1 H NMR (DMSO-d 6 ) δ 8.89 (s, 1H), 8.26 (s, 3H), 8.12 (m, 2H), 7.72 (t, 1H), 7.64 (dd, 1H), 7.48 (dd, 1H), 7.21 (s, 1H), 5.49 (s, 2H), 4.77 (m, 1H), 4.17 (t, 1H), 3.98 (s, 2H), 3.79 (m, 1H), 3.43 (m, 2H), 1.83 (s, 3H)
Example 20
Preparation of (S)-3-(4-(2-(2-oxo-3-glycyloxypyrrolidin-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 5)
[0186] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 2-(2-oxo-3-hydroxypyrrolidin-1-yl)-5-bromopyridine as a starting material, to prepare the title compound.
[0187] 1 H NMR (DMSO-d 6 ) δ 8.60 (s, 1H), 8.33 (d, 1H), 8.28 (s, 3H), 8.25 (m, 1H), 8.05 (d, 1H), 7.63 (m, 2H), 7.42 (dd, 1H), 5.78 (t, 1H), 4.78 (m, 1H), 4.16 (q, 2H), 3.98 (s, 2H), 3.85 (m, 1H), 3.78 (m, 1H), 3.43 (m, 2H), 2.62 (m, 1H), 2.12 (m, 1H), 1.83 (s, 3H)
Example 21
Preparation of (S)-3-(4-(2-(5-glycyloxymethyl-[1,2,4]oxadiazol-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 6)
[0188] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 2-(5-hydroxymethyl-[1,2,4]oxadiazol-3-yl)-5-bromopyridine as a starting material, to prepare the title compound.
[0189] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.32 (s, 3H), 8.21 (m, 3H), 7.75 (t, 1H), 7.65 (dd, 1H), 7.47 (d, 1H) 5.67 (s, 1H), 4.78 (m, 1H), 4.18 (t, 1H), 4.05 (s, 2H), 3.80 (m, 1H), 3.43 (m, 2H), 1.83 (s, 3H)
Example 22
Preparation of (S)-3-(4-(2-(5-glycyloxymethyl-4,5-dihydroisoxazol-3-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 7)
[0190] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 2-(5-hydroxymethyl-4,5-dihydroisoxazol-1-yl)-5-bromopyridine as a starting material, to prepare the title compound.
[0191] 1 H NMR (DMSO-d 6 ) δ 8.81 (s, 1H), 8.27 (t, 1H), 8.24 (s, 3H), 8.05 (m, 2H), 7.69 (m, 2H), 7.44 (d, 1H) 5.04 (m, 1H), 4.76 (m, 1H), 4.41 (dd, 1H), 4.32 (m, 1H), 4.17 (t, 1H), 3.86 (s, 2H), 3.77 (m, 1H), 3.60 (m, 1H), 3.44 (m, 2H), 1.83 (s, 3H)
Example 23
Preparation of (S)-3-(4-(4-(4-glycyloxymethylthiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide trifluoroacetic Acid (Compound 30)
[0192] The same procedure as in Example 17 was conducted, except for using, instead of 2-(2-oxo-4-hydroxymethylpyrrolidin-1-yl)-5-bromopyridine, 4-(4-hydroxymethyl thiazol-2-yl)-bromobenzene as a starting material, to prepare the title compound.
[0193] 1 H NMR (DMSO-d 6 ) δ 8.25 (s, 3H), 8.00 (d, 2H), 7.85 (s, 1H), 7.69 (m, 4H), 7.44 (dd, 1H), 5.63 (s, 2H), 4.76 (m, 1H), 4.16 (t, 1H), 3.93 (s, 2H), 3.79 (dd, 1H), 3.43 (m, 2H), 1.83 (s, 3H)
Example 24
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,4]triazol-1-yl)methyl oxazolidin-2-on (Compound 4)
[0194] 1. The Primary Step
[0195] In 14 ml of methylenechloride was dissolved 1 g of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (compound 10). The solution was added with 0.46 g of methansulfonylchloride 0.46 g and 0.75 ml of triethylamine at room temperature and stirred at the same temperature for 30 minutes. Water and brine were added to the reaction mixture for washing, followed by extraction. The organic layer was dehydrated, filtrated and concentrated in vacuo thereby to provide (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methansulfonyloxymethyl oxazolidin-2-on 1 g. Yield 82%.
[0196] 2. The Secondary Step
[0197] In 15 ml of dimethylformamide was dissolved the compound prepared in the primary step. The solution was added with 300 mg of 1,2,4-triazol 300 mg and 100 mg of sodiumhydride (60%) at room temperature and stirred for 2 days. The reaction mixture was extracted with ethyl acetate and then the organic layer, thus separated, was washed with water and brine. The organic layer was dehydrated, filtered and concentrated in vacuo. The residue, prepared by concentrating, was purified by column chromatography to provide the title compound 400 mg. Yield 43%.
[0198] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.57 (s, 1H), 8.19 (m, 2H), 7.74 (t, 1H), 7.58 (dd, 1H), 7.42 (dd, 1H), 5.13 (m, 1H), 4.64 (m, 2H), 4.46 (s, 3H), 4.28 (t, 1H), 3.99 (dd, 1H)
Example 25
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(1,2,3-triazol-2-yl)methyl oxazolidin-2-on (compound 8) and (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on (Compound 9)
[0199] The same procedure as in Example 24 was conducted, except for adding, instead of 1,2,4-triazol, 1,2,3-triazol, to obtain compound 8 and compound 9, and then the compounds were divided by column chromatography.
[0200] (compound 8) 1 H NMR (DMSO-d 6 ) δ 8.90 (s, 1H), 8.19 (m, 2H), 7.82 (s, 2H),
[0201] 7.71 (t, 1H), 7.59 (dd, 1H) 7.41 (dd, 1H), 5.22 (m, 1H), 4.86 (m, 2H), 4.46 (s, 3H), 4.30 (t, 1H), 3.98 (dd, 1H) (compound 9) 1 H NMR (DMSO-d 6 ) δ 8.90 (s, 1H), 8.18 (m, 3H), 7.75 (s, 1H),
[0202] 7.72 (t, 1H), 7.59 (dd, 1H) 7.42 (dd, 1H), 5.22 (m, 1H), 4.86 (m, 2H), 4.46 (s, 3H), 4.30 (t, 1H), 3.98 (dd, 1H)
Example 26
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on (Compound 13)
[0203] The same procedure as in Example 24 was conducted, except for adding 1,2,3-triazo and using the compound 16 as a starting material, to obtain the title compound.
[0204] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.20 (s, 2H), 8.17 (s, 1H), 7.75 (s, 1H), 7.73 (t, 1H), 7.61 (dd, 1H) 7.43 (dd, 1H), 5.18 (m, 1H), 4.85 (m, 2H), 4.29 (t, 1H), 3.96 (dd, 1H), 2.62 (s, 3H)
Example 27
Preparation of (R)-3-(4-(2-([1,2,4]triazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on (Compound 14)
[0205] The same procedure as in Example 24 was conducted, except for adding 1,2,3-triazol and using the compound 17 as a starting material, to obtain the title compound.
[0206] 1 H NMR (DMSO-d 6 ) δ 9.40 (s, 1H), 8.70 (s, 1H), 8.32 (s, 2H), 8.25 (d, 1H), 8.17 (s, 1H), 7.96 (d, 1H), 7.75 (s, 1H), 7.71 (t, 1H), 7.60 (dd, 1H) 7.42 (dd, 1H), 5.18 (m, 1H), 4.86 (m, 2H), 4.29 (t, 1H), 3.96 (dd, 1H)
Example 28
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-fluoromethyl oxazolidin-2-on (Compound 18)
[0207] In 5 ml of methylenechloride was dissolved 100 mg of the compound 10. The solution was added with 43 mg of diethylaminosulfurtrifloride (DAST) and 0.078 ml of triethylamine and then stirred for 24 hours. After being concentrating, the reaction mixture was purified by column chromatography to obtain the title compound 75 mg. Yield 75%.
[0208] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.19 (m, 2H), 7.74 (t, 1H), 7.66 (dd, 1H) 7.49 (dd, 1H), 5.06 (m, 1H), 4.89 (m, 2H), 4.46 (s, 3H), 4.23 (t, 1H), 3.95 (dd, 1H)
Example 29
Preparation of (S)-3-(4-(2-(imidazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-5-aminomethyl oxazolidin-2-on hydrochloride (Compound 19)
[0209] In 3.4 ml of ethanol and 30.6 ml of pyridin was dissolved 2.5 g of (S)-3-(4-(2-(imidazol-1-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide. The solution was added with 2.36 g of hydroxylamine at room temperature and stirred for 10 hours at the temperature 100° C. The reaction mixture was extracted with ethyl acetate and the organic layer, thus separated, was washed with water and brine. The organic layer was dehydrated, filtered and concentrated in vacuo. The residue, obtained by concentrating, was purified by column chromatography and then dissolved in tetrahydrofuran solution, saturated hydrochloric acid, and stirred for 10 minutes. The solid, prepared by the above reaction, was recrystallized to provide the title compound 1 g.
Example 30
Preparation of (S)-3-(4-(4-(4,5-dimethyloxazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 11)
[0210] The same procedure as in Example 1 was conducted, except for adding 4-(4,5-dimethyloxazol-2-yl)-bromobenzene and using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material, to obtain the title compound.
[0211] 1 H NMR (DMSO-d 6 ) δ 8.24 (m, 1H), 7.96 (m, 2H), 7.62 (m, 4H), 7.45 (dd, 1H), 4.78 (m, 1H), 4.16 (t, 1H), 3.79 (dd, 1H), 3.41 (m, 2H), 2.32 (s, 3H), 2.10 (s, 3H), 1.83 (s, 3H)
Example 31
Preparation of (S)-3-(4-(2-(4,5-dimethyloxazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 15)
[0212] The same procedure as in Example 1 was conducted, except for adding 4-(4,5-dimethyloxazol-2-yl)-5-bromopyridine and using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material, to obtain the title compound.
[0213] 1 H NMR (DMSO-d 6 ) δ 8.81 (s, 1H), 8.24 (t, 1H), 8.07 (m, 2H), 7.77 (t, 1H), 7.62 (dd, 1H), 7.45 (dd, 1H), 4.78 (m, 1H), 4.18 (t, 1H), 3.79 (dd, 1H), 3.42 (m, 2H), 2.35 (s, 3H), 2.12 (s, 3H), 1.84 (s, 3H)
Example 32
Preparation of (S)-3-(4-(2-([1,2,3]triazol-2-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 25)
[0214] The same procedure as in Example 1 was conducted, except for adding 2-([1,2,3]triazol-2-yl)-5-bromopyridine and using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material, to obtain the title compound.
[0215] 1 H NMR (DMSO-d 6 ) δ 8.74 (s, 1H), 8.24 (m, 2H), 8.19 (s, 2H), 8.11 (d, 1H), 7.72 (t, 1H), 7.64 (dd, 1H), 7.45 (dd, 1H), 4.79 (m, 1H), 4.18 (t, 1H), 3.79 (dd, 1H), 3.43 (m, 2H), 1.84 (s, 3H)
Example 33
Preparation of (S)-3-(4-(4-(4(S)-hydroxymethyl-4,5-dihydrooxazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 26)
[0216] The same procedure as in Example 1 was conducted, except for adding 4-(4(S)-hydroxymethyl-4,5-dihydrooxazol-2-yl)-bromobenzene and using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material, to obtain the title compound.
[0217] 1 H NMR (DMSO-d 6 ) δ 8.23 (t, 1H), 7.91 (d, 2H), 7.62 (m, 4H), 7.42 (dd, 1H), 4.82 (t, 1H), 4.78 (m, 1H), 4.41 (t, 1H), 4.28 (m, 2H), 4.16 (t, 1H), 3.79 (dd, 1H), 3.61 (m, 1H), 3.48 (m, 1H), 3.43 (m, 2H), 1.84 (s, 3H)
Example 34
Preparation of (S)-3-(4-(4-(4-cyanomethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 31)
[0218] The same procedure as in Example 1 was conducted, except for adding 4-(4-cyanomethyl thiazol-2-yl)-bromobenzene and using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material, to obtain the title compound.
[0219] 1 H NMR (DMSO-d 6 ) δ 8.25 (t, 1H), 8.00 (d, 2H), 7.67 (m, 4H), 7.44 (dd, 1H), 4.79 (m, 1H), 4.23 (s, 2H), 4.14 (t, 1H), 3.79 (dd, 1H), 3.43 (m, 2H), 1.83 (s, 3H)
Example 35
Preparation of (R)-3-(4-(4-(4-hydroxymethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on (Compound 36)
[0220] The same procedure as in Example 1 was conducted, except for adding 4-(4-hydroxymethyl thiazol-2-yl)-bromobenzene and using (R)-3-(4-trimethylstannyl-3-fluorophenyl)-5-[1,2,3]triazol-1-yl oxazolidin-2-on as a starting material, to obtain the title compound.
[0221] 1 H NMR (DMSO-d 6 ) δ 8.16 (s, 1H), 8.00 (d, 2H), 7.75 (s, 1H), 7.64 (dd, 2H), 7.62 (t, 1H), 7.52 (dd, 1H), 7.48 (s, 1H), 7.36 (dd, 1H), 5.40 (t, 1H), 5.18 (m, 1H), 4.85 (d, 2H), 4.62 (d, 2H), 4.28 (t, 1H), 3.95 (dd, 1H)
Example 36
Preparation of (R)-3-(4-(4-(4-glycyloxymethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-([1,2,3]-triazol-1-yl)methyl oxazolidin-2-on trifluoroacetic acid (Compound 37)
[0222] The same procedure as in Example 10 was conducted, except for using (R)-3-(4-(4-(4-hydroxymethyl thiazol-2-yl)phenyl)-3-fluorophenyl)-5-[1,2,3]triazol-1-ylmethyl oxazolidin-2-on as a starting material, to obtain the title compound.
[0223] 1 H NMR (DMSO-d 6 ) δ 8.29 (s, 3H), 8.17 (s, 1H), 8.00 (d, 2H), 7.85 (s, 1H), 7.75 (s, 1H), 7.69 (dd, 2H), 7.67 (t, 1H), 7.55 (dd, 1H), 7.43 (dd, 1H), 5.36 (s, 2H), 5.19 (m, 1H), 4.86 (d, 2H), 4.28 (t, 1H), 4.28 (t, 1H)
Example 37
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methoxymethyl oxazolidin-2-on (Compound 33)
[0224] In 10 ml of methanol was dissolved 400 mg of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methansulfonyloxymethyl oxazolidin-2-on prepared in the secondary step of the Example 24. The solution was added with 90 mg of sodiummethoxide at room temperature and then stirred for one day at room temperature. The solution was extracted with ethyl acetate and the organic layer, thus separated, was washed with water and brine. The organic layer was dehydrated, filtered, concentrated in vacuo and purified by column chromatography to provide the title compound 200 mg. Yield 58%.
[0225] 1 H NMR (CDCl 3 ) δ 8.90 (s, 1H), 8.29 (d, 1H), 8.04 (d, 1H), 7.61 (dd, 1H), 7.58 (t, 1H), 7.38 (dd, 1H), 4.80 (m, 1H), 4.45 (s, 3H), 4.08 (t, 1H), 3.96 (dd, 1H), 3.67 (m, 2H), 3.43 (s, 3H)
Example 38
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(N,N-dimethylaminomethyl)oxazolidin-2-on (Compound 40)
[0226] In 5 ml of dimethylformamide was dissolved 100 mg of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methansulfonyloxymethyl oxazolidin-2-on prepared in the secondary step of the Example 24. The solution was added with 30 mg of dimethylamine hydrochloride at room temperature. The solution was stirred for 30 hours at the temperature of 60° C. And then the solution was extracted with ethyl acetate and the organic layer, thus separated, was washed with water and brine. The residue, prepared by dehydrating, filtering and concentrating the organic layer, was purified by column chromatography to provide the title compound 70 mg. Yield 76%.
[0227] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.19 (m, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 4.98 (m, 1H), 4.63 (s, 3H), 4.27 (m, 3H), 3.94 (dd, 1H), 2.79 (s, 3H), 2.74 (s, 3H)
Example 39
Preparation of (S)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-N-methylaminomethyl oxazolidin-2-on (Compound 41)
[0228] In 7 ml of dimethylformamide was dissolved 200 mg of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-methansulfonyloxymethyl oxazolidin-2-on, prepared in the primary step of the Example 24. The solution was added with 100 mg of methylamine hydrochloride and 240 mg of potasiumcarbonate at room temperature. The solution was stirred for 30 hours at the temperature of 80° C. The solution was added with ethyl acetate and then the organic layer, thus separated, was washed with water and brine. The residue, prepared by dehydrating, filtering and concentrating the organic layer, was purified by column chromatography to obtain the title compound 80 mg. Yield 45%.
[0229] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.18 (m, 2H), 7.73 (t, 1H), 7.66 (dd, 1H), 7.47 (dd, 1H), 7.17 (m, 1H), 4.94 (m, 1H), 4.46 (s, 3H), 4.25 (m, 3H), 3.85 (dd, 1H), 2.49 (d, 3H)
Example 40
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 42)
[0230] The same procedure as in Example 10 was carried out to provide the title compound using BOC-L-alanine instead of BOC-glycine.
[0231] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.42 (s, 3H), 8.20 (m, 2H), 7.75 (t, 1H), 7.67 (dd, 1H), 7.48 (dd, 1H), 5.05 (m, 1H), 4.61 (dd, 1H), 4.46 (s, 3H), 4.41 (dd, 1H), 4.26 (t, 1H), 4.18 (m, 1H), 3.96 (dd, 1H), 1.36 (d, 3H)
Example 41
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride (Compound 43)
[0232] 500 mg of compound 20, prepared in Example 11, was dissolved in water. The solution was controlled to pH 5 with the addition of sodium bicarbonate aqueous solution. The aqueous layer was extracted with ethyl acetate and then the organic layer was slowly added with ether solution saturating of hydrochloric acid. The solid prepared by the above method was filtered and concentrated in vacuo to provide the title compound 200 mg. Yield 46%.
[0233] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.54 (bs, 3H), 8.20 (m, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.04 (m, 1H), 4.58 (dd, 1H), 4.46 (s, 3H), 4.41 (dd, 1H), 4.26 (t, 1H), 3.95 (m, 2H), 2.17 (m, 1H), 0.97 (d, 3H), 0.94 (d, 3H)
Example 42
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 44)
[0234] With the exception of using compound 42, the same procedure as in Example 41 was conducted to prepare the title compound.
[0235] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.52 (bs, 3H), 8.20 (m, 2H), 7.75 (t, 1H), 7.66 (dd, 1H), 7.49 (dd, 1H), 5.05 (m, 1H), 4.60 (dd, 1H), 4.46 (s, 3H), 4.41 (dd, 1H), 4.26 (t, 1H), 4.18 (m, 1H), 4.00 (dd, 1H), 1.37 (d, 3H)
Example 43
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride (Compound 45)
[0236] With the exception of using the compound 12, the same procedure as in Example 41 was conducted to prepare the title compound.
[0237] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.48 (bs, 3H), 8.18 (m, 2H), 7.75 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.03 (m, 1H), 4.48 (m, 2H), 4.46 (s, 3H), 4.24 (t, 1H), 3.99 (dd, 1H), 3.86 (m, 2H)
Example 44
Preparation of (S)-3-(4-(4-(4-hydroxymethylthiazol-2-yl)phenyl)-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide (Compound 28)
[0238] With the exception of using (S)-3-(4-trimethylstannyl-3-fluorophenyl)-2-oxo-5-oxazolidinylmethyl acetamide as a starting material and 4-(4-hydroxymethylthiazol-2-yl)-bromobenzene, the same procedure as in Example 1 was conducted to prepare the title compound.
[0239] 1 H NMR (DMSO-d 6 ) δ 8.24 (t, 1H), 7.98 (d, 2H), 7.65 (m, 2H), 7.59 (m, 2H), 7.43 (s, 1H), 7.41 (dd, 1H), 5.40 (t, 1H), 4.79 (m, 1H), 4.63 (d, 2H), 4.16 (t, 1H), 3.79 (dd, 1H), 3.43 (m, 2H), 1.84 (s, 3H)
Example 45
(R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 46)
[0240] With the exception of using BOC-L-proline, instead of BOC-glycine, the same procedure as in Example 10 was conducted to prepare the title compound.
[0241] 1 H NMR (DMSO-d 6 ) δ 9.25 (bs, 2H), 8.91 (s, 1H), 8.20 (m, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.48 (dd, 1H), 5.05 (m, 1H), 4.57 (dd, 1H), 4.45 (s, 3H), 4.41 (dd, 1H), 4.26 (t, 1H), 3.96 (dd, 1H), 3.23 (m, 2H), 2.21 (m, 1H), 1.92 (m, 3H)
Example 46
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on hydrochloride (Compound 47)
[0242] With the exception of using the compound 46, the same procedure as in Example 41 was conducted to prepare the title compound.
[0243] 1 H NMR (DMSO-d 6 ) δ 9.11 (bs, 2H), 8.91 (s, 1H), 8.20 (m, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.05 (m, 1H), 4.55 (dd, 1H), 4.46 (s, 3H), 4.41 (dd, 1H), 4.25 (t, 1H), 4.01 (dd, 1H), 3.36 (m, 2H), 2.07 (m, 1H), 1.89 (m, 3H)
Example 47
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride (Compound 48)
[0244] With the exception of using the compound 27, the same procedure as in Example 41 was conducted to prepare the title compound.
[0245] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.48 (s, 3H), 8.21 (s, 2H), 7.76 (t, 1H), 7.66 (dd, 1H), 7.48 (dd, 1H), 5.04 (m, 1H), 4.47 (m, 2H), 4.23 (t, 1H), 3.94 (m, 1H), 3.84 (d, 2H), 2.62 (s, 3H)
Example 48
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 49)
[0246] With the exception of using BOC-β-alanine, instead of BOC-glycine, the same procedure as in Example 10 was conducted to prepare the title compound.
[0247] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.20 (m, 2H), 7.75 (t, 1H), 7.73 (bs, 3H), 7.68 (dd, 1H), 7.48 (dd, 1H), 5.02 (m, 1H), 4.46 (s, 3H), 4.36 (m, 2H), 4.26 (t, 1H), 3.93 (dd, 1H), 3.02 (m, 2H), 2.70 (t, 2H)
Example 49
Preparation of (R)-3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 50)
[0248] With the exception of using the compound 49, the same procedure as in Example 41 was conducted to prepare the title compound.
[0249] 1 H NMR (DMSO-d 6 ) δ 8.91 (s, 1H), 8.22 (m, 2H), 8.11 (bs, 3H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.48 (dd, 1H), 5.02 (m, 1H), 4.46 (s, 3H), 4.36 (m, 2H), 4.23 (t, 1H), 3.95 (m, 1H), 3.00 (m, 2H), 2.74 (t, 2H)
Example 50
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid (Compound 51)
[0250] With the exception of using the compound 16 and BOC-L-alanine, the same procedure as in Example 10 was conducted to prepare the title compound.
[0251] 1 H NMR (DMSO-d 6 ) δ 8.93 (s, 1H), 8.39 (bs, 3H), 8.21 (s, 2H), 7.76 (t, 1H), 7.68 (dd, 1H), 7.49 (dd, 1H), 5.04 (m, 1H), 4.61 (dd, 1H), 4.40 (dd, 1H), 4.28 (t, 1H), 4.18 (dd, 1H), 3.95 (dd, 1H), 2.62 (s, 3H), 1.36 (d, 3H)
Example 51
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 52)
[0252] With the exception of using the compound 51, the same procedure as in Example 41 was conducted to prepare the title compound.
[0253] 1 H NMR (DMSO-d 6 ) δ 8.93 (s, 1H), 8.61 (bs, 3H), 8.21 (s, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.05 (m, 1H), 4.58 (dd, 1H), 4.39 (dd, 1H), 4.25 (t, 1H), 4.12 (m, 1H), 4.00 (dd, 1H), 2.62 (s, 3H), 1.36 (d, 3H)
Example 52
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic acid (Compound 53)
[0254] With the exception of using the compound 16 and BOC-L-valline, the same procedure as in Example 10 was conducted to prepare the title compound.
[0255] 1 H NMR (DMSO-d 6 ) δ 8.93 (s, 1H), 8.40 (bs, 3H), 8.21 (s, 2H), 7.75 (t, 1H), 7.68 (dd, 1H), 7.48 (dd, 1H), 5.04 (m, 1H), 4.62 (dd, 1H), 4.40 (dd, 1H), 4.26 (t, 1H), 3.99 (d, 1H), 3.92 (dd, 1H), 2.62 (s, 3H), 2.12 (m, 1H), 0.97 (d, 3H), 0.94 (d, 3H)
Example 53
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride (Compound 54)
[0256] With the exception of using the compound 53, the same procedure as in Example 41 was conducted to prepare the title compound.
[0257] 1 H NMR (DMSO-d 6 ) δ 8.93 (s, 1H), 8.60 (bs, 3H), 8.21 (s, 2H), 7.75 (t, 1H), 7.67 (dd, 1H), 7.49 (dd, 1H), 5.04 (m, 1H), 4.58 (dd, 1H), 4.42 (dd, 1H), 4.26 (t, 1H), 3.92 (m, 1H), 2.62 (s, 3H), 2.12 (m, 1H), 0.97 (d, 3H), 0.94 (d, 3H)
Example 54
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on trifluoroacetic acid (Compound 55)
[0258] With the exception of using the compound 16 and BOC-L-prroline, the same procedure as in Example 10 was conducted to prepare the title compound.
[0259] 1 H NMR (DMSO-d 6 ) δ 9.20 (bs, 2H), 8.93 (s, 1H), 8.21 (s, 2H), 7.77 (t, 1H), 7.66 (dd, 1H), 7.50 (dd, 1H), 5.04 (m, 1H), 4.59 (dd, 1H), 4.43 (m, 2H), 4.26 (t, 1H), 3.96 (dd, 1H), 3.21 (m, 2H), 2.62 (s, 3H), 2.21 (m, 1H), 1.95 (m, 1H), 1.89 (m, 2H)
Example 55
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-prolinyloxy)methyl oxazolidin-2-on hydrochloride (Compound 56)
[0260] With the exception of using the compound 55, the same procedure as in Example 41 was conducted to prepare the title compound.
[0261] 1 H NMR (DMSO-d 6 ) δ 9.18 (bs, 2H), 8.93 (s, 1H), 8.21 (s, 2H), 7.76 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.05 (m, 1H), 4.57 (dd, 1H), 4.43 (m, 2H), 4.26 (t, 1H), 4.00 (dd, 1H), 3.21 (m, 2H), 2.62 (s, 3H), 2.21 (m, 1H), 1.95 (m, 1H), 1.89 (m, 2H)
Example 56
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic acid (Compound 57)
[0262] With the exception of using the compound 16 and BOC-β-allanine, the same procedure as in Example 10 was conducted to prepare the title compound.
[0263] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.21 (s, 2H), 7.88 (bs, 3H), 7.76 (t, 1H), 7.68 (dd, 1H), 7.49 (dd, 1H), 5.02 (m, 1H), 4.36 (m, 2H), 4.25 (t, 1H), 3.94 (dd, 1H), 3.03 (m, 2H), 2.70 (t, 2H), 2.62 (s, 3H)
Example 57
Preparation of (R)-3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 58)
[0264] With the exception of using the compound 57, the same procedure as in Example 41 was conducted to prepare the title compound.
[0265] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.21 (s, 2H), 8.08 (bs, 3H), 7.76 (t, 1H), 7.68 (dd, 1H), 7.49 (dd, 1H), 5.02 (m, 1H), 4.36 (m, 2H), 4.25 (t, 1H), 3.96 (dd, 1H), 3.00 (m, 2H), 2.71 (t, 2H), 2.62 (s, 3H)
Example 58
Preparation of mono-[(R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate (Compound 72) and (R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate (Compound 59)
[0266] 1. The Primary Step
[0267] In 10 ml of mixture solvent (tetrahydrofuran:methylenechloride=1:1) was dissolved 1 g of compound 10. The solution was added with 0.6 g of tetrazole and 2.3 g of di-tetrabuthyl diisoprophylphosphoamidite and stirred for 15 hours at room temperature. The reaction mixture was refrigerated to −78° C., added with 0.7 g of metachloroperbenzoic acid and stirred for 2 hours. After being cooling to −78° C., the reaction mixture was added with metachloroperbenzoic acid (0.7 g). When the reaction mixture was stirred for 2 hours, the temperature of the reaction mixture was raised to room temperature. The reaction mixture was then added with ethyl acetate. The organic layer, thus separated, was washed with sodiumbisulfate, sodiumbicarbonate and brine, dehydrated, filtered and concentrated in vacuo, followed by purification with column chromatography thereby to provide (R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl phosphoric acid ditetrabuthylester (0.71 g, 71%).
[0268] 1 H NMR (DMSO-d 6 ) δ 8.90 (s, 1H), 8.18 (m, 2H), 7.74 (t, 1H), 7.68 (dd, 1H), 7.49 (dd, 1H), 4.98 (m, 1H), 4.46 (s, 3H), 4.23 (t, 1H), 4.18 (m, 1H), 4.09 (m, 1H), 3.89 (dd, 1H), 1.39 (s, 9H), 1.38 (s, 9H)
[0269] The crystal prepared the above method was dissolved in a mixture of methanol and chloroform. And then the solution added with 3.4 ml of sodiummethoxide (0. 3M methanol solution) at the room temperature and stirred for 10 hours. The reaction mixture was concentrated to prepare the residue. The residue was crystallized and filtered thereby to obtain the title compound (compound 59) 300 mg.
[0270] 1 H NMR (D 2 O) δ 8.27 (s, 1H), 7.56 (dd, 2H), 7.06 (m, 2H), 6.90 (m, 1H), 4.79 (m, 1H), 4.63 (s, 3H), 3.90 (m, 4H)
[0271] 2. The Secondary Step
[0272] In 30 ml of methylenechloride was dissolved the compound (0.7 g) in the Primary Step. The solution was added with 15 ml of trifluoroacetic acid and then stirred for 1 hour at room temperature. The reaction mixture was concentrated in vacuo to prepare the residue. The residue was crystallized with ethanol and ethyl ether to obtain mono-[(R)-[3-(4-(2-(2-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate (compound 72) 400 mg.
[0273] 1 H NMR (DMSO-d 6 ) δ 8.92 (s, 1H), 8.20 (m, 2H), 7.74 (t, 1H), 7.66 (dd, 1H), 7.500 (dd, 1H), 4.95 (m, 1H), 4.46 (s, 3H), 4.21 (t, 1H), 4.05 (m, 2H), 3.91 (dd, 1H)
Example 59
Preparation of (R)-[3-(4-(2-(2-methyl-[1,3,4]oxadiazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate (Compound 60)
[0274] Using the compound 16, the title compound was prepared in a manner similar to that of the Example 58.
[0275] 1 H NMR (D 2 O) δ 8.33 (s, 1H), 7.65 (dd, 2H), 7.17 (m, 2H), 6.90 (m, 1H), 4.79 (m, 1H), 4.63 (s, 3H), 3.94 (t, 1H), 3.78 (m, 3H)
Example 60
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-hydroxymethyl oxazolidin-2-on (Compound 61)
[0276] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 1.
[0277] 1 H NMR (DMSO-d 6 ) δ 8.98 (s, 1H), 8.30 (m, 2H), 7.75 (m, 2H), 7.53 (dd, 1H), 5.25 (t, 1H), 4.76 (m, 1H), 4.44 (s, 3H), 4.14 (t, 1H), 3.89 (dd, 1H), 3.69 (m, 1H), 3.58 (m, 1H)
Example 61
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on trifluoroacetic Acid (Compound 62)
[0278] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 10.
[0279] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.20 (s, 3H), 8.19 (m, 2H), 7.80 (t, 1H), 7.69 (dd, 1H), 7.49 (dd, 1H), 5.00 (m, 1H), 4.46 (m, 2H), 4.45 (s, 3H), 4.24 (t, 1H), 3.92 (dd, 1H), 3.90 (s, 2H)
Example 62
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-glycyloxymethyl oxazolidin-2-on hydrochloride (Compound 63)
[0280] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 43.
[0281] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.50 (bs, 3H), 8.21 (m, 2H), 7.80 (t, 1H), 7.65 (dd, 1H), 7.49 (dd, 1H), 5.03 (m, 1H), 4.48 (m, 2H), 4.43 (s, 3H), 4.24 (t, 1H), 3.99 (dd, 1H), 3.86 (m, 2H)
Example 63
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 64)
[0282] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 40.
[0283] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.43 (s, 3H), 8.25 (m, 2H), 7.77 (t, 1H), 7.68 (dd, 1H), 7.48 (dd, 1H), 5.05 (m, 1H), 4.63 (dd, 1H), 4.44 (s, 3H), 4.42 (dd, 1H), 4.24 (t, 1H), 4.18 (m, 1H), 3.98 (dd, 1H), 1.36 (d, 3H)
Example 64
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 65)
[0284] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 42.
[0285] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.53 (bs, 3H), 8.24 (m, 2H), 7.77 (t, 1H), 7.67 (dd, 1H), 7.49 (dd, 1H), 5.05 (m, 1H), 4.60 (dd, 1H), 4.43 (s, 3H), 4.42 (dd, 1H), 4.26 (t, 1H), 4.20 (m, 1H), 4.00 (dd, 1H), 1.37 (d, 3H)
Example 65
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 66)
[0286] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 11.
[0287] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.42 (s, 3H), 8.25 (m, 2H), 7.79 (t, 1H), 7.70 (dd, 1H), 7.48 (dd, 1H), 5.05 (m, 1H), 4.64 (dd, 1H), 4.44 (s, 3H), 4.43 (dd, 1H), 4.30 (t, 1H), 4.01 (d, 1H), 3.93 (dd, 1H), 2.14 (m, 1H), 0.98 (d, 3H), 0.95 (d, 3H)
Example 66
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(L-valyloxy)methyl oxazolidin-2-on hydrochloride (Compound 67)
[0288] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 41.
[0289] 1 H NMR (DMSO-d 6 ) δ 8.94 (s, 1H), 8.57 (bs, 3H), 8.22 (m, 2H), 7.79 (t, 1H), 7.67 (dd, 1H), 7.49 (dd, 1H), 5.04 (m, 1H), 4.59 (dd, 1H), 4.43 (s, 3H), 4.41 (dd, 1H), 4.27 (t, 1H), 3.99 (m, 2H), 2.17 (m, 1H), 0.97 (d, 3H), 0.94 (d, 3H)
Example 67
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on trifluoroacetic Acid (Compound 68)
[0290] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 48.
[0291] 1 H NMR (DMSO-d 6 ) δ 8.94 (s, 1H), 8.24 (m, 2H), 7.77 (t, 1H), 7.73 (bs, 3H), 7.70 (dd, 1H), 7.49 (dd, 1H), 5.02 (m, 1H), 4.44 (s, 3H), 4.36 (m, 2H), 4.27 (t, 1H), 3.93 (dd, 1H), 3.05 (m, 2H), 2.70 (t, 2H)
Example 68
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-(β-alanyloxy)methyl oxazolidin-2-on hydrochloride (Compound 69)
[0292] Using 2-(1-methyltetrazol-5-yl)-5-bromopyridine, the title compound was prepared in a manner similar to that of the Example 49.
[0293] 1 H NMR (DMSO-d 6 ) δ 8.96 (s, 1H), 8.25 (m, 2H), 8.13 (bs, 3H), 7.79 (t, 1H), 7.66 (dd, 1H), 7.48 (dd, 1H), 5.02 (m, 1H), 4.43 (s, 3H), 4.36 (m, 2H), 4.25 (t, 1H), 3.97 (m, 1H), 3.01 (m, 2H), 2.74 (t, 2H)
Example 69
Preparation of mono-[(R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate (Compound 73) and (R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl disodiumphosphate (Compound 70)
[0294] 1. The Primary Step
[0295] Using the compound 61, (R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl phosphoric acid ditetrabuthylester was prepared in a manner similar to that of the Example 58.
[0296] 1 H NMR (DMSO-d 6 ) δ 8.94 (s, 1H), 8.20 (m, 2H), 7.78 (t, 1H), 7.68 (dd, 1H), 7.49 (dd, 1H), 4.98 (m, 1H), 4.44 (s, 3H), 4.21 (t, 1H), 4.18 (m, 1H), 4.10 (m, 1H), 3.89 (dd, 1H), 1.39 (s, 9H), 1.38 (s, 9H)
[0297] 2. The Secondary Step
[0298] Using the compound provided in the Primary Step, 400 mg of mono-[(R)-[3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-2-oxo-5-oxazolidinyl]methyl]phosphate (compound 73) was prepared in a manner similar to that of the Example 58
[0299] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.23 (m, 2H), 7.76 (t, 1H), 7.66 (dd, 1H), 7.500 (dd, 1H), 4.95 (m, 1H), 4.44 (s, 3H), 4.21 (t, 1H), 4.05 (m, 2H), 3.91 (dd, 1H)
[0300] The title compound (compound 70) was obtained in a manner similar to that of the Example 58.
[0301] 1 H NMR (D 2 O) δ 8.29 (s, 1H), 7.60 (dd, 2H), 7.10 (m, 2H), 6.90 (m, 1H), 4.79 (m, 1H), 4.60 (s, 3H), 3.90 (m, 4H)
Example 70
Preparation of (R)-3-(4-(2-(1-methyltetrazol-5-yl)pyridin-5-yl)-3-fluorophenyl)-5-([1,2,3]triazol-1-yl)methyl oxazolidin-2-on (Compound 71)
[0302] Using the compound 61, the title compound was prepared in a manner similar to that of the Example 24.
[0303] 1 H NMR (DMSO-d 6 ) δ 8.95 (s, 1H), 8.21 (m, 3H), 7.77 (s, 1H), 7.75 (t, 1H), 7.59 (dd, 1H) 7.42 (dd, 1H), 5.22 (m, 1H), 4.86 (m, 2H), 4.44 (s, 3H), 4.31 (t, 1H), 3.98 (dd, 1H)
Experimental Example 1
Assay for in Vitro Antibacterial Activity
[0304] To test an antibacterial activity of the derivatives of oxazolidinone, the antibacterial activity, including methicillin resistant Staphylococcus aureus (MRSA) and vancomycin resistant Enterococci (VRE), was represented as Minimum Inhibitory Concentration (MIC 50 , μg/ml) using agar dilution described in a art (Chemotherapy, 29(1), 76, (1981)). Zyvox of Pharmacia & Upjohn Inc, corresponding to Formula 3, was used as control. The results are shown in Table 2.
[0000]
TABLE 2
Minimum Inhibitory
Concentration
(MIC 50 , μg/ml)
Compound
MRSA
VRE
Zyvox
2
2
1
1
0.25
2
0.5
0.125
3
0.25
0.25
4
2
2
5
0.5
0.25
6
NA
NA
7
0.5
0.5
8
16
16
9
0.25
0.125
10
0.5
0.25
11
0.5
0.25
12
0.5
0.25
13
0.25
0.25
14
0.25
0.25
15
1
1
16
0.5
1
17
1
1
18
1
2
19
32
32
20
0.5
0.25
21
1
1
22
1
1
23
2
2
24
0.5
0.5
25
0.25
0.125
26
0.5
0.5
27
0.5
1
28
0.5
0.5
29
0.5
1
30
0.5
0.5
31
0.5
0.5
32
0.5
1
33
2
2
34
1
1
35
1
1
36
0.5
0.5
37
0.5
0.5
38
0.5
1
39
1
1
40
4
8
41
4
8
42
0.5
0.25
43
0.5
0.25
44
0.5
0.25
45
0.5
0.25
46
0.5
0.25
47
0.5
0.25
48
0.5
1
49
0.5
0.25
50
0.5
0.25
51
0.5
1
52
0.5
1
53
0.5
1
54
0.5
1
55
0.5
1
56
0.5
1
57
0.5
1
58
0.5
1
59
0.5
0.25
60
0.5
1
61
0.5
0.25
62
0.5
0.25
63
0.5
0.25
64
0.5
0.25
65
0.5
0.25
66
0.5
0.25
67
0.5
0.25
68
0.5
0.25
69
0.5
0.25
70
0.5
0.25
71
0.5
0.125
72
32
32
73
32
32
NA: Not determined
MRSA: methicillin resistant Staphylococcus aureus
VRE: vancomycin resistant Enterococci
[0305] As illustrated in Table 2, the derivatives of the present invention had sufficient efficiency on antibacterial activity against Staphylococcus aureus (MRSA) and Enterococci (VRE) in spite of using lower concentration of the derivatives than that of the Zyvox. Accordingly, the compounds of the present invention may be useful as antibiotics.
(i) Experimental Example 2
Assay for Solubility
[0306] To test a solubility of the derivatives of the present invention, an experiment was carried out below. The derivatives of the present invention were added to 200 μl of distilled water and then the solution was stiffed for 2 minutes. The turbidity of the solution was watched through naked eye.
[0307] When the derivatives were not dissolved completely, 50 μl of distilled water was added to the solution and then the turbidity of the solution was assayed in the above manner to find a point of becoming transparent solution.
[0308] When 2 mg of the derivatives was first added to distilled water and completely dissolved so that the solution became transparent, 2 mg of the derivatives was added more to the solution and then state of the solution was watched. The derivatives of the present invention were added to the five times and then solubility of the solution was assayed for. The assay for solubility was carried out the three times repeatedly in the above method and the results were averaged. The averages were shown in Table 3.
[0000]
TABLE 3
Compound
Solubility
Zyvox
3
mg/ml
10
10
μg/ml
12
28
mg/ml
16
20
μg/ml
20
4.7
mg/ml
27
>50
mg/ml
42
>50
mg/ml
43
4.2
mg/ml
44
>50
mg/ml
45
12
mg/ml
46
<1.63
mg/ml
47
2
mg/ml
48
>50
mg/ml
49
2.6
mg/ml
50
20.4
mg/ml
51
>50
mg/ml
52
>50
mg/ml
53
30.3
mg/ml
54
2.9
mg/ml
55
7.2
mg/ml
56
>50
mg/ml
57
>50
mg/ml
58
5.5
mg/ml
59
>50
mg/ml
60
>50
mg/ml
62
28
mg/ml
64
>50
mg/ml
66
4.7
mg/ml
68
2.6
mg/ml
70
>50
mg/ml
[0309] As shown in table 3, the solubility of the compound 42(>50 mg/ml) that is prodruged, of the derivatives was enhanced as compared with those of Zyvox (3 mg/ml) and the compound 10(10 μg/ml).
[0310] Accordingly, when the derivatives of the present invention were formulated for oral administration, absorption of the derivatives may be enhanced. When the derivatives were formulated as injection, various formations of the derivatives may be obtained.
Experimental Example 3
Test of Acute Toxicity by Oral Administrating the Derivatives to Mouse
[0311] To test acute toxicity of the compounds of the present invention, the following experiment was carried out.
[0312] A mixture of 1% hydroxyprophylmethylcellulose and 200 mg of one selected from the group consisting of the compounds 10, 12, 16, 17, 20, 22, 24 and 27 was administrated to 5 ICR mice (5-Week old males, 20 g±2 g by weight). And then lethality for 2 weeks, weight, symptoms etc. was watched to determine Minimum Lethal Dose (MLD, mg/kg). Zyvox of Pharmacia & Upjohn Inc was used as control. The results were represented in Table 4.
[0000]
TABLE 4
Compound
Minimum Lethal Dose (MLD, mg/kg)
Zyvox
>1000
10
>1000
12
>1000
16
>1000
17
>1000
20
>1000
22
>1000
24
>1000
27
>1000
[0313] Observation of survival, change in weight, tests in blood, and toxicity syndrome, etc. proved that administration of the composition of the present invention has no toxic effects
[0314] The compounds of the present invention have excellent efficiency on antibacterial activity without any toxicity present according to Table 4.
Example Formulation
Preparation of Pharmaceutical Composition
Preparation as Powder
[0315]
[0000]
Derivative of oxazolidinone
2 g
Lactose
1 g
[0316] The above materials were mixed and then the mixture was filled into a closed pack to prepare as powder.
Preparation as Tablet
[0317]
[0000]
Derivative of oxazolidinone
500 mg
Corn starch
100 mg
Lactose
100 mg
Magneisuim stearate
2 mg
[0318] The above materials were mixed and then the mixture was tabletted by the known method to prepare as tablet.
[0319] 3. Preparation of Capsule
[0000]
Derivative of oxazolidinone
500 mg
Corn starch
100 mg
Lactose
100 mg
Magneisuim stearate
2 mg
[0320] The above materials were mixed and the mixture was filled into gelatin capsule by the known method to prepare as capsule.
[0321] 4. Preparation of Injection
[0000]
Derivative of oxazolidinone
500 mg
Citrate buffer
maintaining of pH 3.5
Dextrose
isotonicity
[0322] The derivative of oxazolidine, salt of sodium citrate, citratic acid and dextrose were filled in 20 ml of vial, sterilized, for injection and then sealed off using aluminum cap. The mixture was dissolved in distilled water for injection and then diluted in distilled water solution, having appropriate volume, for injection. | The present invention relates to novel derivatives of oxazolidinone, a method thereof and pharmaceutical compositions comprising the derivatives for use in an antibiotic. The oxazolidinone derivatives of the present invention show inhibitory activity against a broad spectrum of bacteria and lower toxicity. The prodrugs, prepared by reacting the compound having hydroxyl group with amino acid or phosphate, have an excellent efficiency on solubility thereof against water. Further, the derivatives of the present invention may exert potent antibacterial activity versus various human and animal pathogens, including Gram-positive bacteria such as Staphylococi, Enterococci and Streptococi, anaerobic microorganisms such as Bacteroides and Clostridia , and acid-resistant microorganisms such as Mycobacterium tuberculosis and Mycobacterium avium . Accordingly, the compositions comprising the oxazolidinone are used in an antibiotic. | 0 |
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to a cleaning and lubricating solution for guns, gun bores, cartridges, and gun parts, and more especially for black powder guns, gun bores, cartridges, and gun parts.
The present invention comprises a cleaning and lubricating solution containing a fatty acid compound such as an oleate, an oxidizing agent preferably hydrogen peroxide solution, and an alcohol. A bittering agent is generally included, but is not essential to the performance of the cleaning and lubricating solution.
Unlike modern firearms, black powder firearms are not blued or chromed in that the black powder, (“also known as blasting powder”), contains a brown or black explosive mixture of potassium nitrate, charcoal, and sulfur which is corrosive to such a finish. In some cases, sodium nitrate is substituted for potassium nitrate. Typical proportions are 75%, 15%, and 10%, respectively. Originally gun powder was made in powder form, whereas today it is formed into grains of various sizes. It is sensitive to heat and deflagrates rapidly. It does not detonate, but is a dangerous fire and explosion hazard. Besides gunpowder, black powder is still used for time fuses for blasting, in large caliber artillery shells, in igniter and primer assemblies for propellants, pyrotechnics, and mining.
2. Description of the Prior Art
Due to the corrosive chemical nature of black powder on steel, black powder guns must be cleaned immediately upon use, and may rust in less than two hours within use. Black powder guns, whether inline, caplock, flintlock, or large caliber military guns need to be cleaned after every shot or two to maintain good accuracy. Because of the corrosiveness of black powder cleaning is very important in protecting an investment in these weapons.
Conventional methods of cleaning black powder guns consisted of filling the barrel with hot soapy water and swapping a patch back and forth through the barrel bore until the patch was white indicating the barrel bore was clean. Typically the gun barrel and bore was lubricated with a light oil to prevent rust.
Furthermore, black powder weapons accumulate a seasoning over time like an “iron skillet”. Conventional petroleum-based cleaners now on the market tend to strip all of that seasoning out of the gun barrel bore leaving the weapon vulnerable to rust in that it strips the protective patina from the metal.
SUMMARY OF THE INVENTION
The present invention is used to clean dirt and debris from the bores and other parts of black powder firearms and accessories. The solution cleans the bore and coats it with a lubricant comprising an oil such as a GRAS vegetable oil. The solution is safe for use with modern firearms, whether nickel plated, blued, or stainless steel, as well as carbon steel antique weapons, and is considered to be an “environmentally-friendly” product.
The cleaning and lubricating solution of the present invention may be used straight from the container and poured into a gun barrel bore, or even onto the metal surface of the gun. Moreover, the cleaning and lubricating solution may be incorporated into gun oil, pre-lubricated muzzle loader patches, bore conditioners, and or bullet lubricants.
It is an object of the present invention to provide an inexpensive cleaning and lubricating solution which may be used for black powder guns in a single step so that the treated gun bore is cleaned and a lubricant film is formed upon draining from the barrel.
It is another object of the present invention to provide a cleaning and lubricating solution for black powder guns which is environmentally friendly and generally recognized as safe for the user.
It is another object of the present invention to be able to use the cleaning and lubricating solution in a short time span.
It is another object of the present invention to provide a solution which may be applied by brush, spray, dipping, and/or swabbing.
It is another object of the present invention to provide a cleaning solution which will not harm the lubrication seasoning in the bore.
It is another object of the present invention to provide a cleaning and lubricating solution which is compatible with existing gun oils and lubricants.
It is another object of the present invention to provide a cleaning and lubricating solution which exhibits a foaming action thereby providing a self cleaning lubricant which penetrates into the cracks and crevices of the metal to clean and lubricate.
It is another object of the present invention to provide a cleaning and lubricating solution which acts to passivate the metal.
It is yet another object of the present invention to provide a cleaning and lubricating solution for black powder applications wherein the amount of fouling in the bore make no difference.
Finally, it is an object of the present invention to provide a solution which may be used to wipe off the metal around the lock to prevent corrosion.
The foregoing objects are accomplished by the cleaning and lubricating solution of the present invention.
Preferred compositions of the black powder cleaning and lubricating solution typically contain a hydrogen peroxide solution in an amount ranging from about 15 percent to about 50 percent by weight of the total weight percent of the composition based on a 4% solution; an alcohol in an amount ranging from about 15 percent to about 50 percent by weight of the total weight percent of the composition; and a fatty acid soap in an amount ranging from about 15 percent to 60 percent by weight of the total weight percent of the composition. One preferred embodiment comprises about one-third of a fatty acid, about one-third of an alcohol, and about one-third of a 4% hydrogen peroxide solution. One or more bittering agents may be utilized with the above aforementioned ingredients.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The cleaning and lubricating solution of the present invention is formulated to provide a single use solution for use in storage or in the field. However, it is contemplated that the solution may be combined with existing lubricants, cleaners and oils to enhance the performance characteristics especially demonstrated by the deep cleaning foaming action of the solution. Moreover, the formulation may be adjusted to provide more cleansing or lubricating advantages as desired.
As set forth heretofore, the preferred compositions of the black powder cleaning and lubricating solution typically contain a hydrogen peroxide solution in an amount ranging from about 15 percent to about 50 percent by weight of the total weight percent of the composition based on a 4% solution; an alcohol in an amount ranging from about 15 percent to about 50 percent by weight of the total weight percent of the composition; and a fatty acid soap in an amount ranging from about 15 percent to 60 percent by weight of the total weight percent of the composition. One preferred embodiment comprises about one-third of a fatty acid, about one-third of an alcohol, and about one-third of a 4% hydrogen peroxide solution. One or more bittering agents may be utilized with the above aforementioned ingredients. The individual components of the solution are set forth in more detail as follows:
Fatty Acid Lubricant
Natural occurring vegetable oil such as corn oil, sunflower oil, olive oil, soybean oil, peanut oil, or other such naturally occurring oil may be utilized in the present invention as well as a potassium hydroxide based soap. The fatty acid is preferably non-volatile, non-corrosive oil of a relatively low viscosity providing a light film residue which blends with readily with oils or greases which may be subsequently applied to protect the bore surface.
A preferred fatty acid of the present invention is a carboxylic acid derived from or contained in an animal or vegetable fat or oil. It is composed of a chain of alkyl groups containing from 4 to 22 carbon atoms characterized by a terminal carboxyl group —COOH. The generic formula for all above acetic is CH 3 (CH 2 ) x COOH, wherein the carbon atom count includes the carboxyl group.
The preferred fatty acid is an unsaturated fatty acid in which there are one or more double bonds between the carbon atoms in the alkyl chain. These acids are usually vegetable-derived and consist of alkyl chains containing 18 or more carbon atoms with the characteristic end group —COOH. Most vegetable oils are mixtures of several fatty acids or their glycerides. The most common unsaturated acids are oleic, linoleic, and linolenic (all C 18 Safflower oil is high in linoleic acid, peanut oil contains 21% linoleic acid, olive oil is 38% oleic acid.
Soaps such as sodium, potassium, and ammonium salts of oleic and stearic acids are particularly preferred fatty acid soaps.
More particularly, oleic acid, (cis-9-octadecenoic acid), defined as CH 3 (CH 2 ) 7 CH:CH(CH 2 ) 7 COOH, is a mono-unsaturated fatty acid which is a component of almost all natural fats as well as tall oil. Most oleic acid is derived from animal tallow or vegetable oils. The fatty acid group is typically formed by saponification of oleic acid provides a neutralized soap completely miscible with water, and biodegradable. The preferred embodiment utilizes fatty acid soaps selected from the oleic acid group, preferably potassium oleate, (C 17 H 33 COOK), and/or ammonium oleates (C 17 H 33 COONH 4 ). The oleic acid component of the present invention is insoluble in water, but soluble in alcohol and is a solvent for other oils, fatty acids and oil-soluble materials. It is also contemplated that olein, (glyceryl trioleate), the triglyceride of oleic acid occurring most fats and oils may also be used in place of or in combination with other fatty acids. It constitutes from about 70 to about 80 percent of olive oil.
The present invention incorporates a fatty acid, such as a vegetable oil or oleic acid compound in an amount ranging from about 10 percent to about 50 percent by volume, more preferably from about 20 to about 40 percent by volume; and most preferably about 30 percent by volume.
Alcohols
Alcohols which may be used in the present invention comprise a broad class of hydroxyl-containing organic compounds occurring naturally in plants and made synthetically from petroleum derivatives such as ethylene. These include: I Monohydric (10H group) such as 1) aliphatic including paraffinic (ethanol) and olefinic (allyl alcohol), 2) alicyclic (cyclohexanol), 3) aromatic (phenol, benzyl alcohol), 4) heterocyclic (furfuryl alcohol) and 5) poly cyclic (sterols); II dihydric (2OH groups) such as glycols and derivatives (diols); and III trihydric (3 OH groups) such as glycerol and derivatives.
The most preferred alcohol is isopropyl alcohol, (CH 3 ) 2 CH 2 O which is a colorless liquid, soluble in water. Other alcohols which may be used in the present invention include ethyl, and butyl alcohol. It is contemplated that water-soluble alcohols containing from 1 to about 4 carbon atoms and 1 to about 3 hydroxy groups may be used including the glycols or glycol ethers and monoethers such as the methyl, ethyl, propyl, and butyl ethers of ethylene glycol; diethylene glycol, propylene glycol, and dipropylene glycol.
The present invention incorporates an alcohol, such as isopropyl alcohol in an amount ranging from about 5 percent to about 50 percent by volume, more preferably from about 15 to about 40 percent by volume; more preferably from about 25 to about 35 percent by volume; and most preferably about 30 percent by volume.
Oxidizing Agents
The present invention utilizes an oxidizing agent which is a compound that spontaneously evolves oxygen either at room temperature or under slight heating. The oxidizing agents which may be used in the present invention include chemicals such as peroxides, chlorates, percholrates, nitrates, and permanganates.
The preferred oxidizing agent for the instant invention is hydrogen peroxide having a molecular formula of H 2 O 2 and a structural formula of H—O—O—H. It is soluble in both water an alcohol. It is a very strong oxidizing agent and concentrated solutions are highly toxic; therefor, a very weak solution of 4% is utilized in the preferred embodiment of the present invention. Solutions ranging from 0.1 to 10% may be used depending upon the desired characteristics of the solution.
It is believed that the oxidizing agent serves to passivate the metal of the gun bore in that the metals within the bore lose their normal chemical activity in a corrosive environment after treatment with a strong oxidizing agent such as the nitric acid produced by ignition of black powder. Treatment with the oxidizing agent of the present invention provides oxygen thereby forming an oxide coating and protecting the seasoning of the metal.
The present invention incorporates an oxidizing agent, such as 0.1 to 10.0 percent and more preferably from 2.0 to 4.0 percent strength solution of hydrogen peroxide in an amount ranging from about 0.1 percent to about 60 percent by volume, more preferably from about 1 to about 50 percent by volume; more preferably from about 10 to about 40 percent by volume; more preferably from about 20 to 35 percent by volume and most preferably about 30 percent by volume.
Bittering Agents
A bittering agent may be added to the formulation in an amount of less than 5% and usually in an amount ranging from about 0.1 to 1.0 percent. Bitrex also known as denatonium benzoate may be used and/or benzylidiethyl.
METHOD OF USE
For example, to clean a black powder gun barrel bore, with the cleaning and lubricating solution of the present invention, simply plug the nipple or flash vent hole with an object, even a toothpick.
For field cleaning, run a patch dampened with the cleaning and lubricating solution of the present invention through the bore several times. After removing the plug, run a dry patch through the bore.
For final cleaning, plug and pour the cleaning and lubricating solution into the bore to within about two inches of the muzzle. Let the gun stand upright for approximately ten minutes. Pour the cleaning and lubricating solution from the barrel bore and run a dry patch therethrough. The bore will not only be clean but have a thin coat of lubricant thereon. Of course in saltwater or humid conditions it is recommended to apply a fine coat of oil to the bore. A light oil or other lubricant may be used in combination with or in addition to the present composition after cleaning to further remove any neutralized residue and supplement the protective coating formed by the present invention.
It should be noted that upon pouring the solution into the barrel bore, the solution will fizzle and bubble as it reacts with the gunpowder residue neutralizing same. The solution poured from the barrel will generally remain clear as before use. After several applications the solution will cease to bubble and adopt a gray tint or cast indicating the effectiveness is gone.
Modifications
Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
Reference to documents made in the specification is intended to result in such patents or literature cited are expressly incorporated herein by reference, including any patents or other literature references cited within such documents as if fully set forth in this specification.
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims. Accordingly, this invention is not intended to be limited by the specific exemplifications presented hereinabove. Rather, what is intended to be covered is within the spirit and scope of the appended claims. | This invention relates to a cleaning and lubricating solution for guns, gun bores, cartridges, and gun parts, and more especially for black powder guns, gun bores, cartridges, and gun parts. The solution is used to clean dirt and debris from the bores and other parts of black powder firearms and accessories. The solution cleans the bore and the residual material forms a protective coating or film of a light lubricating oil. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a control system for a multi-cylinder internal combustion engine, and more specifically, to a system for controlling the number of working (active) cylinders in a multi-cylinder engine and its operation.
2. Description of Prior Art
For improvement of fuel economy in multi-cylinder internal combustion engines for vehicles such as automobile, there has been proposed a strategy for controlling the number of working cylinders in an engine, depending upon a load applied thereon. A multi-cylinder engine has higher energy efficiency (the ratio of outputted mechanical energy to inputted fuel energy) when a load per cylinder is high. Thus, in this strategy, some of cylinders, e.g. a half number of cylinders, in an engine are selectively rendered inactive and a load per working cylinder is increased when the total load on the engine is low. This operation of a multi-cylinder engine while reducing the number of active cylinders is often called “cylinder reducing operation” or “partial operation”. Several examples of devices and methods executing cylinder reducing operation control for a multi-cylinder engine are seen in Japanese Patent Laid-Open Publications 05-272367, 7-180575, 11-182275, 11-350995, 5-332172, 6-193478, 10-103097, etc.
In cylinder reducing operation control as described in those publications, a total load on an engine is monitored through engine revolution speed and an accelerator or throttle opening or intake air pressure. Based upon a map of these parameters, the operation mode of an engine is switched between full cylinder operation, where all cylinders are active, and reduced cylinder operation, where only a half of cylinders are active and the rest of cylinders are inactive. Upon the switching of the operation mode, i.e. the changing of the number of working cylinders, a positive or negative surge of torque or power outputted from an engine occurs due to the variation of the mass of motion of an engine before and after the switching of the operation modes and the retardation of response of intake air flow amount variation. Such an output torque or power surge would cause a mechanical shock or impact on a driving system around an engine and a vehicle body, deteriorating the stability of the driving system and the drivability and driving stability of a vehicle. Thus, several strategies for avoiding a torque or output power surge upon the switching of the operation mode have been proposed also.
For instance, JP 5-332172, 6-193478 and 10-103097 disclose that ignition timing and throttle opening are varied for suppressing torque variation upon the switching of the operation mode. JP 5-272367 and 7-180575 each show that a map of engine revolution speed and an intake air pressure for determining an operation mode to be executed is modified depending upon a gear ratio of a transmission. JP 11-182275 and 11-350995 disclose a hybrid engine and dynamotor system where toque difference outputted from the engine before and after the changing of the number of active cylinders is cancelled through the operation of dynamotors.
Since the cylinder reducing operation control is employed mainly for increasing fuel efficiency of an engine, the engine should be operated in the reduced cylinder mode as long as torque or power requested of the engine, e.g. for driving a vehicle, can be generated by a reduced number of working cylinders. Ideally, the operation mode should be switched when the output power of an engine is at the maximum level available in the reduced cylinder mode. Then, each working cylinder will be operated at high load even when a total engine load is low.
Actual output torque or power from an engine, however, depends upon not only an intake air amount or throttle opening but also an engine temperature, environmental conditions of the engine, such as atmospheric pressure. It is difficult or cumbersome to estimate engine output torque/power precisely from an intake air amount, etc. Thus, when the operation mode at a certain condition is determined based upon only parameters such as throttle opening used so far, the switching of the operation mode will not always be executed at an ideal condition for providing output power requested in operating the engine while saving fuel. For instance, the premature switching of the operation mode into the reduced cylinder mode (and delayed switching into the full cylinder mode) would cause unexpected shortage of torque/power. On the other hand, when the switching into the reduced cylinder is too late, fuel would be wasted.
Accordingly, for further improvement of output performance and fuel economy of an engine, it will be preferable to provide a control strategy for cylinder reducing operation, enabling the switching of the operation mode at a more appropriate timing than ever, irrespective of the variation of internal and external (environmental) conditions of an engine.
SUMMARY OF INVENTION
According to the present invention, there is provided a novel control device of cylinder reducing operation for a multi-cylinder engine, controlling an operation mode of the engine more appropriately for fuel economy while ensuring the operational stability of the engine and comfortable drivability of a vehicle.
The inventive control device for cylinder reducing operation selectively inactivating some cylinders of a multi-cylinder internal combustion engine comprises a detector detecting engine output torque and judges if cylinder reducing operation is to be executed while referring to the engine output torque detected with the detector.
As described above, engine output torque or power varies with a plurality of parameters of external and internal conditions of the engine. Thus, the judgment of an operation mode between full cylinder and reduced cylinder operations based upon a map employing an intake air amount or a throttle opening as in the conventional control devices is often inappropriate: the switching is not always executed at a power level to be executed in the reduced cylinder mode.
In the present invention, however, since engine output torque is directly monitored, the judgment of the switching of an operation mode can be done when an actually generated output power level reaches to the level to be executed in the reduced cylinder mode or the normal mode (around the maximum level available in the reduced cylinder mode), thereby ensuring the generation of torque/power requested in operating an engine while saving fuel. In other words, the switching of an operation mode into the reduced cylinder mode will be done without unexpected lack of torque/power while saving fuel as much as possible, irrespective of the variation of the conditional and/or environmental parameters of the engine. Especially for a hybrid driving system having an internal combustion engine and dynamotors, where a target value of torque or power to be generated is determined with an input device, e.g. an accelerator pedal of a driver, the direct monitoring of the output torque solely from the engine makes it easy to adjust the total output power (from the engine plus dynamotors) to the target level.
In the inventive device, when an output shaft of a multi-cylinder engine is operationally linked to a dynamotor e.g. through a planetary gear, a dynamotor may be useful as the detector detecting engine output torque. In a hybrid driving system where the output shaft of an internal combustion engine is operationally linked to an electric motor and an electric generator and wheels of a vehicle are driven with a shaft of the planetary gear linked to the motor, the torque detector will be the electric generator. In this case, the engine output torque can be detected precisely from reaction torque on the generator during driving the wheels. In this regard, as noted, upon the switching of an operation mode, an abrupt variation or a surge in torque is generated due to the variation of the mass of motion of an engine accompanied by the transient variation of engine revolution. In order to avoid transient variation of torque and revolution, the output torque may be modified for following its target value, e.g. by operating the electric motor or generator. The direct monitoring of the actual output torque makes the torque modification much easier.
By the way, the output performance of an engine varies with difference within tolerance in manufacturing an engine, abrasion in parts due to use of an engine, etc. Accordingly, individual engines have different maximum power available per cylinder, supplied with a certain fuel amount at wide opened throttle, and thus different ideal conditions for the switching of an operation mode. The maximum power available per cylinder in each engine also varies with environmental conditions, e.g. on a highland. Thus, the judgment criteria in determining an operation mode may be modified appropriately for individual engines through a learning process. In one embodiment of the present invention, when an engine is operated in the reduced cylinder mode, output torque at a certain engine revolution and at a predetermined upper limit of throttle angle is, preferably automatically, set to the upper limit of engine output torque at the certain engine revolution in the reduced cylinder mode.
With respect to the way of the judgment of an operation mode, since maximum available torque generated by each cylinder is dependent upon engine revolution, the judgment of the operation mode based upon actually outputted torque from the engine may be performed by using a two-dimensional map of engine revolution and engine torque, which map is divided into full cylinder operation (normal operation) region and reduced cylinder operation region. An operation mode to be executed may be judged according to which region a current engine operating condition defined with torque and revolution is fallen into. Then, it is allowed to execute the reduced cylinder operation mode to the full extent while ensuring the generation of output torque requested of the engine, and thereby improving fuel economy while suppressing the emission of exhaust gas. In this regard, as noted, maximum available torque/power per cylinder also varies with internal and external conditions of an engine, such as atmospheric pressure and temperature. Thus, the map for determining the operation mode may be modified appropriately in conjunction with the environmental conditions of the engine. The map may be modified through a learning process as described above.
Thus, it is an object of the present invention to provide new and novel control devices for cylinder reducing operation for a multi-cylinder engine, enabling the switching of an operation mode at a more appropriate timing than ever, and thereby allowing reduced cylinder operation to the full extent while ensuring the generation of required output torque and improving fuel economy.
It is another object of the present invention to provide such devices directly monitoring the output torque from an engine, and thereby avoiding unexpected shortage of output torque/power upon the switching of the operation mode due to the variation of environmental conditions of the engine.
It is a further object of the present invention to provide such devices wherein, through monitoring actual output torque from an engine, the transient variation of torque or power is modified for preventing any mechanical shock on an engine system or a vehicle body equipped therewith.
It is a further object of the present invention to provide such devices in which criteria for judging an operation mode of an engine are modified through a learning process in order to execute the switching of the operation mode appropriately for individual engines.
Other objects and advantages of the present invention will be in part apparent and in part pointed out hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings,
FIG. 1 is a diagram of a hybrid driving system for a vehicle incorporating a multi-cylinder engine and a control device for cylinder reducing operation of one embodiment according to the present invention.
FIG. 2 shows a map of engine output torque Te and revolution Ne, defining a normal (full cylinder) operation region and a reduced cylinder operation region according to the present invention.
FIG. 3 is a flowchart showing cylinder reducing operation control routine executed in the preferred embodiment in the vehicles in FIG. 1 according to the present invention;
FIG. 4 shows diagrams of time variations of throttle valve opening and engine output torque during the switching from the normal mode to the reduced cylinder mode (A) and from the reduced cylinder mode to the normal mode (B).
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a diagram of a hybrid driving system for a vehicle, having a multi-cylinder internal combustion engine 10 and dynamotors 16 and 18 , cooperating to generate power appropriately determined under the control of Electronic Control Unit (ECU) 38 . A control device for cylinder reducing operation of a preferred embodiment according to the present invention is implemented in Electronic Control Unit (ECU) 38 by installing appropriate software.
In the illustrated system, an output shaft (crank shaft) 12 of the engine 10 is linked to one of three rotational elements of a planetary gear 14 , and the other two rotational elements of the planetary gear each are linked to an electric generator (dynamotor G) 16 and an electrical motor (dynamotor M) 18 , respectively. A gear 20 , mounted on the linkage between the planetary gear 14 and motor 18 , engages a gear 22 , through which the rotation from the planetary gear 14 (the crankshaft 12 ) and motor 18 is transmitted to a differential gear 24 and wheel axles 26 and 28 driving a pair of wheels 30 , 32 . The generator 16 , driven with the engine 10 via the planetary gear, charges a battery 36 through an inverter 34 , and the motor 18 is driven with electric current supplied from the battery 36 through the inverter 34 .
ECU 38 , which may incorporate a computer which may be of an ordinary type including a central processor unit, a read only memory, a random access memory, input and output port means and a common bus interconnecting these elements, electronically controls the operation of the engine 10 , generator 16 , motor 18 and inverter 34 in accordance with software. ECU 38 , typically receiving signals indicating engine operating conditions and external (environmental) conditions of the engine and vehicle from appropriate sensors, determines a target value of torque/power to be generated in the driving system and operates portions to be controlled in the system such as a throttle valve, in order to bring actual torque/power into conformity with the target value. In the cylinder reducing operation control, the number of working cylinders is controlled by rendering a half number of the cylinders inactive selectively in the manner as described below.
In operation, ECU 38 first judges an operation mode of the engine with a two-dimensional map of engine output torque Te and engine revolution Ne, as shown in FIG. 2 , stored elsewhere in ECU. The output torque from the engine, used for the judgment of the operation mode of the engine, may be obtained from a signal indicating reaction force or torque in the generator 16 against the engine torque during driving the wheels. As seen from FIG. 2 , the map includes a region of a normal operation mode and a region of a reduced cylinder operation mode. When an engine condition defined with output torque Te and revolution Ne is fallen into the normal operation region, the engine is to be operated in the normal operation mode where all of cylinders are operated. If, however, a condition defined with output torque Te and revolution Ne is fallen into the reduced cylinder operation region, the engine is to be operated in the reduced cylinder mode.
For the purpose of improvement of fuel economy, the reduced cylinder operation region should be set out such that the reduced cylinder operation is to be executed as long as the generation of the target torque or power is accomplished by the reduced number of working cylinders. This is because energy efficiency of an engine is high when the load per cylinder is high as described above. Thus, preferably, the upper limit of torque in the reduced cylinder region will be set to a substantial maximum torque available solely with working cylinders in the reduced cylinder mode (a half number of cylinders in the engine). Between the normal and reduced cylinder operation regions, a neutral zone (“hysteresis zone”) where no switching of the operation mode is executed is provided for avoiding control hunting upon the mode switching.
The map of torque vs. revolution as shown in FIG. 2 is set out during manufacturing the engine on the assumption that the engine is operated under a standard condition. The output performance of the engine, however, is dependent upon its environmental conditions and individual engines have different output characteristics within tolerance, abrasion due to use, etc. Thus, the map of torque vs. revolution as shown in FIG. 2 may be appropriately modified. One of the ways of the map modification is through a learning process, which will be described below in more detail.
Upon the switching of the operation mode, the engine output torque or power varies transiently due to the variation of revolution induced from the inertial mass change of the engine and the retardation of response of intake airflow. In the present invention, however, since actual torque outputted solely from the engine 10 is monitored as described above, transient torque or power variation upon the mode switching can easily be compensated under the control of ECU 38 by using a dynamotor, and thereby undesirable mechanical impact on the driving system can be effectively suppressed.
In the followings, the operation of the inventive control device is explained about with an exemplary flowchart as shown in FIG. 3 .
The control according to the flowchart may be started by a closure of an ignition switch (not shown in FIG. 1 ) and cyclically repeated at a cycle time of millisecond order during the operation of the vehicle.
In step S 1 , the signals, required for the following process from sensors provided elsewhere in the driving system, including the signal of engine revolution Ne and the signal of reaction torque in the generator 16 , i.e. torque applied from the engine 10 onto the rotational element in the planetary gear 14 linked to the generator 16 , are read in. Then, in step S 2 , actual output torque Te solely from the engine 10 is determined based upon the torque signal from the generator.
Then, through steps S 3 -S 9 , compensation of transient variation of torque after the switching of the operation mode is executed. The detailed explanation of these steps will be described later.
In steps S 10 - 19 , by using the map of actual output torque Te vs. engine revolution Ne in FIG. 2 , the operation mode is judged to either of the normal operation and reduced cylinder operation modes. Firstly, in step S 10 , it is judged if a condition defined with Te and Ne is fallen into the normal operation region. If so, it is judged if the engine is operated in the normal mode (step S 11 ). If so, the normal mode is maintained (S 14 ). If the engine is operated in the reduced cylinder mode, the operation mode is switched into the normal mode (step S 12 ) and a first timer of transient term tq, which will be used in the torque compensation in steps S 3 -S 9 in the subsequent cycles, is set to its initial value tq 0 .
If a condition of Te and Ne is fallen into in the reduced cylinder region, the process goes through steps S 15 and, in step S 16 , it is judged if the engine is operated in the reduced cylinder mode. If so, the reduced cylinder operation is maintained (S 19 ). If, however, the normal operation is executed, the mode is switched into the reduced cylinder mode in step S 17 and a second timer of transient term tp is set to its initial value tp 0 .
If the condition is fallen into the hysterisis zone, the process reaches to step S 20 via step S 15 , and it is judged if the engine is operated in the normal mode. If so, the normal operation is maintained (step S 14 ), and otherwise, the reduced cylinder operation is maintained (step S 19 ). Accordingly, when a current condition is within the hysterisis zone, no switching of the operation mode is executed, and thus control hunting upon the switching is prevented.
Returning to steps S 3 -S 9 , in order to avoid a mechanical impact due to torque variation upon the changing of the number of working cylinders, the transient torque compensation routine is executed after the switching of the operation mode.
Referring to FIG. 4(A) , when the engine operation is switched from the normal into the reduced cylinder mode (at t 1 ) in response to the reduction of the output torque (demanded by ECU 38 through the closure of throttle opening), the output torque from the engine is excessively reduced as indicated in the bold line in the lower graph in FIG. 4(A) because of the reduction of the number of working cylinders. This is because, although the throttle opening of the engine is increased in response to the mode switching as shown in the upper graph in FIG. 4(A) for recovering the required torque, the response of the output torque is delayed due to the variation of the inertial mass of the rotation and the retardation of intake airflow. Thus, in order to compensate for transient, excessive reduction or shortage in the output torque after the mode switching, the additional torque generated with the motor 18 is added into the output torque, and thereby smoothly connecting the output torque before and after the mode switching as indicated by a thin line in FIG. 4(A) .
Similarly, referring to FIG. 4 ( 13 ), when the engine operation is switched from the reduced cylinder mode into the normal mode in response to the increase of the output torque, the output torque from the engine is excessively increased, as indicated in the bold line in the lower graph in FIG. 4(B) , because of the increase of the number of working cylinders. In this case, the excessively increased torque or transient surplus torque is absorbed with the generator 16 and thereby the output torque from the driving system varies smoothly before and after the mode switching as indicated by a thin line in FIG. 4(B) .
For the above-mentioned torque compensation, the first and second timers tq, tp, each value of which is reduced to zero during cycling the routine, are employed for judging if the state of the engine is in a transient phase after the mode switching. Once the mode switching is executed, the first or second timer tq, tp is set to tq 0 or tp 0 , respectively, as described above (At the staring of the control, the first and second timers tq, tp is set to 0.). The amounts of tq 0 and tp 0 may be appropriately determined based upon engine parameters. Then, when the process returns to START, it is judged if tp or tq is larger than 0 in steps S 3 or S 4 .
If tp >0(n step S 3 ), indicating that the engine is in the transient phase after the switching from the normal mode into the reduced cylinder mode, the second timer tp is decremented by Δtp, a small amount corresponding to one cycle time of the routine, in step S 6 . Then, the shortage of driving torque outputted from the system is compensated by adding the amount calculated with fp(tp), a function of elapsed time (the timer value), to the output torque, as indicated by thin solid line in FIG. 4 (A) in step S 7 . The compensation for the output torque shortage is repeated during the subsequent cycles until the counter tp reaches to zero.
Similarly, if tq >0 (in step S 4 ), indicating that the engine is in the transient phase after the switching from the reduced cylinder mode into the normal mode, the first counter tq is decremented by Δtq, a small amount corresponding to one cycle time of the routine, in step S 8 . Then, the surplus in torque is compensated by absorbing the amount calculated with −fq (tq) from the output torque as indicated by thin solid line in FIG. 4 (B) in step S 9 . The compensation for the output torque surplus is repeated during the subsequent cycles until the counter tq reaches to zero.
When both tp and tp is not larger than 0, these values are set to 0 in step S 5 .
As described above, the upper limit of torque or power available in the reduced cylinder operation can vary with internal and environmental conditions and the use of the engine. Thus, preferably, in order that the reduced cylinder operation is executed to the full extent, the upper limit of the reduced cylinder operation region in the map is modified automatically through a learning process. The routine for modifying the map may be incorporated in the routine of FIG. 3 .
Referring to steps S 21 -S 24 , the learning modification of the map is executed when the engine is operated in the reduced cylinder mode. After step S 19 , it is judged in step S 21 if tp is still larger than 0. If so, the operation of the engine is still in a transient phase. A transient phase, in which the output torque is not stable, is not suitable for the map modification. Thus, the process returns to Start without the map modification.
If the transient phase has ended (tp=0), it is judged in step S 22 whether or not the current throttle opening or angle θ is equal to or exceeds a predetermined maximum allowable value θma (Ne) at the current revolution. If the throttle opening reaches to the maximum allowable level, 5 no further torque can be gained in the reduced cylinder operation. In other words, the output torque from the engine at the substantial full throttle opening is considered to be the upper limit of the reduced cylinder operation. Thus, when the maximum allowable throttle opening is detected, the current torque is set to the upper limit of the reduced cylinder operation region. In this regard, the maximum allowable throttle opening is dependent upon engine revolution so that θma is determined as a function of engine revolution.
In the flowchart, if θ>θma is detected, the current torque Te is stored as the upper limit of the reduced cylinder operation region at the current revolution, Temax(Ne) in step S 23 , and in step S 24 , the upper boundary of the reduced cylinder operation region is modified such that the boundary line passes through the point of Temax (Ne) newly stored in step S 23 . Together with the modification of the upper boundary of the reduced cylinder operation region, preferably, the lower boundary of the normal operation region is modified for keeping the width of hysteresis zone enough to avoid control hunting. Accordingly, the criteria of the judgment of an operation mode are adapted for the current output performance of the engine.
If θ>θma is not detected in step S 22 , the process returns to START without the map modification.
Although the present invention has been described in detail with respect to preferred embodiments thereof and some partial modifications thereof, it will be apparent for those skilled in the art that other various modifications are possible with respect to the shown embodiments within the scope of the present invention. | A control device for cylinder reducing operation of a multi-cylinder engine for a vehicle controls the number of working cylinders in the engine more appropriately for fuel economy while ensuring the operational stability of the engine and comfortable drivability of the vehicle. The control device comprises a detector detecting engine output torque and judges if cylinder reducing operation is to be executed while referring to the engine output torque. Because of the detection of engine output torque, cylinder reducing operation will be executed as long as torque requested of the engine is available from the reduced number of working cylinders, thereby ensuring the generation of torque required in operating the engine while saving fuel as much as possible. Through a learning process, criteria for the judgment of execution of cylinder reducing operation are modified to be adapted for any variation of engine output performances. | 8 |
RELATED APPLICATIONS
This patent application claims priority to U.S. Provisional Patent Application Ser. No. 60/977,317, having title “Case Erector”, filed on 3 Oct. 2007 in the United States, commonly assigned herewith, and hereby incorporated by reference.
BACKGROUND
Cases (e.g. cardboard boxes) are commonly sold in a folded flat (i.e. a knocked down) configuration. A case erector is a machine that assembles cases from the folded flat configuration into a three-dimensional form, typically having bottom box flaps taped or glued shut.
Known case erectors have two arms, typically configured with suction or vacuum cups, which grasp two adjacent sides of the box, respectively. Each arm then moves through 45 degrees thereby opening the box. In an application with a single arm, the single arm may move through 90 degrees. In either application, such arms are supported by bearing surfaces, which allow the pivotal rotation.
It is desirable to locate the fold between the two adjacent sides of the box that are grabbed by the two arms co-linearly with an axis about which the two arms pivot. This results in a design challenge, in that it is desirable to locate a (usually) vertical shaft (about which the arms pivot) in the same location that it is desirable to locate the fold in the box.
Two solutions are common. In a first solution, the fold in the box (between the two adjacent sides that are grasped by the arms) can be located “near” (but not exactly collinear with) the shaft about which the two arms pivot. This will cause the box to skew as it is opened. The skew occurs because the fold between the two adjacent sides of the box and the two arms do not pivot about the same virtual center point. This skew is generally unacceptable, and therefore a second solution is common.
In the second solution, the shaft about which the two arms pivot is located above (or below) the box, so that if the shaft were extended in one's imagination, the shaft would be co-linear with the fold between adjacent sides of the box. Since the shaft is located above the box as the box is moved into position to be opened, the arms must extend laterally outward from the shaft and also extend down to the box, so that vacuum cups carried by the arms may contact the adjacent sides of the box. This makes the overall device heavier and more complex, and requires arms having increased strength due to their length and other factors. While this solution allows the arms to be kept parallel to the box sides, (the arms reach down from above or up from below) the structure required to support the erecting arms must be more robust which will increase cost, complexity and overall size of the mechanism.
SUMMARY
A case erector is configured to open folded cases. In one example, the case erector provides first and second arms, each having at least one suction or vacuum device. A planar bearing surface allows at least one of the arms to move between an open position and a closed position. The planar surface defines a semi-circular channel about a virtual center point. In operation, a fold between two adjacent sides of the case is moved into a virtual line passing through the virtual center point while the arms are in the open position, thereby allowing space for the case to enter. The arms are then moved to the closed position, wherein the first and second arms grasp the two adjacent sides, respectively, of the folded flat case. The case is then opened by moving the arms into the open position while the arms maintain their grasp of the case. Movement to the open position is performed by moving each arm through 45 degrees or one arm through 90 degrees. Movement of the arms in a rotary manner about the virtual line results from rotation of a plate supporting each arm, wherein each plate moves against the planar bearing surface and wherein the plate has one or more attached flanges moving through the semi-circular channel defined in the planar bearing surface.
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 or essential features of the claimed subject matter, nor is it intended for use as an aid in determining the scope of the claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description is described with reference to the accompanying figures. In the figures, the left-most digit(s) of a reference number identifies the figure in which the reference number first appears. The use of the same reference numbers in different figures indicates similar or identical items.
FIG. 1 shows an isometric view of an example case erector, with the arms in the open position.
FIG. 2 shows an isometric view of the case erector of FIG. 1 , with the arms in the closed position.
FIG. 3 shows an orthographic top (plan) view of an example case erector, with the arms in the open position.
FIG. 3A shows an isometric view similar to that of FIG. 3 .
FIG. 4 shows an orthographic top (plan) view of the case erector of FIG. 3 , with the arms in the closed position and a case in the unassembled position.
FIG. 5 shows an orthographic top (plan) view of the case erector of FIG. 3 , with the arms in the open position and a case in the erected or open position.
FIG. 6 shows an orthographic side view of an example case erector, with the arms in the open position.
FIG. 7 shows an orthographic top view of an example case erector, with the arms in the open position.
FIG. 8 shows a section view of the bearing assembly of FIG. 7 .
FIG. 9 shows a further example of a bearing surface that could be used in an embodiment of the case erector.
DETAILED DESCRIPTION
Overview
The following discussion is directed to systems and methods that erect cases (e.g. systems that open cardboard boxes from a disassembled state to an assembled state). In one example, a case erector configured to open folded cases provides first and second arms, each having at least one attachment device, such as a suction or vacuum device or clamp assembly. A planar bearing surface allows at least one of the arms to move between an open position (wherein a folded flat case is received) and a closed position (wherein the folded case is grabbed) and then moved to the open position (wherein the case is opened into a 3-D box-like shape with open or no flaps on the top and flaps on bottom). In a preferred configuration, each of the two arms moves through approximately 45 degrees. The planar bearing surface defines a semi-circular channel about a virtual center point. In operation, a fold between two adjacent sides of the case is moved into coincidence with a virtual line passing through the virtual center point. Once the fold of the case is in position in the virtual line passing through the virtual center point, the first and second arms move from the open position to the closed position to grasp the two adjacent sides, respectively. Each arm is supported by a plate that moves against a planar bearing surface, wherein the plate is held in place by at least one flange that moves within a semi-circular channel defined within the planar bearing surface. Thus, the plate supporting each arm moves (rotates) in a circular manner, about the virtual center point. The case is then opened as both arms move through 45 degrees from the closed position to the open position, thereby opening the case. Because the fold (i.e. the corner) of the case was located in a virtual line passing through the virtual center point of the semi-circular channel, the arms will remain parallel to the two adjacent box sides, as the box opens in a square or non-skewed manner.
Examples of Case Erectors
FIG. 1 shows an isometric view of an example case erector 100 , with the arms in the open position. In particular, first and second arms 102 , 104 are separated by 90 degrees in the open position, which allows a case to be moved into position between the arms. The 90 degrees between the arms 102 , 104 also holds adjacent sides of a box in the appropriate configuration when the box is opened. Each arm 102 , 104 may include one or more attachment devices, such as suction cups 106 , which are typically powered by a vacuum source. Alternatively, a clamping assembly could be used.
The arm 102 is supported by a plate 108 that rotates against a planar bearing surface 110 . (The arm 104 is supported by a similar plate, which is on the other side of base 118 and therefore unseen in FIG. 1 .) While a plastic or UHMW material is used for the bearing surface 110 in the example of FIG. 1 , metal or alternative material may also be used. A flange 112 attached to the plate 108 moves within a channel 114 defined in the bearing surface 110 . Thus, rotation of the plate 108 is in a circular direction, due to the movement of the flange within the semi-circular channel 114 . Accordingly, the circular rotation of the plate 108 moves the attached arm 102 in a circular direction. The channel 114 is semi-circular, to allow rotation of the plate 108 between an open position wherein the arm 102 allows a folded case to enter, a closed position wherein the folded case is grasped by the arm 102 , and back to the open position wherein the case is opened. Thus, the plate 108 and attached arm 102 moves over approximately 45 degrees, and the bearing surface 110 remains fixed. Similarly, the second arm 104 moves according to rotation of a second plate over 45 degrees, wherein the rotation is through a second semi-circular channel defined a second bearing surface better seen in FIG. 6 .
The channel 114 defined in the bearing surface 110 is typically semi-circular in shape, and may extend over approximately 270 degrees of a circle, depending on the application. The center of the circle (about which the semi-circular channel 114 is defined) can be thought of as a “virtual center” since no component is positioned at that location. In fact, the bearing surface 114 defines a notch (best seen as 308 in FIG. 3 ), which allows a fold between two sides of a case (i.e. a “corner” of the case) to be located at the center or “virtual center” of the semi-circular channel 114 .
The arms 102 , 104 are moved by actuators 116 and 117 , which may operate using a compressed air power source. Alternative technology, such as motor and/or gears may be substituted. In one example, the actuators 116 , 117 are attached to plates 108 and 604 (see FIG. 6 ); alternatively, the actuators are attached to the arms 102 , 104 . In either case, the actuators provide the force to move plates 108 and 604 against the fixed-location bearing surfaces 110 and 602 (see FIG. 6 ), whereby the plate and attached arm rotate about the center point.
Both arms 102 , 104 , supporting plates and bearing surfaces, actuators 116 , 117 and other components are supported by a base 118 and two bearings 120 . The bearings 120 allows the arm assembly to move along a shaft 122 . Typically, the case, once opened, is moved along the shaft 122 into a plow, which aids in closing and sealing the bottom flaps of the case. A hose assembly 124 has a linkage design, which supports the hoses as the arm and bearing surface assembly moves along the shaft 122 .
In the example of FIG. 1 , the attachment devices 106 (e.g. vacuum cups) are attached to an adjustment plate 126 defining a plurality of adjustment slots 128 . A bracket 130 holding the attachment device 106 can therefore be positioned in any desired location.
FIG. 2 shows an isometric view of the case erector 100 , with the arms 102 , 104 in the closed position. Note that in the closed position, the suction cups 106 of the second arm 104 are separated from the suction cups of the first arm 102 by only the thickness of the disassembled case. Thus, FIG. 2 shows the arms 102 , 104 in the “closed” position wherein they are grasping the still closed case. The case is not shown in this view, for clarity of illustration. Once the two adjacent sides of the case are grasped by the arms 102 , 104 , the arms are again rotated into the “open” configuration seen in FIG. 1 .
A comparison of FIGS. 1 and 2 shows that the plate 108 has rotated counter-clockwise by 45 degrees. This has caused the attached arm 102 to rotate 45 degrees. The plate 108 was constrained in its rotation by the flange 112 , attached to the plate 108 , which travels within the channel 114 of the bearing surface 110 . The arm 104 has similarly rotated 45 degrees. However, the plate to which it is attached is located under supporting plate 118 , and is therefore not shown. Note that the plate 108 somewhat resembles a piece of pizza with a portion near the center point removed. Removal of this portion near the center point results in an open area that allows the fold of the case to move into a collinear position with a virtual center line passing through the virtual center point, wherein the virtual center point is the center of the semi-circle formed by the channel 114 .
FIG. 3 shows an orthographic top (plan) view of an example case erector 100 , with the arms 102 , 104 in the open position. In this view, an unopened case 300 is shown. The fold 302 between a first side 304 and a second side 306 of the case 300 is located at the center or virtual center 308 of the semi-circle defined by the channel 114 defined in the bearing surface 110 (better seen in FIG. 1 ). Thus, the center 308 of the semi-circular channel 114 (see FIG. 1 ) is located (referring now to FIG. 3A ) in a notch 310 defined in the bearing surface 110 . Similarly, a notch 312 is defined in the plate 108 , which prevents the plate from extending to the center 308 . And further, the supporting plate 118 had defined in it a similar notch 314 . Thus, the notch 310 in the bearing surface 110 , the notch 312 in the plate 108 and the notch 314 in the supporting plate 118 allow the fold 302 of the case 300 to be located at the center point 308 .
Note that in the view of FIG. 3 , the actuator 116 has extended to rotate the plate 108 supporting arm 102 into its most clockwise position. The plate supporting the arm 104 (and a bearing surface within which is defined a channel that controls movement of the plate) will be better seen in later figures, and is located below the plate 118 .
FIG. 4 shows an orthographic top (plan) view of the case erector 100 , with the arms 102 , 104 in the closed position. Two adjacent sides of the box 300 have been grasped by the arms. The actuator 116 has retracted, and the plate 108 supporting the arm 102 has rotated counter clockwise in response. Note that when the arms 102 , 104 open again to the positions seen in FIG. 3 , the box 300 will be opened, with the two adjacent sides 304 , 306 still attached to arms 102 , 104 , respectively.
FIG. 5 shows an orthographic top (plan) view of the case erector 100 , with the arms 102 , 104 in the open position and the case fully opened. Two adjacent sides 304 , 306 of the box 300 have been moved to separate them by 90 degrees, thereby opening the case (box). The actuator 116 has extended, and the plate 108 supporting the arm 102 has rotated clockwise in response. Note that when the arms 102 , 104 open again to the positions seen in FIG. 3 , the box 300 will be opened, with the two adjacent sides 304 , 306 still attached to arms 102 , 104 , respectively.
FIG. 6 shows an orthographic side view of an example case erector 100 , with the arms 102 , 104 in the open position. Note that if an opened box were held by the arms, then the assembly 100 would be ready to move to the right along the bearings 120 and supported by the shaft 122 . The hose assembly 124 would extend as the arm assembly moved along the shaft 122 .
FIG. 6 shows the plate 108 supporting the arm 102 and the bearing surface 110 seen in perspective in FIG. 1 . Below the bearing surface is a flange or base 118 . Below the base 118 is a second bearing surface 602 against which rotates a plate 604 . The second bearing surface 602 and plate 604 are associated with the second arm 104 . The second bearing surface 602 defines a semi-circular channel through which a flange attached to the plate 604 moves. Thus, the bearing surface 602 is stationary, but an actuator 117 moves the plate 604 through approximately 45 degrees in either direction, thereby moving the arm 104 through 45 degrees. The semi-circular channel in the bearing surface 602 has a center point that is along a vertical line that also includes the center point of the channel 114 defined in the bearing surface 110 . Thus, both arms 102 , 104 pivot about the same virtual center point, and the fold between the two adjacent sides of a case to be opened is positioned along a vertical line through those center points.
FIGS. 7 and 8 show orthographic views of an example case erector.
FIG. 9 shows a further example of a bearing surface that could be used in an embodiment of the case erector. Thus, the plastic surface 110 having channel 114 could be replaced by a constant radius rail, or similar, as shown.
CONCLUSION
Although aspects of this disclosure include language specifically describing structural and/or methodological features of preferred embodiments, it is to be understood that the appended claims are not limited to the specific features or acts described. Rather, the specific features and acts are disclosed only as exemplary implementations, and are representative of more general concepts. | A case erector is configured to open folded cases. In one example, the case erector includes a planar bearing surface. A semi-circular channel is defined in the planar bearing surface about a center point. Additionally, a notch is located so that the planar bearing surface does not extend to the center point of the semi-circular channel. A plate is in contact with the planar bearing surface. The plate has at least one flange sized for travel within the semi-circular channel so that the plate rotates against the planar bearing surface in a circular manner about the center point. A notch is defined in the plate so that the plate does not extend to the center point of the semi-circular channel. An arm is connected to the plate so that the plate and the arm rotate together with respect to the planar bearing surface. In operation, a folded edge of a folded case is positioned at the center point. One or two arms, moved by plates rotating on bearing surfaces, attach to and open the folded case. | 1 |
DIVISIONAL REISSUE APPLICATIONS
Notice: More than one reissue application has been filed for the reissue of U.S. Pat. No. 6 , 611 , 361 . The other reissue applications are application Ser. Nos. 11 / 212 , 137 , 11 / 808 , 423 , 11 / 892 , 177 , 11 / 892 , 179 , and 11 / 892 , 176 .
DOMESTIC PRIORITY INFORMATION
This is a direct divisional of application Ser. No. 11 / 212 , 137 , filed Aug. 26 , 2005 ; the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an image process technique, and in particular to a method for restoring a compressed image by using a hybrid motion compensation discrete cosine transform (hybrid MC/DCT) mechanism, and an apparatus therefor.
2. Description of the Background Art
In general, image compression techniques, such as MPEG1 and MPEG2 employ a hybrid motion compensation discrete cosine transform (hereinafter, referred to as “hybrid MC/DCT”) mechanism in order to improve compression efficiency. The hybrid MC/DCT mechanism is roughly divided into an encoding process and a decoding process. In the encoding process, an original image is divided into a plurality of blocks in order to compress information in a spatial section, a second-dimensional discrete cosine transform is performed on each block, and redundancy information in the image or between the images is reduced by using the correlation on a time axis among the images in order to decrease information in a temporal section. In the decoding process, the steps of the encoding process are performed in a reverse order. An encoder and a decoder are necessary to carry out the hybrid MC/DCT mechanism.
FIG. 1 is a block diagram illustrating an image encoder according to a related art. As shown therein, an input image signal is subtracted from an image signal moved from and compensated by an image memory 9 , passed through a first switching unit 2 , and inputted to a DCT unit 3 . The DCT unit 3 performs a discrete cosine transform on the inputted image signal. A quantization unit 4 quantizes the image signal, and outputs a DCT coefficient (q). An inverse quantization unit 6 inversely quantizes the DCT coefficient (q), and an inverse DCT unit 7 carries out an inverse discrete cosine transform thereon, thereby restoring the original image signal. The restored image signal is added to an image signal restored in a previous stage by an adder 8 , and inputted to an image memory 9 . A controller 5 controls switching of the first and second switching units 2 , 10 , and transmits INTRA/INTER information (p=mtype; flag for INTRA/INTER), transmission information (t; flag for transmitted or not), and quantization information (qz=Qp; quantizer indication) to a decoder (not shown in FIG. 1 ). The image memory 9 outputs a motion vector information (v=MV; motion vector) to the decoder. The DCT unit 3 outputs the DCT coefficient (q) to the decoder.
However, information of the original image signal is lost during the process of coding the image signal described above, especially during the quantization process, thereby causing blocking artifacts and ringing effects to the image which is reconstructed in the decoder. The blocking artifacts imply irregularity between the blocks generated due to information loss resulting from the quantization of the low-frequency DCT coefficients, and the ringing effects result from quantization errors of the high-frequency DCT coefficients.
That is, in accordance with a coding technique using the DCT in a coding system of a static image or dynamic image, an image is divided into a plurality of blocks, and the DCT is performed on each block. On the other hand, when the DCT is carried out on the original image, its important information is mainly included in low-frequency elements, and becomes lesser in high-frequency elements. Furthermore, the low-frequency elements include a lot of information relating to adjacent blocks. The DCT does not consider the correlation between the blocks, and quantizes the low-frequency elements by blocks, thereby destroying continuity of the adjacent blocks. It is called the blocking artifacts.
In addition, when the coefficients obtained by performing the DCT are quantized, as a quantization interval is increased, the elements to be coded are decreased, and thus the number of the bits to be processed is reduced. As a result, the information of the high-frequency element included in the original image is reduced, thereby generating distortion of the reconstructed image. It is called the ringing effects. The ringing effects generated by increasing the quantization interval are serious especially in a contour of an object in the reconstructed image.
As techniques for removing the blocking artifacts and the ringing effects, employed are a low pass filtering method and a regularized image restoration method.
According to the low pass filtering method, a plurality of pixels around a predetermined pixel are selected, and an average value thereof is computed. Here, a filter tap or filter coefficients are set by experience. For example, referring to FIG. 2 , there is provided a block of N*N size. Reference numerals A to F depict pixels. Pixels C, D are adjacent to a boundary of the block. In order to reduce irregular variations between the pixels C, D, a k-tap (here, 7-tap) filtering is performed, and a threshold value replacing a D pixel value is computed according to local statistics. There is an advantage in that a computation amount is reduced by utilizing a predetermined threshold value according to the comparison with the local statistics. However, an adaptive processing power in accordance with a quantization parameter is deficient, and thus a screen quality of the restored image is excessively smoothed according to the kind of the images and compression ratio.
The regularized image restoration method adaptively deals with the blocking artifacts in accordance with statistical properties of the image. That is, irregular information around the boundary of the block or in the block is all computed. However, the computed values form a matrix shape, and thus a real time processing is difficult due to the great computation amount. In addition, an average value obtained by a computation result of the irregular information is equally applied to the pixels, regardless of a degree of irregularity. Accordingly, when a block has a high degree of irregularity, it can be reduced. However, in case of a block having a low degree of irregularity, it may be increased. Thus, the system is not adaptive. Also, the information in the temporal section is not processed, and thus irregularity between the images cannot be adaptively processed.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method for restoring a compressed image of an image processing system and an apparatus therefor which can reduce the blocking artifacts and ringing effects generated in a restored image signal.
It is another object of the present invention to provide a method for restoring a compressed image of an image processing system and an apparatus therefor which consider a smoothing degree of an image and reliability for an original image by pixels having an identical property in image block units, during a decoding process.
In order to achieve the above-described objects of the present invention, there is provided a method for restoring a compressed image of an image processing system including: a step of defining a smoothing functional having a degree of smoothing an image and reliability for an original image by pixels having an identical property in image block units; and a step of computing a restored image by performing a gradient operation on the smoothing functional in regard to the original image.
These and other objects of the present application will become more readily apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The present invention relates to a method of decoding a current image.
In one embodiment, the method includes obtaining a pixel value in a current block and at least one adjacent pixel value, obtaining a difference value between the pixel value in the current block and the adjacent pixel value, and obtaining a smoothing value of the current image based on the difference value. A pixel value around a boundary of the current block is smoothed based on the smoothing value and quantization information for the current block. For example, in one embodiment, the quantization information includes a quantization parameter.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become better understood with reference to the accompanying drawings which are given only by way of illustration and thus are not limitative of the present invention, wherein:
FIG. 1 is a block diagram illustrating an image encoder according to a related art;
FIG. 2 illustrates pixels in order to explain a low pass filtering method carried out in the image encoder of FIG. 1 ;
FIG. 3 is a block diagram illustrating an apparatus for restoring a compressed image of an image processing system in accordance with an embodiment of the present invention;
FIG. 4 illustrates an example of a configuration of original pixels in a block of an original image in accordance with the present invention;
FIG. 5 illustrates directions of the irregular smoothing degree of the pixels in accordance with the present invention;
FIG. 6 illustrates an image moved and compensated in regard to a temporal section in accordance with the present invention; and
FIG. 7 illustrates a flowchart of the apparatus for restoring the compressed image of the image processing system in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 3 is a block diagram illustrating an apparatus for restoring a compressed image of an image processing system in accordance with the present invention. As shown therein, a decoder 210 receives INTRA/INTER information (p=mtype), transmission information (t), quantization information (qz=Qp), a discrete cosine transform (DCT) coefficient (q) and motion vector information (v=MV; motion vector) from an encoder (as depicted in FIG. 1 ), and performs decoding. The encoder and the decoder 210 are connected by a communication channel or network. A post processing unit 220 receives image signals Y, U, V, a quantization variable (qz=Qp), a macro block type (mtype) and a motion vector (v=MV) from the decoder 210 , and carries out an operation of restoring the compressed image in accordance with the present invention.
According to the present invention, a smoothing functional is defined in regard to pixels having an identical property by blocks, a regularization parameter is computed based on the smoothing functional, and available values are applied to the regularization parameter, thereby obtaining an image to be restored. Thereafter, an iterative technique, a discrete cosine transform (DCT), a projection and an inverse DCT are sequentially performed on the obtained image, thereby restoring a similar image to the original image. The whole processes will now be described in detail.
Definition of Smoothing Functional
When an original image (f) is compressed and transmitted, an image (g) reconstructed in the decoder 210 is represented by the following equation.
g=f+n (1)
Here, “g” and “f” indicate row vectors re-arranged in a stack-order, namely a scanning order, and “n” indicates a quantization error. When it is presumed that a size of the image is M×M, the original image (f), the reconstructed image (g) and (n) are column vectors having a size of M×1.
An original pixel for the original image (f) is represented by f(i,j). Here, “i” and “j” indicate a position of the pixel in the image.
FIG. 4 illustrates configuration of the original pixels f(i,j) in the block of the original image (f) in order to explain the present invention. Reference numerals in FIG. 4 depict information of the respective pixels. 8×8 pixels are shown in a single block.
The 8×8 pixels in the block are classified into the pixels having an identical property. That is, the pixels are divided in accordance with their position, vertical direction, horizontal direction and smoothing variation in the temporal section. Accordingly, it is defined that a set of the pixels positioned at a boundary of the block in a vertical direction is C VB , a set of the pixels positioned inside the block in the vertical direction is C VW , a set of the pixels positioned at a boundary of a block in a horizontal direction is C HB , a set of the pixels positioned inside the block in the horizontal direction is C HW , and a set of the pixels moved and compensated in the temporal section is C T . The sets C VB , C VW , C HB , C HW , C T are represented by the following expressions.
C VB ={f(i,j): i mod 8=0,1, and j=0,1, . . . , M−1}
C VW ={f(i,j): i mod 8=0,1, and j=0,1, . . . , M−1} (2)
C HB ={f(i,j): j mod 8=0,1, and i=0,1, . . . M−1}
C HW ={f(i,j): j mod 8=0,1, and i=0,1, . . . , M−1}
C T ={f(i,j): f(i,j)εMB inter or f(i,j)εMB not coded }
Here, the set C T is a set of the pixels having a macro block type of “inter” or “not coded” in order to remove temporal redundancy information.
The smoothing functional M(f) for using the regularization restoration method from the above-defined sets C VB , C VW , C HB , C HW , C T is defined as follows.
M(f)=M VB (f)+M HB (f)+M VW (f)+M HW (f)+M T (f) (3)
Here, M VB (f) is a smoothing functional for the set C VB , M HB (f) is a smoothing functional for C HB , M VW (f) is a smoothing functional for the set C VW , M HW (f) is a smoothing functional for the set and C HW , and M T (f) is a smoothing functional for the set C T . The smoothing fuctionals are respectively defined as follows.
M VB (f)=∥Q VB f∥ 2 +α VB ∥g−f∥ 2 W1
M HB (f)=∥Q HB f∥ 2 +α HB ∥g−f∥ 2 W2
M VW (f)=∥Q VW f∥ 2 +α VW ∥g−f∥ 2 W3
M HW (f)=∥Q HW f∥ 2 +α HW ∥g−f∥ 2 W4
M T (f)=∥Q T f∥ 2 +α T ∥g−f∥ 2 W5
Here, first terms in each expression indicate a smoothing degree for the original pixel (reference pixel) and adjacent pixel, and second terms indicate reliability for the original pixel and the restored pixel. “|.|” indicates the Euclidean norm. Q VB , Q VW , Q HB , Q HW , Q T indicate high pass filters for smoothing the pixels in the sets C VB , C VW , C HB , C HW , C T .
The first term at the right side is represented by the following expression.
Q VB f 2 = ∑ n = 0 M - 1 ∑ m ( f ( m , n ) - f ( m - 1 , n ) ) 2 , m = 0 , 8 , 16 , …
Q HB f 2 = ∑ n ∑ m = 0 M - 1 ( f ( m , n ) - f ( m , n - 1 ) ) 2 , n = 0 , 8 , 16 , …
Q VW f 2 = ∑ n = 0 M - 1 ∑ m ( f ( m , n ) - f ( m - 1 , n ) ) 2 , m ≠ 0 , 8 , 16 , …
Q HW f 2 = ∑ n ∑ m = 0 M - 1 ( f ( m , n ) - f ( m , n - 1 ) ) 2 , n ≠ 0 , 8 , 16 , …
Q T f 2 = ∑ n ∑ m ( f MC ( m , n ) - f ( m , n ) ) 2 ( 5 )
The smoothing functionals represented by Expression (4) are quadratic equations, respectively. Thus, local minimizers of each smoothing functional become global minimizers.
FIG. 5 illustrates directions of the irregular smoothing degree of the pixels. There are a single pixel at the center and eight pixels therearound. There are also shown horizontal and vertical arrows starting from the pixel at the center. The arrows respectively depict the directions of the irregular smoothing degree in regard to the four adjacent pixels. That is to say, the irregular smoothing degree is considered in four directions in respect of a single pixel.
FIG. 6 illustrates an image moved and compensated in regard to the temporal section in accordance with the present invention. Arrows depict the correlation of a currently-restored image with a previously-restored image and a succeedingly reconstructed image, respectively.
α VB , α HB , α VW , α HW , α T included in the second terms of Expression (4) are regularization parameters in regard to each set, indicate a ratio of the smoothing degree and reliability, and imply an error element. W 1 , W 2 , W 3 , W 4 , W 5 indicate diagonal matrixes having a size of M×M in order to determine whether each set has an element, and have a value of “1”, or “0” according to whether each pixel is included in a corresponding set. That is, if the respective pixels are included in the corresponding sets, the value of the diagonal elements is “0”. If not, the value of the diagonal elements is
Thereafter, the regularization parameters, α VB , α HB , α VW , α HW , α T are approximated as follows.
Approximation of Regularization Parameters
Approximation of the regularization parameters is a major element determining performance of the smoothing functional. In order to reduce the computation amount, presumptions are made as follows.
(1) A maximum value of the quantization error generated in the quantization process of the DCT region is Qp, and thus it is presumed that the quantization variables Qp are regular in each macro block. For this, the maximum quantization error of the DCT coefficients of each macro block is regularly set to be Qp. (2) It is also presumed that the DCT quantization errors have the Gaussain distribution property in the spatial section.
Under the above presumptions, in case a set theoretic is applied, each regularization parameter is approximated as follows.
α VB = Q VB f 2 g - f W 1 2 = Q VB g 2 g - f W 1 2 = Q VB g 2 ∑ n ∑ m w 1 ( m , n ) Qp 2 ( m , n )
α HB = Q HB f 2 g - f W 2 2 = Q HB g 2 g - f W 2 2 = Q HB g 2 ∑ n ∑ m w 2 ( m , n ) Qp 2 ( m , n )
α VW = Q VW f 2 g - f W 3 2 = Q VW g 2 g - f W 3 2 = Q VW g 2 ∑ n ∑ m w 3 ( m , n ) Qp 2 ( m , n )
α HW = Q HW f 2 g - f W 4 2 = Q HW g 2 g - f W 4 2 = Q HW g 2 ∑ n ∑ m w 4 ( m , n ) Qp 2 ( m , n )
α T = Q T f 2 g - f W 5 2 = Q T g 2 g - f W 5 2 = Q T g 2 ∑ n ∑ m w 5 ( m , n ) Qp 2 ( m , n ) ( 6 )
Here, Q 2 P (m,n) is a quantization variable of a macro block including a (m,n)th pixel of a two-dimensional image.
In Expression (6), denominator terms of the respective regularization parameters are a sum of the energy for the quantization noise of the elements included in each group. As described above, the values of the regularization parameters may be easily computed by applying the set theoretic under the two presumptions.
Computing Pixels to be Restored From Smoothing Functional
Only the original image needs to be computed. However, the smoothing functional includes a square term of the original image. Accordingly, in order to compute the original image, a gradient operation is carried out on the smoothing functional in regard to the original image. A result value thereof is “0”, and represented by the following expression.
∇ f M(f)=2Q T VB Q VB +2Q T HB Q HB +
2Q T VW
Q VW +2Q T HW Q HW +2Q T
TQ T −2α VB W T 1 W 1 (
g−f)−2α HB W T 2 W 2 (
g−f)−2α VW W T 3 W 3 (
g−f)−2α HW W T 4 W 4 (
g−f)−2α T (g−f)=0 (7)
Here, a superscript “T” indicates a transposition of the matrix.
A restored image similar to the original image (f) can be obtained by Expression (7). However, operation of an inverse matrix must be performed, and thus the computation amount is increased. Thus, in accordance with the present invention, the restored image is computed by an iterative technique which will now be explained.
Iterative Technique
When Expression (7) is iterated k times, an iterative solution f k+1 is represented by the following expression.
f k+1 =f k +β[Ag−Bf k ],
A=α VB W 1 +α HB W 2 +α VW W 3 +α HW W 4 +α T W 5 (8)
B=(Q T VB Q VB +Q T HB Q HB +Q T VW Q VW +Q T HW Q HW +Q T T Q T )+A
In Expression (8), “β” is a relaxation parameter having a convergence property. Expression (8) can be represented by the following expression by computing consecutive iterative solutions.
(f k+1 −f K )=(I−B)(f k −f k−1 ) (9)
Here, “I” is an identity matrix, and the matrix B has a positive definite property. Therefore, when the following condition is satisfied, the iterative solutions are converged.
∥I−B∥<1 (10)
Expression (10) can be summarized as follows.
0 < β < 2 1 + max i λ i ( A ) ( 11 )
In Expression (11), “λ(A)” depicts an eigen value of the matrix A. A considerable amount of computation is required to compute the eigen value λ(A). However, the high pass filters have a certain shape determined according to the positions of the respective pixels, regardless of the image. Accordingly, before computing Expression (8), the eigen value λ(A) can be replaced by a fixed value. The value may be computed by a power method which has been generally used in interpretation of numerical values.
For example, a computation process of an eigen value of an iterative solution will now be explained.
x k+1 =Kx k
Here, “x k ” is a vector of M×1, and “K” is a positive-definite symmetric M×M matrix. The eigen value λ′ of the matrix K is approximated as follows.
λ ′ = ( x k + 1 ) T x k ( x k T ) x k
In the above expression, if “k” is to infinity, the eigen value λ′ is approximated to a real value.
Thus, the iterative solution represented by Expression (8) is computed. The next thing to be considered is a time of finishing the iterative technique, in order to determine the number of iteration. Here, two standards are set as follows.
Firstly, a predetermined threshold value is set before starting iteration, an image obtained after iteration, namely a partially-restored image is compared with the previously-set threshold value, and it is determined whether the iteration technique is continuously performed according to a comparison result.
Secondly, the iteration technique is performed as many as a predetermined number, and then finished.
According to the first standard, a predetermined threshold value is set in performing iteration, and thus a wanted value is obtained. However, although the iteration number is increased, it may happen that the predetermined threshold value is not reached. On the other hand, the second standard is performed by experience, but can reduce a computation amount. Therefore, the two standards may be selectively used according to the design specification.
FIG. 7 is a flowchart of the apparatus for restoring the compressed image of the image processing system in accordance with the present invention. As shown therein, in the step S 1 , the quantization variable Qp and the image signals Y, U, V are inputted, and the regularization parameter is approximated as described above. In the step S 2 , the gradient operation is performed on the smoothing functional in regard to the original image. In the step S 3 , an iterative solution, namely a wanted restored image is obtained by the iteration technique. In this step, employed are the image signals Y, U, V and the motion vector MV which is moved and compensated.
In the step S 4 , the DCT is performed on the restored image corresponding to the iterative solution f k+1 obtained in the step S 3 . An (u,v)th DCT coefficient of the two-dimensional restored image is expressed as F k+1 (u,v), and must exist in the following section in accordance with a property of the quantization process.
G(u,v)−Qp≦F k+1 (u,v)≦G(u,v)+Qp (12)
Here, “Qp” is a maximum quantization error as explained above, and “G(u,v)” is a two-dimensional DCT coefficient obtained by performing the DCT on the reconstructed image (g). The DCT coefficients F k+1 (u,v) and G(u,v) are represented as follows. In Expression (13), “B” indicates a block DCT.
F k+1 (u,v)=(Bf k+1 )(u,v), and G(u,v)=(Bg)(u,v) (13)
In the step S 6 , a section of the DCT coefficient of the restored image is set as in Expression (12). Accordingly, in case the DCT coefficient F k+1 (u,v) of the restored image is not in the predetermined section, it must be projected as follows. A projection process is carried out in the step S 7 , and represented by Expression (14).
P(F k+1 (u,v))=G(u,v)−Qp, if F k+1 (u,v)<G(u,v)−Qp
P(F k+1 (u,v))=G(u,v)+Qp, if F k+1 (u,v)>G(u,v)−Qp 14
P(F k+1 (u,v))=F k+1 (u,v), otherwise.
Expression (14) will now be described.
When F k+1 (u,v) is smaller than G(u,v)−Qp, the projected restored image P(F k+1 (u,v)) is mapped to G(u,v)−Qp. In case F k+1 (u,v) is greater than G(u,v)+Qp, the projected restored image P(F k+1 (u,v)) is mapped to G(u,v)+Qp. Otherwise, the projected restored image P(F k+1 (u,v)) is mapped as it is.
In the step S 8 , the inverse DCT is performed on the mapped image P(F k+1 (u,v)) in the spatial section. The finally restored image is represented by Expression (14).
f k+1 =B T PBf k+1 (15)
Here, “B” indicates the DCT, “P” indicates mapping, and “B T ” indicates the inverse DCT.
The restored image is stored in a frame memory in the post processing unit 220 (Step S 9 ). The post processing unit 220 performs motion compensation based on the motion vector MV (Step S 10 ). The motion and compensation image is employed for generation of the regularization parameter for a succeeding image and the iteration technique.
The post processing unit 220 outputs the restored motion and compensation image as a video signal to a display (not shown) (Step S 11 ).
As discussed earlier, the present invention can restrict a section of the restored image for the respective pixels by using the various regularization parameters. In addition, the present invention prevents flickering which may occur in the dynamic image compression technique.
Consequently, the present invention adaptively prevents the blocking artifacts and the ringing effects for the pixels having an identical property in image block units, and thus can be widely used for the products of the hybrid MC-DCT mechanism.
As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiment is not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims. | The present invention relates to an image processing technique, and in particular to a method for restoring a compressed image by using a hybrid motion compensation discrete cosine transform (hybrid MC/DCT) mechanism, including: a step of defining a smoothing functional having a smoothing degree of an image and reliability for an original image by pixels having an identical property in image block units; and a step of computing a restored image by performing a gradient operation on the smoothing functional in regard to the original image, thereby preventing the blocking artifacts and the ringing effects in regard to the pixels having an identical property in image blocks.In one embodiment, the method includes obtaining a pixel value in a current block and at least one adjacent pixel value, obtaining a difference value between the pixel value in the current block and the adjacent pixel value, and obtaining a smoothing value of the current image based on the difference value. A pixel value around a boundary of the current block is smoothed based on the smoothing value and quantization information for the current block. | 7 |
FIELD OF THE INVENTION
Embodiments of the present invention relate to semiconductor device fabrication, and more particularly to reduced substrate resistance characteristics.
BACKGROUND OF THE INVENTION
For power metal oxide semiconductor field effect transistors (MOSFET), substrate resistance contributes to the total on-state resistance as a parasitic component. A vertical semiconductor device like a vertical double-diffused MOSFET (VDMOSFET), a trench MOSFET (TMOSFET), an insulated gate bipolar transistor (IGBT), or the like, represent a power switch. The resistance in the on-state of the switch is composed of a series connection of resistive elements.
FIG. 1A shows a cross sectional view of an VDMOSFET device employed in the conventional art. While FIG. 1B shows a corresponding series connection of resistive elements modeling the conductive path in the device in the on-state employed in the conventional art. The on-state resistance (R ds-on ) comprises metal film resistance (Rm) 110 , 120 , junction between metal film and semiconductor (i.e. drain and source) resistance (Rj) 130 , 140 , channel resistance (Rc) 150 , drift region resistance (Rd) 160 , and substrate region resistance (Rs) 170 . In the case of current low voltage power MOSFETs the substrate resistance (Rs) 170 contribution can be at least 40% of the total on-state resistance (Rds-on). Reducing the on-state resistance is beneficial to making the switch more efficient.
As semiconductor technology progresses, reduced on-state resistance becomes critical. In the conventional art, thinning the substrate by a method such as back-lapping and polishing the wafer can achieve some reduced on-state resistance. Wafer thickness is currently about 200 μm. Thinner wafers are possible. However, thin wafers can easily break during handling thereby resulting in lower manufacturing yields. It would be desirable to reduce the on-state resistance of the power switch without resulting in the poor manufacturing yields attributed to very thin wafers.
SUMMARY OF THE INVENTION
Thus, there is a need for a semiconductor device having improved on-state resistance. What is needed further is a means for reducing on-state resistance of a semiconductor power switch without reducing manufacturing yields, e.g., without making the wafer overly thin.
In one embodiment of the present invention, a method for fabricating semiconductor devices comprises forming an active region about a front-side of a substrate. A plurality of trenches is then formed about a back-side of the substrate. A grid of banks separates the trenches. The trenches act to reduce the on-state resistance, while the grid of banks maintains the structural strength of the wafer.
In another embodiment of the present invention, a method for fabricating semiconductor devices comprises forming an active region about a front-side of a substrate. A plurality of trenches is then formed about a back-side of the substrate. A grid of banks separates the trenches. A conductive layer is then deposited on the back-side of the substrate. The trenches act to reduce the on-state resistance, while the grid of banks maintains the structural strength of the wafer. The conductive layer further improves the resistance of the substrate during the on-state of the device.
In another embodiment of the present invention, a method for fabricating semiconductor devices comprises forming an active region about a front-side of a substrate. A plurality of trenches is then formed about a back-side of the substrate. A grid of banks separates the trenches. A conductive material is then deposited on the back-side of the substrate and fills the trenches. The trenches act to reduce the on-state resistance, while the grid of banks maintains the structural strength of the wafer. The conductive material and trenches further increases thermal and electrical conductivity of the substrate during the on-state of the device.
Embodiments of the invention reduce substrate resistance measured across the wafer without any negative impact on yield of the device during manufacturing. The solution according to the invention is to modify the substrate by etching trenches from the back-side and filling them with a conductive material. In one embodiment, the trenches being randomly distributed across the wafer collect the majority of the current flowing between the device contacts on the front-side of the substrate and its back-side metallization. In another embodiment, the trenches being aligned to the layout of the devices at the front-side of the wafer collect the majority of current flowing between the device contacts on the front-side of the substrate and its back-side metallization.
In one embodiment, the trenches are etched after the completion of the front-side manufacturing of the device. The front-side of the processed wafer is covered with an insulating film called a passivation layer. The wafers leave the clean room and are grinned from the back-side to a predefined thickness, e.g. 200 μm.
In one example, the back-side of the substrate is covered with a photoresist which is used as a mask to etch the trenches. The mask openings are not aligned to the devices located at the front-side of the substrate. The opening dimensions are less than one quarter (¼) of the edge dimension of the device die in one example, and the opening locations are random with respect to the device dies. The depth of the trenches may exceed half the thickness of the finished wafer. The photoresist mask is removed and a standard back-side metal can be deposited. In an exemplary embodiment, the back-side metal may be solderable, e.g., it can consist of a tri-metal layer of tin, nickel, and silver (Ti/Ni/Ag).
In one embodiment, a photoresist mask is applied to the front side of the wafer and pad openings may be etched in the passivation layer to define the location of the electric contacts to the devices. The wafer is sawed to singulate the dies and the trenches from the back-side are filled with a conductive material, e.g. it can be a solder paste or a conductive epoxy.
As another embodiment of the present invention, the trenches are filled with the conductive material after the deposition of the back-side metal and before the singulation of the dies.
Accordingly, embodiments of the present invention provide semiconductor devices having trenches and a conducting layer on the back-side of the substrate, adapted to reduce substrate resistance. Embodiments of the present invention also provide semiconductor devices having banks on the back-side of the substrate, adapted to assure mechanical stiffness of the substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of example and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
FIG. 1A shows a cross sectional view of a VDMOSFET device employed in the conventional art.
FIG. 1B shows a corresponding series connection of resistive elements modeling the conductive path in a VDMOSFET ( FIG. 1A ) device employed in the conventional art.
FIG. 2 shows a flow diagram of a process for reducing substrate resistance in accordance with one embodiment of the present invention.
FIGS. 3A , 3 B, 3 C, 3 D, 3 E, and 3 F show side-sectional views of a wafer being processed in accordance with one embodiment of the present invention.
FIG. 4 shows a back-side plain view of a patterned photoresist layer on a wafer in accordance with one embodiment of the present invention.
FIG. 5 shows a back-side plain view of a wafer having a grid of trenches etched therein in accordance with one embodiment of the present invention.
FIG. 6 shows a back-side plain view of a wafer having a grid of trenches etched therein in accordance with another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to the embodiments of the invention, examples of which are illustrated in the accompanying drawings. While the invention will be described in conjunction with the preferred embodiments, it will be understood that they are not intended to limit the invention to these embodiments. On the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be obvious to one of ordinary skill in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the present invention.
Embodiments of the present invention reduce substrate resistance by etching trenches into the substrate from the back-side and filling the trenches with a conductive material. Embodiments of the present invention also maintain the structural strength of the substrate. Thus, embodiments of the present invention advantageously reduce on-state resistance without reducing manufacturing yield.
Referring now to FIG. 2 , a flow diagram of a process for reducing substrate resistance in accordance with one embodiment of the present invention is shown. As depicted in FIG. 2 , device fabrication begins with various well known device fabrication processes, at steps 210 . The various device fabrication processes may include deposition, implanting, diffusion, etching, masking, photolithography, and the like. The various device fabrication processes result in formation of an active layer on the front-side of the substrate.
The active layer is comprised of a plurality of die regions. Each die region is comprised of one or more components, interconnects, and the like. The plurality of die regions is laid out in a pattern on the front-side of the wafer. Each die region is separated from another by scribing borders. The scribing borders allow for separation of the die regions at the end of processing, so that they may be packaged as individual devices.
A passivation layer is then formed on the front-side of the substrate, at step 215 . The passivation layer may be formed by any well-known method, such as deposition, evaporation, sputtering, chemical vapor deposition (CVD), or the like. The passivation layer provides electrical component isolation. The passivation layer also provides physical protection for the active region, during subsequent handling and fabrication processes.
The substrate is then thinned, at step 220 . The substrate may be thinned by any well-known method, such as back-lapping and polishing or the like. The back-lapping and polishing process is performed on the back-side of the wafer. In an exemplary configuration, the resulting substrate has a final thickness of 150-300 μm.
A photoresist is then coated on the back-side of the wafer, at step 225 . The photoresist is then patterned at step 230 . The patterning may de done by any well-known method, such photolithography, or the like.
Photolithography typically utilizes a photomask and ultraviolet light, wherein the photoresist is selectively exposed to form a desired pattern of areas covered with photoresist and uncovered areas. In one implementation, the shape, size and location of the mask openings may be of any configuration. In another implementation, the mask provides a pattern of openings not aligned to the die regions on the front-side of the substrate. The opening locations are random with respect to the die regions. In another implementation, the mask opening dimensions are less than one-quarter (¼) of the edge dimension of the die region. Thus, there are a few openings placed on the back-side, corresponding to the area of a die region. In another implementation, the openings are in the shape of small squares forming a modified chessboard pattern. In another implementation, the openings are arranged so that areas on the back-side of the wafer, which correspond with the scribing borders on the front-side of the wafer, do not contain openings. Aligning the pattern of die regions on the front of the wafer and the openings on the back of the wafer can be accomplished with any well-known means.
The back-side of the substrate is then etched at step 235 . The etching may be done by any well-known method, such as wet etching, dry etching or the like. The etching process forms a pattern of one or more trenches and banks on the back-side of the substrate, as defined by the patterned photoresist.
In one implementation, the etching process may have a significant isotropic component. Thus, the openings of the resulting trenches are greater than the opening in the patterned photoresist. In another implementation, the isotropic etching process results in trench walls with sloped sides. In an exemplary configuration, the slope of the trench walls is less than 85°.
In another implementation, the banks form a common grid assure mechanical stiffness of the wafer. In another implementation, the banks do not form any straight lines corresponding to the pattern of the die regions. In another implementation, areas on the back-side of the wafer, which correspond with the scribing borders on the front-side of the wafer, do not contain trenches.
The photoresist is then removed from the back-side of the wafer, at step 240 . The photoresist removal process may be done by any well-known method, such as chemical resist strip, resist ashing, or the like.
The back-side of the wafer is then subjected to a metallization process, at step 245 . The metallization process can be performed by any well-known means, such as evaporation, sputtering, or the like. In one implementation, the resulting conductive layer conformal coats the back-side of the substrate, including the banks, trench side-walls, and trench floors.
In one implementation of the present invention, the conductive layer is formed by a tri-metal multi-layer, which provides good electric contact to the substrate and a solderable surface. In an exemplary configuration the tri-metal multi-layer consists of tin, nickel and silver (Ti/Ni/Ag). In another implementation, the conductive layer is a conductive material, which planarizes the back-side of the wafer. The planarizing conductive material fills the trenches. In an exemplary configuration, the planarizing conductive material is a solder paste. In another exemplary configuration, the planarizing conductive material is a conductive epoxy.
Device fabrication then continues with various device fabrication processes, at steps 250 . The various device fabrication process steps may include forming contact pad regions, singulation of the wafer into individual die, die attachment, wire bonding, and the like.
In an alternative embodiment of the present invention, the trenches are filled with a conductive material after the deposition of the metal layer on the back-side of the wafer and before the singulation of the dies. The conductive material planarizes the back-side of the wafer prior to singulation.
The methods of the present embodiments provide the advantage of reducing substrate resistance. The methods of the present embodiments also provide the advantage of collecting the majority of current flowing between the device contacts, by the back-side metallization. The methods of the present embodiments also provide the advantage of maintaining structural strength of the substrate.
Referring now to FIGS. 3A-3F , side-sectional views of a wafer 305 being processed in accordance with one embodiment of the present invention are shown. As depicted FIG. 3A , the wafer 305 initially comprises a substrate 310 with an active region formed thereon 315 (i.e. front-side). A passivation layer 320 covers the active region. In one exemplary configuration, the wafer 305 has a thickness of 150-300 μm.
As depicted in FIG. 3B , a photoresist layer 325 is deposited on the substrate 310 (e.g. back-side). The photoresist is patterned to form a plurality of openings 330 . Trenches 335 are formed in the substrate 310 under the plurality of openings 330 in the photoresist layer 325 . Banks 337 of substrate 310 remain where the photoresist layer 325 is present.
In one implementation of the present invention, the depth of the trenches 335 exceeds half the thickness of the substrate 310 and does not extend to the active region 315 . In an exemplary configuration, the depth of the trenches 335 is approximately 100-200 μm. In another implementation, the sides 340 of the trenches 335 are sloped. In an exemplary configuration, the sloped sides 340 of the trenches 335 have an angle α, which is less than 85°. In another implementation, the size, shape and spacing of the trenches 335 may be of any configuration. In another implementation, the trenches 335 are randomly spaced with respect to corresponding die regions on the front-side of the wafer 305 . In another implementation, the trenches 335 are not located corresponding to scribing borders between the die regions on the front-side of the wafer 305 . In another implementation, the plurality of trenches 335 are located in a region corresponding to each die region on the front-side of the wafer 305 .
In another implementation, the width and/or length of the trenches 335 is a fraction of the edge length and/or width of the die regions. In an exemplary configuration, the width and/or length of the trenches 335 is approximately one quarter (¼) of the edge length and/or width of the die regions. In another implementation, the shape of the trenches 335 are square and arranged to form a modified chessboard pattern with a grid of banks separating the trenches. In one implementation, the trenches 335 should not be of sufficient length and/or width to form a straight groove, susceptible to cleaving, in the pattern of the grid of banks 337 . Thus, the banks 337 form a common grid assuring mechanical stiffness of the wafer 305 .
As depicted in FIG. 3C , the photoresist layer 325 is stripped and a conformal conductive layer 345 is deposited on the substrate 310 (e.g. back-side).
In one implementation of the present invention, the conductive layer 345 is a tri-metal multi-layer, which provides good electric contact to the substrate, and a solderable surface. In an exemplary configuration the tri-metal multi-layer consisting of Ti/Ni/Ag.
As depicted in FIG. 3D , the passivation layer 320 is patterned to define contact pad openings 350 .
As depicted in FIG. 3E , the wafer 305 is separated, along the scribing borders, into individual die 355 (a single die is shown for illustrative purposes). Furthermore, the trenches are filled with a conductive material 360 , which planarizes the back-side of the substrate 310 . In an exemplary configuration, the planarizing conductive material 360 is a solder paste. In another exemplary configuration, the planarizing conductive material 360 is a conductive epoxy.
As depicted in FIG. 3F , the die 355 is packaged on a frame 365 . The die and frame form a subassembly of the final device packaging, such as TO-type package, small outline integrated circuit (SOIC), or the like.
In an alternative embodiment of the present invention, the trenches 335 are filled with a conductive material 360 after the deposition of the back metal layer 345 and before singulation of the dies.
The present embodiments provide the advantage of reducing substrate 310 resistance. The present embodiments also provide the advantage of collecting the majority of current flowing between the device contacts, by the back-side metallization 345 . The present embodiments also provide the advantage of maintaining structural strength of the substrate 310 .
The present embodiments provide the advantage of reducing substrate 310 resistance, both thermal and electrical. The substrate 310 is thinner and the back-side conductive layer 345 and/or conductive material 360 is closer to the active region 315 . Therefore, the thinner substrate 310 provides for reduced electrical resistance. Furthermore, the back-side conductive layer 345 and/or conductive material 360 readily removes thermal heat generated in the substrate 310 . While, the back-side conductive layer 345 and/or conductive material 360 also collects the majority of current flowing between device contacts, such as front-side source contacts and back-side drain contact. Thus, the present embodiments also provide the advantage of increasing device reliability by reducing thermal and electrical resistance. The present embodiments also provide the advantage of maintaining structural strength of the wafer 305 .
Referring now to FIG. 4 , a back-side plain view of a patterned photoresist layer 410 on a wafer 405 in accordance with one embodiment of the present invention is shown. As depicted in FIG. 4 , the back-side of the wafer 405 is substantially covered with a photoresist 410 . Sections of the photoresist 410 have been removed to define a pattern of openings 415 .
In one implementation, the size, shape and spacing of the openings 415 may be of any configuration. In another implementation, the openings 415 are randomly spaced with respect to corresponding die regions on the front-side of the wafer 405 . In another implementation, the width and/or length of the openings 415 is a fraction of the edge length and/or width of the die regions. In an exemplary configuration, the width and/or length of the openings 415 is less than one quarter (¼) of the edge length and/or width of the die regions. In another implementation, the openings 415 are arranged so that the areas on the back-side of the wafer 405 , which correspond with scribing borders on the front-side of the wafer 405 , do not contain openings 415 . In another implementation, a plurality of openings 415 are located corresponding to each die region on the front-side of the wafer 405 . In another implementation, the shape of the openings 415 are square and arranged to form a modified chessboard pattern with a grid of photoresist 410 separating the openings 415 . In another implementation, the openings 415 should not be of sufficient length and/or width to form a straight groove in the pattern of the grid of photoresist 410 .
Referring now to FIG. 5 , a back-side plain view of a wafer 505 in accordance with one embodiment of the present invention is shown. As depicted in FIG. 5 , the back-side of the wafer 505 has a plurality of trenches 515 etched into a substrate 510 . Banks 520 separate the trenches 515 .
In one implementation of the present invention, the depth of the trenches 515 exceeds half the thickness of the substrate 510 . In an exemplary configuration, the depth of the trenches 515 is approximately 100-200 μm, for a wafer 505 of approximately 150-300 μm thick. In another implementation, the sides of the trenches 515 are sloped. In an exemplary configuration, the sloped sides of the trenches 515 have an angle α, which is less than 85°. In another implementation, the size, shape and spacing of the trenches 515 may be of any configuration. In another implementation, the trenches 515 are randomly spaced with respect to corresponding die regions on the front-side of the wafer 505 . In another implementation, the width and/or length of the trenches 515 is a fraction of the edge length and/or width of die regions on the front-side of the wafer 505 . In an exemplary configuration, the width and/or length of the trenches 515 is approximately one quarter (¼) of the edge length and/or width of the die regions. In another implementation, areas on the back-side of the wafer 505 , which correspond with scribing borders on the front-side of the wafer 505 , do not contain trenches 515 . In another implementation, the shape of the trenches 515 are square and arranged to form a modified chessboard pattern with a grid of banks 520 separating the trenches 515 . In another implementation, the trenches 515 should not be of sufficient length and/or width to form a straight groove, susceptible to cleaving, in the pattern of the grid of banks 520 . Thus, the banks 520 form a common grid assuring mechanical stiffness of the wafer 505 .
The present embodiment provides the advantage of reducing substrate 510 resistance, both thermal and electrical. The present embodiment also provides the advantage of maintaining structural strength of the wafer 505 .
Referring now to FIG. 6 , a back-side plain view of a wafer 605 having a grid of trenches 615 etched therein in accordance with another embodiment of the present invention is shown. As depicted in FIG. 6 , the back-side of the wafer 605 has a plurality of trenches 615 etched into a substrate 610 . Banks 620 separate the trenches 615 .
In one implementation of the present invention, the depth of the trenches 615 exceeds half the thickness of the substrate 610 . In an exemplary configuration, the depth of the trenches 615 is approximately 100-200 μm, for a wafer 605 of approximately 150-300 μm thick. In another implementation, the sides of the trenches 615 are sloped. In an exemplary configuration, the sloped sides of the trenches 615 have an angle α, which is less than 85°. In another implementation, the size, shape and spacing of the trenches 615 may be of any configuration. In another implementation, the trenches 615 are randomly spaced with respect to corresponding die regions on the front-side of the wafer 605 . In another implementation, the width and/or length of each trench 615 is a fraction of the edge length and/or width of the die regions. In an exemplary configuration, the width and/or length of each trench 615 is approximately one quarter (¼) of the edge length and/or width of the die regions. In another implementation, areas on the back-side of the wafer 605 , which correspond with scribing borders on the front-side of the wafer 605 , do not contain trenches 615 .
In another implementation, a plurality of trenches 615 are placed in a region corresponding to each die region on the front-side of the wafer 605 . In another implementation, the shape of the trenches 615 are various sized squares and arranged to form a modified chessboard pattern with a grid of banks 620 separating the trenches 615 . In another implementation, the trenches 615 should not be of sufficient length and/or width to form a straight groove, susceptible to cleaving, in the pattern of the grid of banks 620 . Thus, the banks 620 form a common grid assuring mechanical stiffness of the wafer 605 .
The present embodiment provides the advantage of reducing substrate 610 resistance, both thermal and electrical. The present embodiment also provides the advantage of maintaining structural strength of the wafer 605 .
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents. | In one embodiment of the present invention, a method for fabricating semiconductor devices comprises forming an active region about a front-side of a substrate. A plurality of trenches are then formed about a back-side of the substrate. A grid of banks separates the trenches. A conductive material is then applied to the back-side of the substrate. The trenches and the conductive material act to reduce the on-state resistance of the substrate and enhance thermal conductivity, while the grid of banks maintains the structural strength of the wafer. | 7 |
BACKGROUND OF THE INVENTION
1. Fields of the Invention
The present invention pertains to arched buildings and roofs. More directly, it relates to the skeletal arched frameworks which must resist the high and variable wind and snow loads such arched structures are exposed to.
Historically, arched structures have been large bridges and buildings for public uses such as auditoriums and sports arenas. These structures have large spans and arch shapes which are close to the funicular shape for the dead load. An open-web steel arch bridge spans 1,652 feet at Bayonne, N.J. (Ref. 1, McGraw-Hill Encyclopedia of Science & Technology, 7th Ed., 1992, pg. 50). A reinforced concrete arched vault spans 262 feet in the Turin Exhibition Hall (Ref. 2, Luigi Nervi, Aesthetics and Technology in Building, Harvard University Press, Cambridge, Mass., 1965). Laminated wood arched structures have spans over 200 feet, with monolithic three-hinged arches (Ref. 1, pg. 51) and over 500 feet as a lamella dome in Tacoma, Wash. (Ref. 3, Wood Handbook: Wood as an Engineering Material, Agriculture Handbook 72, Forest Service, USDA, 1987, pg. 10-4).
This invention relates to open-web arches which may be freely shaped to meet aesthetic and functional ends, independent of building site and resulting live loads. Such arches have non-funicular shapes and are primarily stressed by internal bending moments resulting from structure live loads of wind and snow. They will primarily be used in residential structures having clear spans less than fifty feet.
2. Description of the Related Art
Nine U.S. Patents have been found which disclose compound arched structures composed of two or more arches which are spaced apart in directions radial to their common cross section areal centroid curve and connected by a set of sturctural parts. Four of the older inventions (1889-1944) used wooden arches and four of the later ones (1942-1970) used structural steel arches. One (1969), an arched tower of approximately funicular shape rather than a moment resisting structure frame, used glass reinforced plastic arches, for their electrical and structural properties.
The relevance of these open-web arched structures to the present invention can best be seen by first considering the function of a straight, transversely loaded beam. Assume a horizontal beam is loaded vertically downward in its depth direction. The top half of the beam is compressed and tends to shorten. The lower half tends to lengthen under tensile stress. The middle part of the beam develops shear stress to resist relative longitudinal sliding between the top and bottom beam halves. Shear stress and strain in the longitudinal and depth directions produce tensile and compressive stress and strain in directions having acute angles of plus and minus 45° to the longitudinal beam axis. For this reason, the mid-depth portion of a monolithic beam can be replaced by diagonal bars inclined at or near 45° to the beam axis. Such open-web beams are common in steel joist and wood trusses for both floors and flat roofs.
The essential structural requirement for the mid-depth portion of a transversely loaded straight beam is that it have shear rigidity in planes parallel to the beams longitudinal axis and applied loads, which are usually close to coplanar. Further, this shear rigidity must exist over the full length of the beam. It can be provided by the full width of a monolithic wood beam, by the relatively thin web of a steel I beam, or by the diagonal web bars of an open-web steel joist or wood truss. All provide shear rigidity in the coplane of the beams long axis and transverse loads.
Historically, it has been assumed that this requirement for shear rigidity in the plane of the beam's long axis and applied loads and over the beam's full length was also a requirement for curved beams or arches. All eight of the prior-art U.S. patents relating to non-funicular, moment resisting, open-web arches provide arch connecting means which have shear rigidity in the plane containing the cross section areal centroid curve of the arch and they provide it over the full length of the open-web arch.
Open-web wood arches were disclosed in U.S. Pat. No. 401,870, having webs of radial posts and diagonal braces; U.S. Pat. No. 1,438,452, had double bolted and keyed blocks for web connectors over most of the arch length and diagonal braces near the arch ends; U.S. Pat. No. 1,687,850, used one of two shear web means, double bolted tapered blocks, or a diagonal metal tension strap over radial spacing sleeves and bolts, referred to as a tension and shear member; U.S. Pat. No. 2,390,418, used double bolted blocks spaced uniformly over the full length.
Open-web steel arches were disclosed in U.S. Pat. No. 2,278,797, with diagonal web parts welded to arched channels over the full arch length, with the addition of radial web parts and cross braces near the springing of the arch; U.S. Pat. No. 2,612,854, had diagonal bars or braces welded to arched channels; U.S. Pat. No. 2,666,507, provided spacer plates, which were coplanar with the arches cross section areal centroid curve, welded to steel arches of preferably circular cross section; U.S. Pat. No. 3,530,623, had short, transverse truss braces of hollow square cross section welded to steel channels in and near their curved lengths.
U.S. Pat. No. 3,439,107 disclosed an arch shaped electrical transmission tower made from four support rods of arched shape and transverse spacer rods. It appeard to be an intuitive attempt to provide a funicular shape for both the tower and the individual arches so that they were subjected to primarily longitudinal stresses with small bending stresses. Spacer rods obviously spaced the support rods relative to each other and also shortened their buckling length, though there was no discussion of either funicular shape or buckling.
3. Present Needs
There was no discussion in the reviewed art of open-web arches concerning their buckling characteristics. Some were obviously not self-stable against excessive buckling type rotations and lateral deflections under compressive end loading. The leeward arch is subjected to such compressive buckling loads from wind in the arch span direction. All except U.S. Pat. No. 3,439,107 were intended to have purlins or cladding attached to the outside arch in the direction of arch width. In addition, U.S. Pat. Nos. 2,666,507 and 2,390,418 both provided purlins or stringers, in the arch width direction, through the web volume. Lateral support of the open-web arch by attached structural members, such as purlins, stringers and cladding, can significantly reduce arch buckling rotation about its areal centroid curve and lateral buckling deflections in the arch width direction. That is often a partial purpose.
The recent availability of transparent architectural glazing panels of UV light durable polycarbonate and acrylic plastics in four and six foot widths and continuous lengths, makes possible the continuous glazing from base to ridge of an arch framed structure. It is often desirable that this continuous glazing not be interrupted by horizontal purlins or glazing bars for visual and aesthetic reasons and for minimizing horizontal weather seals. Due to the high coefficients of thermal expansion, these plastic glazing panels are not directly connected to the outside arches, but are free to slide between weather seals. Therefore, they provide little or no lateral support for the arched framing members, which must be self supporting against excessive buckling rotations and deflections over their full length from base to structure ridge. This requirement for open-web arches for small span structures which are self-stable under compressive buckling loads is a recent one, resulting from the availability of large plastic glazing panels.
The open-web arches of the prior-art were not aesthetically pleasing and were intended for agricultural, industrial and commercial uses. Arched shapes are inherently pleasing, but the cluttered nature of numerous across web connectors dominate their appearance. Also, open-web wood arches predated the availability of water durable structural adhesives and were "laminated" with bolts and spikes. The welded structural steel open-web arches would have been hot dipped galvanized, painted or used bare. Consequently, there exists a present need for aesthetically pleasing open-web arches.
Any new open-web arch that provides buckling self-stability and a pleasing appearance must also economically provide for an arch depth which varies over the arch length, as does the distribution of internal bending moments under worst-case wind and/or snow loading. Four of the older prior-art patents did not. Four of the newer did.
There is also an increasing need for greater structural efficiency, i.e. providing structures which are sufficiently strong and stiff, but with less structural material. This requires greater arch depth to resist the load moments, with acceptable deflections and less arch material and greater arch width for buckling self-stability.
Much of the turn-key cost of a residential structure is for construction. There is a need for manufactured arched framing members which can be assembled into an arched structure by one or two lay persons using common hand tools and equipment.
SUMMARY OF THE INVENTION
It is an important object of the present invention to provide arched framing members capable of resisting large internal bending moments with acceptable deflections to permit the arch shape to be determined primarily for structure functional and aesthetic reasons rather than primarily for worst-case structure loads. The primacy of functional and aesthetic qualities result in arches of decidedly non-funicular shapes.
It is another important object of the present invention to provide arched framing members which, despite their non-funicular shapes, are strong enough to withstand hurricane winds and mountain snows and stiff enough to meet the standard span/deflection requirements with a minimum of structural material.
In particular, it is an object to provide open-web type arched framing members for arched structures having clear spans generally less than fifty feet for residential type structures.
It is also an object of the present invention to provide arched framing members with high structural efficiencies to conserve structural materials such as renewable wood resources, aluminum and steel.
Another important object according to the present invention is to provide arched framing members which are self-stable against both rotational buckling about the arch cross section areal centroid curve and lateral buckling in the direction of the arch width, without lateral support from other structural members.
A further object is for the arched framing members to facilitate structures having a high percentage of glazed exterior surface, with a minimum of visual obstructions, for providing abundant natural light and exceptional exterior views.
To enhance the above object, it is a further object of this invention to provide arched framing members which facilitate structures with high thermal efficiencies to minimized heating and cooling costs.
It is also an object to provide arched framing members which facilitate air venting and the distribution of utility ducts, pipes and lines throughout the structure.
Another important object of the present invention is to provide arched framing members which are aesthetically pleasing in themselves and in arched structures.
It is a further object to provide open-web arches having a minimum number and size of connectors across the web volume of the arch.
A further important object of this invention is to provide arched framing members which are durable in structures having warm, moist interior environments, such as greenhouses and enclosed swimming pools.
It is an important object of this invention to provide framing members which can be assembled into arched structures, having clear spans up to fifty feet, by one or two lay persons using common hand tools and equipment.
Another important object according to the present invention is to provide framing members for advanced arched structures which have turn-key costs similar to conventional residential construction.
These and other objects which will become apparent from studying the appended description and drawings are provided in a biarch framing member for arched structures, comprising:
a pair of coplanar arches curved in the same direction over at least a portion of the length of their common areal centroid curve, each of said arches having a nearly constant width over said similarly curved length portion; and
a pair of RT ties, spaced apart along said common centroid curve length, each of said RT ties, including its arch connecting means, having sufficient tensile and compressive rigidity, in the direction radial to said centroid curve at the location of said each RT tie, to resist relative displacement between said arches in said radial direction, and also having sufficient shear rigidity in its radial-tangential plane to resist relative displacement between said arches in the direction tangential to said centroid curve at said each RT tie location, at least one of said RT tie pair spacing said arches apart in said radial direction at the location of said least one RT tie; and
at least one RW tie connecting said arch pair in said similarly curved length portion at a location between said RT tie locations and spacing said arches apart in the direction radial to said centroid curve at said RW tie location, said RW tie, including its arch connection means, having sufficient tensile and compressive rigidity in said radial direction to resist relative displacement between said arches in said radial direction, but having considerably less shear rigidity in its radial-tangential plane than the one of said pair of RT ties having the greater shear rigidity in its said radial-tangential plane.
One embodiment of the present invention divides at least one arch of the arch pair into two or more sub-arches and spreads them apart in the width direction to increase the buckling resistance of the biarch framing member.
Another embodiment replaces at least one of the end ties by rigidly attaching one or both of the biarch ends to adjacent structural member/s having shear rigidity in plane/s parallel to the coplane of the biarch framing member.
As will be seen, the present invention provides novel means for obtaining open-web arches of non-funicular shape which can be shaped to meet the functional and aesthetic requirements of small-span, low-rise arched structures which are strong and stiff enough to withstand extreme wind and snow loadings.
This invention derived from both theoretical and experimental work which showed the prior assumption, that curved beams or arches needed shear rigidity in the plane of the arch areal centroid curve and over the full curved arch length, was not realistic. It was discovered that arches need shear rigidity in the coplane of the arch centroid curve only near the arch ends. Throughout the curved length, the mid-depth portion of the arch can be mostly open, with the cross-web connectors having shear rigidity only in planes perpendicular to the arch centroid curve.
It was also discovered that this transverse shear rigidity not only gave open-web arches strength and stiffness against internal bending moments in the arch coplane, but also against buckling type rotations about the centroid curve and lateral deflections normal to the arch coplane.
Transverse cross ties of minimum size, variable spacing and minimum number provide large and variable arch depth to withstand large and variable internal bending moments with a minimum of structural material. Biarch framing members are structurally efficient in spite of their non-funicular shape and resulting large internal bending moments.
These transverse cross ties also provide means for spacing sub-arches in the width direction and limiting buckling type rotations and translations without support from lateral structural members. Buckling self-stability permits glazing nearly all of the exterior structure surface to achieve abundant natural light inside and occupant views of the outside environment with a minimum of visual obstructions.
Arched structures having high thermal efficiencies, even with high percentages of glazed exterior surface, are provided with biarch framing members with continuously curved interior arches to support sliding insulation and low emissivity solar shades.
Radially spaced arches and laterally spaced sub-arches provide a continuously interconnected space useful for distribution, throughout the arched structure, of utilities such as ventilation air, centrally conditioned air (heated, cooled, cleaned and/or humidified), electrical power, communication lines (phone, cable and antenna), water and gas lines.
Limiting the web parts to a few transverse cross ties and two parallel end ties limits the visual obstructions seen on profile views of biarch framing members, thereby preserving the aesthetic qualities inherent in arches having smooth, continuous and generally variable radii of curvature. Biarch framing members will often be open and visible to structure occupants as will the structure profile viewed externally. Naturally finished hardwoods, corrosion resistant aluminum and stainless steel add to the aesthetic appeal of open-web arches made according to the present invention. Such aesthetically pleasing biarch framing members can also be made very durable in warm, moist environments common to sunspace structures such as greenhouses and swimming pool enclosures.
Sub-dividing and laterally spacing a pair of radially spaced arches according to the present invention produces four sub-arches which are light enough in weight to permit one or two lay persons to assemble arched structures having clear spans up to fifty feet using common hand tools and equipment. This permits direct sales and shipment to owners and minimizes manufacturing, sales, distribution and construction costs. Reversible, threaded connectors permit disassembly and compact shipment for future portability of biarch framed structures.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings wherein like elements are referenced alike:
FIG. 1 is a front elevation view of a biarch framing member positioned to serve as one half of a frame spanning the width of an arched structure;
FIG. 2 is a graphical representation showing the rate at which arch height varies with change in chord length, as a function of the ratio of arch height to chord length, for arches of three different shapes, linear, parabolic and circular. FIG. 2 will be used to describe how biarch framing members develop internal tangential arch stress and bending moments in reaction to externally applied loads. More importantly, FIG. 2 will illustrate why the across web connectors need shear rigidity in planes parallel with the plane of the biarch centroid curve only at the ends of the arches and not throughout the biarch length, as is necessary in straight beams;
FIG. 3 is a free body diagram of the lower part of the biarch framing member, shown complete in FIG. 1. Internal reaction force and bending moment balance the applied compressive load. FIG. 3 will be used to develop equations for biarch bending stress and normal stress;
FIG. 4 is a graphical representation of the fundamental equation for the structural function of biarch framing members. The ratio of biarch maximum depth to maximum height above the chord line is shown as a function of arch strain capacity, structure span/deflection limit and biarch structural efficiency. Biarch shape factor is included as a constant. FIG. 4 illustrates what materials are most appropriate for constructing biarch framing members. Optimum biarch materials change with the span/deflection requirements of the sturcture.
FIG. 5 is a perspective view of the lower part of the biarch framing member shown complete in FIG. 1. Eccentricity of internal reaction forces are shown, which produce rotational and translational buckling deflections of the biarch framing member. FIG. 5 will be used to determine the biarch characteristics which are required for self-stability against excess buckling rotations and deflections and an expression for arch buckling stress due to buckling moment;
FIG. 6 is a graphical representation of the ratio of minimum second moment of area (moment of inertia) in the width direction, with respect of the radial axis, to the maximum second moment of area in the depth direction, with respect to the width axis, required to make biarch framing members self-stable against excess buckling, without lateral support. Critical biarch characteristics are arch strain capacity, biarch structural efficiency, the ratio of maximum allowable lateral deflection to maximum expected load eccentricity and the free/fixed nature of the end connections;
FIG. 7 is a front elevation view of the middle segment of the biarch framing member shown complete in FIG. 1. It is enlarged here as a free body diagram to shown internal reaction forces and moments in arches and cross ties. FIG. 7 will be used to develop equations for the cross tie spacings along the two arch centroid curves, arch bending stresses which depend on cross tie spacings and arch shear stresses due to cross tie and end tie forces.
FIG. 8 shows a hypothetical coplane of the biarch framing member illustrated in FIG. 1. Also shown are the cross section areal centroid curves of each arch and the common cross section areal centroid curve of the biarch and their normal projections onto the biarch coplane. Root-mean-square distances of the three centroid curves from the biarch coplane are also shown, greatly exaggerated for clarity.
FIG. 9 shows a transverse RW cross tie, a parallel RT end tie and the biarch centroid curve taken from the lower part of the biarch framing member as illustrated in FIG. 5. RWT axes are located at each tie. The radial-tangential and radial-width planes where radial and shear rigidity is important or requires discussion are also illustrated in FIG. 9.
FIG. 10 shows that the required shear rigidity of a parallel end tie can be provided by an adjacent structural member such as a concrete slab.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
1. Biarch Description
A biarch framing member consists of three essential components: a pair of coplanar arches, transverse cross ties and two parallel end ties, all illustrated in FIG. 1.
A front elevation view of a biarch framing member, generally indicated at 10 in FIG. 1, has a pair of coplanar arches, outside arch 20 and inside arch 30 curved in the same direction and spaced apart and connected by six cross ties 40, which have shear rigidity in planes which are perpendicular to biarch centroid curve 50. In general, the spacing of cross ties 40, along the curved length of centroid curve 50, will increase with its variable radius of curvature 80. The ends of arches 20 and 30 are connected by base end tie 60 and ridge end tie 70, both of which have shear rigidity in planes parallel to the plane of biarch centroid curve 50.
Compressive forces P.sub.Δ/ee acting along chord line 90 are the simplest means of loading biarch 10 to illustrate and describe its function as a framing member in arched structures subjected to worst-case loading by wind and/or snow.
When biarch 10 is sectioned by a plane 5--5 normal to centroid curve 50, through the point of its minimum radius of curvature, the lower portion of biarch 10 would appear in perspective as illustrated in FIG. 5. A right-handed coordinate system TRW is centered at point 100, with radial axis R and width axis W lying in the plane of cross section 5--5 of FIG. 1 and tangent axis T, normal to the plane of cross section 5--5 and tangent to centroid curve 50 at its point of intersection lee by plane 5--5.
Outside arch 20 has been divided into two halves of equal cross section area, forming half arches 23 and 26. Similarly, inside arch 30 consists of half arches 33 and 36. These half arches are spaced apart in the width direction to limit lateral biarch deflection in the width direction, which results when base force P.sub.Δ/ee produces reaction forces F c and F t which are eccentric to axis R by eccentric distances e c and ec t , respectively.
Cross ties 40 are made of a structural steel plate 42, positioned normal to centroid curve 50, with welded end bars 44 drilled to receive countersunk bolts 46, through the center of the half arches in their depth direction. Nuts 48 secure the half arches to the cross ties. Because biarch depth d bn varies along the length of centroid curve 50, planes of end bars 44, which are flat against the inside surface of the half arches, are not quite perpendicular to plates 42. Through bolts 46, with axes perpendicular to the plane of end bars 44, are not quite radial to centroid curve 50. When nuts 48 are tightened, the four half arches are secured together by cross ties 40, which have shear rigidity in planes normal to the biarch centroid curve 50, thereby resisting relative displacements between arches 20 and 30 in both the radial and width directions at the location of each cross tie 40.
Because arches 20 and 30 are divided into equal halves, end ties 60 and 70 are also divided into two similar parts. Half of base tie 60 is connected to half arches 23 and 33, with the other half connected to half arches 26 and 36. Both halves of base tie 60 have welded shear plates 62, which are parallel with the plane of biarch centroid curve 50. These shear plates 62 resist relative displacements between adjacent base ends of arches 20 and 30, in the tangential direction of biarch centroid curve 50, at the base.
When biarch 10 is in use as a member of a frame of an arched structure, both halves of base tie 60 would be bolted to a concrete slab, foundation, wall, floor or other rigid base. If such a base has shear rigidity in planes parallel with the plane of biarch centroid curve 50, shear plates 62 of base tie 60 could be eliminated and all four half arches, 23, 26, 33 and 36 connected directly to the rigid base.
Ridge tie 70 in FIG. 1 is similar to base tie 60, being in two similar halves and having shear plates 72 which are parallel to the plane of centroid curve 50. However, in a typical structure frame, ridge tie 70 would be bolted to a ridge beam running the length of the structure. Such a ridge beam is usually relatively free to rotate about its longitudinal axis. Such rotation would permit relative tangential displacement between adjacent ridge ends of arches 20 and 30, if they were connected individually to the ridge beam. Therefore, ridge tie 70 with shear plates 72, which are parallel with the plane of biarch centroid curve 50, must generally be retained as an integral part of biarch framing member 10.
Relative tangential displacement between adjacent ends of arches 20 and 30 must be rigidly resisted at both ends of biarch 10 for it to reach its maximum structural stiffness. This requires shear rigidity in planes which are parallel with that of the biarch centroid curve 50. Such shear rigidity must be provided by components of the biarch framing member, such as end ties 60 and 70 or by the structure members to which the ends of arches 20 and 30 are attached.
2. Biarch Structures
In general, biarch framing members will be used as the primary structural members in the skeletal frameworks for private-use arched buildings having clear spans of less than fifty feet. Biarch framed structures will provide clear spans for unrestricted use of the interior space, vaulted ceilings for large overhead volumes and a high percentage of glazed exterior surface for abundant natural light.
A typical frame for an arched structure would use two of biarch framing members 10 in FIG. 1. Base end ties 60 would be bolted to a rectangular concrete slab floor near its sides. Ridge end ties 70, bolted to a ridge beam, would complete one frame spanning the full building width. A number of these two member biarch frames spaced in parallel vertical planes uniformly along the building length would form the primary skeletal frame for a biarched framed structure.
Architectural glazing materials such as glass and rigid transparent plastic panels of acrylic or polycarbonate and opaque exterior cladding materials can be attached to and supported by the outside arches of the biarch framing members. Insulation and interior wall/ceiling materials can be attached to and supported by the inside arches of the biarch framing members. The space between the arches can be vented to control moisture condensation on the inside surfaces of exterior cladding materials. This interarch space will also be useful for ventilation air and distributing electrical power, centrally conditioned air, communication lines, water and gas lines throughout biarch framed structures.
3. Biarch Function
The means by which a biarch framing member acts as a unit to resist deformation under applied loads can be understood by considering FIGS. 1 and 2.
Imagine that all six of the cross ties 40 are removed from biarch 10 in FIG. 1 before compressive forces P.sub.Δ/ee are applied along chord line 90. Then as P.sub.Δ/ec are applied, chord length L c will decrease. Outside arch 20 and inside arch 30 will both move outward, increasing their perpendicular distance from chord line 90. However, both arches will not move outward at the same rate. For a given incremental decrease in L c , inside arch 30 will move outward further than will outside arch 20. Thus, the radial distances between the two arches will decrease. Conversely, if the forces P.sub.Δ/ec are reversed in direction and applied as tensile forces, L c would increase, the inside arch 30 would move towards chord line 90 at a faster rate than outside arch 20 and the two arches would move further apart.
The primary purpose of cross ties 40 is to prevent relative displacements between the arch pair 20 and 30 in directions radial to centroid curve 50. When biarch cross ties 40 are in place, as illustrated in FIG. 1, compressive forces acting along chord line 90 load cross ties 40 in compression as they resist the tendency for arches 20 and 30 to move closer together. Conversely, tensile forces along chord line 90 load cross ties in tension as they resist the tendency for arches 20 and 30 to move farther apart.
FIG. 9 is the same view of the lower part of biarch framing member 10 as is shown in FIG. 5 with every item removed except for one cross tie 40, end tie 60 and biarch centroid curve 50. Additionally, FIG. 9 shows an RWT coordinate axes, with the origin located on centroid curve 50 at the location of cross tie 40, assumed near the center of shear plate 42. Plane 49 contains radial axis R and width axis W. The plane of shear plate 42 parallels radial-width plane 49. Cross tie 40 and its arch connecting means must have sufficient tensile and compressive rigidity in the radial direction in RW plane 49 to resist relative displacement between inside arch 30 and outside arch 20, both shown in FIG. 5, in the radial direction R.
Finally, the radial forces produced in the cross ties stress the arches in tangential directions. Compressive chord line forces produce compressive cross tie forces which stress outside arch 20 in tension and inside arch 30 in compression. Tangential tensile stress in outside arch 20 and tangential compressive stress in inside arch 30 produce internal bending moments which balance those produced by applied end compressive forces P L/ec . These tangential arch stresses of opposite direction are transmitted to the arch ends where they tend to produce relative tangential displacement between adjacent ends of arches 20 and 30, which are resisted by end ties 60 and 70, both of which have shear rigidity in planes parallel to the plane of biarch centroid curve 50.
FIG. 9 also shows a RWT coordinate axes, with the origin located on centroid curve 50 at the location of end tie 60, assumed near a line connecting the mass centroids of shear plates 62. Plane 67 contains radial axis R and tangential axis T. The planes of shear plates 62 parallel radial-tangential plane 67. End tie 60 and its arch connecting means must have sufficient shear rigidity in its RT plane 67 to resist relative displacement between inside arch 30 and outside arch 20, both shown in FIG. 5, in tangential direction T. End tie 60 must also have sufficient tensile and compressive rigidity in radial direction R to resist relative displacement between arches 20 and 30 in radial direction R.
The process described above has been quantified in FIG. 2 for three arch shapes: linear, with infinite radius of curvature and a sharp bend; parabolic, with continuously varying radii of curvature; circular, with a constant radius of curvature. It is interesting that curve 120 for a parabolic arch of variable curvature lies between curve 130 for a circular arch of constant curvature and curve 110 for a linear arch of zero curvature, except for the sharp bend. The arches 20 and 30 in biarch 10 of FIG. 1 are hyperbolic in shape with continuously varying radius of curvature, similar to the parabolic arch shape which produced curve 120 in FIG. 2.
Outside arch 20 of biarch 10 in FIG. 1 has a larger H/L and a smaller --ΔH/ΔL than does inside arch 30. Appropriate lines for arches 20 and 30 have been drawn on FIG. 2. An incremental change of one inch in chord length L c would tend to change the length of the larger cross ties 40 near section plane 5--5 by 0.13 inches. When this length change is resisted by rigid cross ties, tangential stresses of about 1800 psi would be produced in hardwood arches having an elastic modulus of 2E6 psi parallel to the grain of the wood.
Real cross ties are of course not perfectly rigid and permit some relative radial displacement between inside arch 20 and outside arch 30. However, the radial rigidity of cross ties 40 and their arch connecting means must be sufficiently large that their length change is small compared to the change in radial distance which would occur, 0.13 inches in the above example, in their absence, under the maximum permitted change in chord length L c .
4. Biarch Strength and Stiffness
About half or more of the ultimate strain or stress capability of the arch pair of a biarch framing member is available to resist bending moments produced by structure loads. The remainder is needed to support large cross tie spacings, which lower costs and improve the appearance of biarch framing members, desired since they will be visible in many of the potential applications, and also needed for normal stress and buckling stress.
The biarch bending stress which results from structure loads is readily derived by considering the lower part of biarch 10, FIG. 5, as a free body subjected to compressive load force P.sub.Δ/ec, as illustrated in a front elevation view in FIG. 3. The dimension arrows for maximum biarch depth d max in FIG. 3 are coplanar with section plane 5--5 in FIG. 1 and the RW plane in FIG. 5.
The TRW coordinate axes are centered at point 100, with the positive width axis W into the plane of the FIG. 3. Assuming the lower part of biarch 10 is a free body, it must be stable under the influence of compressive load P.sub.Δ/ec and neither translate nor rotate. Therefore, a reaction force equal to P.sub.Δ/ec in magnitude and in opposite direction acts at point 100. Also, a counterclockwise bending moment M max acts in the plane of biarch centroid curve 50, about the W axis. Both are illustrated in FIG. 3. To prevent rotation,
M.sub.max =P.sub.Δec *h.sub.max
where h max is the perpendicular distance between the parallel P.sub.Δ/ec forces.
The maximum bending stress in the arches of biarch 10 produced by biarch bending moment M max is,
σ.sub.m max =M.sub.max *d.sub.max /(2*I.sub.d max)
where, I d max is the maximum moment of inertia, or more properly the second moment of area, of arches 20 and 30 in the R, or biarch depth direction, with respect to the W axis. For solid laminated wood arches in FIGS. 3 and 5,
I.sub.d max =A.sub.a *(d.sub.max -t.sub.a).sup.t /2
where, A a is the cross sectional area of each arch 20 and 30, less the projected area of the holes for through bolts 46 in FIG. 5. t a is the arch thickness in radial directional R. This equation also neglects the small contribution of the second moment of area of each arch, with respect to its own width axis.
The maximum normal stress on the cross section areas of arches 20 and 30, due to reaction force--P.sub.Δ/ec centered at point 100 is,
σ.sub.n max =P.sub.Δ/ec /(2*A.sub.a)
This stress will be used later to determine arch bending stress due to cross tie spacing.
The stiffness of biarch 10 in FIGS. 1, 3 and 5 can be quantified as a spring constant, the ratio of compressive load P.sub.Δ/ec along chord line 90 in FIG. 1 to the resulting deflection ΔL c along that line. The deflection of an arch may be computed from (Ref. 4, Timber Construction Manual, 3rd. ed., American Institute of Timber Construction, 1985, pg 5-256, eq. 5-74), ##EQU1## where: ΔL c is the deflection along chord length L c resulting from compressive loads P.sub.Δ/ec ;
L bacc is the curved length of biarch centroid curve 50;
N is the hypothetical number of equal length segments L bacc is divided into for computational purposes;
E is the elastic modulus of arches 20 and 30 in tangential directions;
M n is the biarch bending moment at positions n on centroid curve 50;
I n is the second moment of area, in the R direction, with respect to the W axis, of biarch 10 at positions n;
m n =1*h n is a bending moment at positions n resulting from a hypothetical unit load applied at the location of and in the direction in which deflection ΔL c is desired;
h a is the perpendicular distance from point n on biarch centroid curve 50 to chord line 90, along which P.sub.Δ/ec acts.
The biarch stiffness is therefore, ##EQU2##
5. Fundamental Biarch Equation
The above equations for biarch stiffness P.sub.Δec /ΔL c and bending moment stress σ m max can be combined to obtain a very useful expression governing the structural characteristics of biarch framing members.
d.sub.max /h.sub.max =BSF*e.sub.uit *BSE*(span/deflection)
where: d max /h max is the ratio of maximum biarch depth to maximum biarch height above chord line 90;
BSF is a biarch shape factor, ##EQU3##
e uit is the ultimate useful tangential strain capacity of biarch arches;
BSE=e m max /e uit , is the fraction of the ultimate useful arch strain used to resist the maximum biarch bending moment, produced by the worst-case loading. It serves as a quantitative measure of the structural efficiency of the biarch framing member design in resisting internal bending moments;
Span/deflection, the ratio of clear span to maximum allowable deflection of the biarch structure frame, approximately L bacc /L c ;
BSF, the first term on the right side of the above equation has a value less than two, which depends of the shape of the biarch centroid curve and the radial distances of the arches from it. BSF equaled 1.357 for the hyperbolic shaped biarch 10 in FIG. 1.
The second term e uit is the ultimate useful strain of the arch material in tangential directions. Structural materials with ultimate use strains of 0.1% to 0.25% will be useful for biarch construction.
The third term e m max /e uit can be considered a quantitative measure of the structural efficiency of a specific biarch design. It is the fraction of ultimate useful arch strain which goes to resist the maximum biarch bending moment which results from the worst-case loading of a biarch framed structure. It can be in the range 0.5 to 0.6 for hardwood arches in biarch framing members with generous cross tie spacings. It was slightly less than 0.5 for biarch 10 in FIG. 1.
The fourth term of the right is the ratio of clear span of a two member biarch frame to the maximum allowable frame deflection, which is approximately equal to L bacc /ΔL c max for worst-case wind and/or snow loading. This ratio, which has been determined from long structural experience, is usually specified in building codes.
The term on the left is the ratio of maximum biarch depth to maximum biarch height above the chord line from base to ridge, for a biarch framing member having specific arch shapes and resulting biarch shape factor, which can utilize arches with ultimate strain capacity e uit and meet a specified span/deflection requirement with a desired biarch structural efficiency, BSE. Lower d max /h max ratios will lower biarch structural or increase maximum structural deflections or both. If it is desired to use the arch material selected more efficiently in support of structure loads and/or decrease structure deflections to meet a higher span/deflection requirement, d max /h max will have to be increased. Alternately, the arch material may be changed or arch design and shape factor BSF modified.
The above fundamental equation for biarch structural framing members was used to determine what structural materials would be useful for arches in biarch frames and in what type of end-use structures. Using the biarch shape factor of 1.375, obtained for biarch 10, FIG. 1, d max /h max was computed as a function of e uit , with BSF span deflection limit and BSE as parameters. The results are illustrated in FIG. 4. As an example, arches with ultimate usable strain of 0.2%, used in a biarch design having an biarch structural efficiency of 50%, would meet a 240/1 span/deflection requirement with a d max /h max of 0.325.
The ratio d max /h max has optimum values in any specific arched structure. It is desired high for high biarch structural efficiency and stiff structures. It is desired low for high cross tie spacings, with resulting lower costs, and for the least intrusion of the inside arches into the interior structure volume. On the last point, if d max /h max was two, the inside arches would be straight from base to ridge and the interior clear volume no greater than in a similar A-frame structure. For this reason alone, d max /h max should be less than one, preferably less than 0.5.
6. Biarch Materials
The best arch materials for specific structure purposes can be determined from the above considerations and the computed values using the fundamental biarch equation, as illustrated in FIG. 4.
Structural steel would be the preferred arch material for biarch construction for stiff structures (span/deflection ratios of 500 and 360) with brittle cladding materials such as glass glazing or plaster ceilings.
Hardwood arches are preferred for residential roofs, span/deflection ratio of 240/1, where vaulted ceilings, abundant natural light, clear spans for unrestricted use of interior space and the aesthetic appeal of naturally finished hardwood and arched shapes are desirable characteristics.
Extruded sections of 6053 aluminum formed into arches for biarch construction would be useful in commercial and residential roofs where corrosion resistance is required.
Reinforced concrete with reinforcing steel having tensile yield strengths of 40,000 to 75,000 psi could meet any span/deflection requirement with reasonable ratios of biarch depth to height above the chord line.
A low cost arch material having maximum useful strains e uit in the range 0.3% to 0.5% and durable in wet environments would be useful for commercial greenhouses and agricultural arched structures.
In most cases, the arch material would also be used for the cross ties and end ties. Wood is an exception, due to its low usable shear strength across the grain, which is typically less than 10% of its usable bending strength parallel to the wood grain. To shear the full depth of a wooden arch, cross tie forces must bear on the top and the bottom surfaces of the arches. This is preferably done with steel bolts, through the arch depth to connect with steel cross ties as illustrated in FIGS. 1, 3 and 5. Wood cross ties bolted through the width of wood arches at mid-thickness with steel bolts and split ring timber connectors would require shorter cross tie spacings along the biarch centroid curve 50 and more cross ties. This may be acceptable where wood cross ties are desired for exceptional requirements.
7. Best North American Woods for Biarch Construction
The greatest use of biarch framing members will be in arched structures having span/deflection requirements of 240/1. Hardwoods have ultimate strain capacities in the direction of the wood grain which in 240/1 arched roofs require near optimum ratios of biarch depth to height, d max /h max , of 0.2 to 0.5.
While specific deflection limitations for arches have not been generally established (Ref. 4, pg 5-256), they are likely to be similar to those for present wood frame residential construction using wood truss roofs and stud walls. Maximum deflections, for structural members supporting roofs and exterior walls exposed to wind and/or snow loadings, of 1/240 of the span are recommended for residential structures (Ref. 5, The BOCA R National Building Code/1993, Building Officials & Code Administrators International, Inc).
Hurricane winds produce lift pressures on single story arched roofs of nearly 100 lbs/ft 2 . Snow loads in some mountainous areas can be similar. The following criteria used to rank North American woods for use in biarch framing members capable of safely carrying these loads and meeting the span deflection requirements of applicable building codes:
1. High ratio of elastic modulus in bending E, lbs/in 2 to density ρ, lbs/in 3 , for strong, stiff, light weight structures;
2. High strain at the proportional limit in compression parallel to the grain, S cpgep1 /E, since it is lower in compression than in bending. Average values for wood species (Ref. 6, L. J. Markwardt and T. R. C. Wilson, Strength and Related Properties of Woods Grown in The United States, Tech. Bulletin No. 479, Forest Products Laboratory, U.S.D.A., 1935) were reduced by a factor of 0.8 so that about 95% of the specimens of a species would have greater proportional limit stress values in compression parallel to the grain. This value was reduce further by 1/1.75 to obtain a value applicable for normal duration of load of ten years. This value, divided by E, was then increased by 1.33 to obtain the maximum usable strain in laminated wood biarch members when the worst-case loading is wind, e max wind. The ten year strain value was increased by only 1.15, for worst-case snow load, e max snow.
3. High shear strength parallel to the grain, τ s , for high biarch cross tie force and spacing. This value was also applied across the grain;
4. High compression stress, across the grain, at the proportional limit, S cagep1 , for small cross tie bearing areas.
A somewhat arbitrary product of the above wood properties was used to rank North American woods for use in biarch construction:
E/ρ*(S.sub.cpgep1 /E)*(τ.sub.s *S.sub.cagep1).sup.0.5
In addition to this property product, e max wind and e max snow are listed in the following table for the top 32 North American woods. The Rank is the above property product as a percentage of that for black locust, the best wood for biarch construction using these criteria.
TABLE______________________________________Rank Common Name Scientific Name e.sub.max wind e.sub.max snow______________________________________100 Black Locust Robina pseudoacacia .2017 .174485.3 Persimmon Diospyros virginiana .1933 .167184.3 Blue Gum Eucalyptus globulus .2101 .181777.5 Blue Ash Fraxinus quadrangulata .2371 .205077.3 Canyon Live Oak Quercus chrysolepis .2307 .199575.3 Sugar Maple Acer saccarum .1791 .154875.3 Live Oak Querous virginiana .1572 .135972.9 Honeylocust Gleditsia triacanthos .1958 .169372.3 Sweet Birch Betula lenta .1774 .153470.9 Pacific Yew Taxus brevifolia .2130 .184270.8 Pecan Carya illinoensis .1820 .157470.2 Cherrybark Oak Querous falcata pagodifolia .1693 .146470.2 Biltmore Ash Fraxinus biltmoreana .2155 .186369.0 Green Ash Fraxinus pennsylvanica .1875 .162168.4 White Ash Fraximus americana .1989 .172068.4 Slash Pine Pinus elliottii .1854 .160363.3 Yellow Birch Betula alleghaniensis .1854 .160362.1 Pond Pine Pinus serotina .2189 .189361.2 Black Cherry Prunus serotina .2432 .210360.7 Longleaf Pine Pinus palustris .1879 .162559.5 Swamp White Quercus bicolor .1729 .1495Oak59.4 Western Larch larix occidentalis .2116 .182958.9 Black Walnut Juglans nigra .2092 .180958.6 Douglas Fir, Pseudotsuga taxifolia .2043 .1766coast57.9 Hophornbeam Ostrya virginiana .2067 .178757.3 Scarlet Oak Quercus coccinea .1767 .152855.0 Douglas Fir, Pseudotsuga taxifolia .2054 .1776inter.54.5 Rock Elm Ulmus thomasii .1856 .160454.4 Port Orford Cedar Chamaecyparis lawsoniana .2070 .179050.9 Pin Oak Quercus palustris .1624 .140448.9 Shortleaf Pine Pinus echinata .1758 .152048.7 White Oak Quercus alba .1626 .1406______________________________________
In using the above strain limits for biarch design purposes, realistic safety factors must be considered and the hardwoods would have to be harvested and processed by species not just type, e.g., scarlet oak or pin oak, not red oak.
Many of the above woods will not be used for biarch construction, due to small size, limited supply or other more valuable uses. However, two of the best, black locust and honeylocust, have no other valuable commercial uses and would be better utilized for biarch construction. Also the hardest of the southern yellow pines, which are now used in wood frame construction, have good properties for arches in biarch framing members.
8. Biarch Buckling Resistance
When biarch 10 in FIG. 1 is loaded by compression forces P.sub.Δ/ec along chord line 90, it not only bends in the plane of centroid curve 50 and deflects along chord line 90, it also deflects normal to this plane in the width direction. It may also rotate about tangents to centroid curve 50. These buckling type lateral deflections and rotations occur because centroid curve 50 is not perfectly planar and the compressive load forces P.sub.Δ/ec are not coplanar with the centroid curve. The lateral distance eccentricities can be a significant fraction of the biarch width W bn in FIG. 5.
In practice, a hypothetical reference plane, for which the root-mean-square, rms, distance of the biarch centroid curve 50 from the reference plane is a minimum, can be considered the "coplane" of the biarch centroid curve. Biarch framing members, of specific design, manufacture and assembly in an arched structure, must have a rms distance of its centroid curve from its coplane which is less than some specified maximum distance, to be acceptable for use in its intended application.
FIG. 8 illustrates one example of the concept of biarch coplane used herein. Arch areal centroid curves 25 of outside arch 20 and 35 of inside arch 30 will almost never be perfectly planar, shown deviating from plane 110 by distance arrows 41 oriented perpendicular to plane 110. Biarch centroid curve 50 is the curve of centroid points of the combined areal cross sections of arches 20 and 30. The perpendicular projections of centroid curves 25, 35 and 50 onto plane 110 are shown as curves 24, 34 and 54, respectively. Behind coplane 110, these centroid curves are shown as dashed lines and in front of it as center lines. For simplicity, the perpendicular distance deviations, arrows 41, of all three centroid curves from coplane 110 were assumed as half periods of sine functions. End arrows 21 for centroid curve 25, 31 for centroid curve 35 and 51 for centroid curve 50 are the rms distances of the respective centroid curves from coplane 110. If the arch and biarch centroid curve shapes are assumed fixed and plane 110 was translated or rotated about any axis, the rms distance of biarch centroid curve 50 from plane 110 would increase. The orientation of plane 110 for which the rms distance of biarch centroid curve 50 from plane 110 is a minimum is herein considered to be the biarch coplane.
The required buckling characteristics of biarch framing members can be understood by considering the lower part of biarch 10 as illustrated in a perspective view in FIG. 5. Rotational buckling about centroid curve 50 will be considered first, followed by a quantitative determination of lateral buckling requirements.
Reaction forces F c and F t , which are assumed normal to plane RW, are eccentric to axis R by distances ec c and ec t , respectively. The eccentricity of internal reaction tensile force Ft produces a moment equal to F t * ec t which tends to deflect outside arch 20 in the negative W direction, towards the R axis. The moment of internal reaction compressive force F c times its eccentric distance ec c tends to move inside arch 30 in the positive W direction, further away from the R axis. Taken together, these two displacements are a shear displacement in the RW plane. If cross ties 40 have shear rigidity in RW planes, which are perpendicular to centroid curve 50, relative shear displacements between outside arch 20 and inside arch 30 will be resisted and the two arches will act as a unit, i.e. as a biarch, and tend to rotate in RW planes about tangents to centroid curve 50.
However, such rotational buckling is resisted by the polar moment of inertia,
I.sub.p =I.sub.d +I.sub.w
Lateral buckling, to be considered below, is controlled by I w , the second moment of area, in the width direction W, with respect to the depth or radial axis R. I w of biarch 10 is constant over the length L bacc of centroid curve 50. Since I d , which varies along L bacc , is much greater than I w , rotational buckling is much less than lateral buckling when cross ties 40 have shear rigidity in planes perpendicular to centroid curve 50. This is the second most important function of cross ties 40.
FIG. 9 shows cross tie 40 with its shear plate 42 essentially coplanar with its radial-width plane 49. These shear plates 42 and their arch connecting means, welded end bars 44, bolts 46 and nuts 48, all shown in FIG. 5, have sufficient shear rigidity in RW plane 49 to resist relative displacement in the width direction between inside arch 30 and outside arch 20.
The most important function of cross ties 40, to resist relative radial displacements between arches 20 and 30, requires cross tie rigidity in radial directions R. Their second most important function, to resist relative shear displacements in RW planes between arches 20 and 30, requires shear rigidity in those RW planes. Cross ties 40 must also be rigid in the width direction W to maintain lateral spacing of sub-arches 23 and 26 and sub-arches 33 and 36. Requiring cross ties 40 to have shear rigidity in all directions in their RW planes is sufficient, since shear rigidity in any direction assures tensile and compressive rigidity in directions plus or minus 45° to the shear direction.
For the above reasons, it is realistic to refer to cross ties 40 as RW ties. The tensile and compressive rigidity of RW ties and their arch connecting means in directions radial to the biarch centroid curve at RW tie locations must be sufficient to resist relative radial displacement between arches 20 and 30, as described above. They should additionally have, with their arch connecting means, sufficient shear rigidity in the radial-width plane to resist relative displacement between arches 20 and 30 in the width direction, also as described above. This will force the biarch framing member to act as a unit, resisting rotational buckling with the polar moment of inertial of the entire biarch and not just with the sum of the much lower polar moments of inertia of the individual arches 20 and 30.
Analysis of the lateral buckling of arches uses the same theory as the buckling of columns in directions of minimum second moments of area (Ref. 7, S. Timoshenko and G. H. MacCullough, Elements of Strength of Materials, 3rd. ed., D. Van Nostrand Co., Inc.). Consider biarch 10 in FIG. 1. The minimum second moment of area, in the width direction, with respect to the R axis, which biarch 10 must have in order to limit the maximum lateral deflection ΔW max in the W direction, as a fraction of the initial maximum eccentricity ec max of compression forces P.sub.Δ/ec is,
I.sub.w min =P.sub.Δ/ec *L.sub.bacc.sup.2 /[(k.sup.2 *E*ArcCos.sup.2 (1/(1+ΔW.sub.max /ec.sub.max))]
where: I w min is the minimum second moment of the biarch area, in the W direction, with respect to the R axis, which in biarch 10 does not vary along centroid curve 50;
k is the number of quarter waves in the buckled length L bacc , the length of centroid curve 50 between points of intersection with chord line 90. k=2, where both biarch ends are pinned and free to rotate about the R axis. k=3, in the more likely case where the ridge end is pinned and the base end can be considered fixed and not free to rotate about the R axis;
ec max is the maximum expected initial eccentricity of compressive loads P.sub.Δ/ee in the W direction considering biarch design, manufacture and installation in an arched structure.
ΔW max is the maximum permissible lateral deflection of biarch 10 in the W direction;
P.sub.Δ/ec, L abcc and E are defined above.
Using P.sub.Δ/ec =M max /h max , M max =2*σ m max *I d max /d max , ##EQU4##
Here, I w min is the minimum second moment of area, with respect to the R axis, as a percentage of I d max, of biarch 10 which will limit lateral buckling deflection to ΔW max , as a fraction of the maximum expected initial eccentricity ec max of applied compressive loads P.sub.Δ/ec. All factors in this equation are defined above.
Assuming values for L bacc , h max and d max of biarch 10, FIG. 1, quantitative effects of allowable ΔW max /ec max , arch tangential strain capacity e uit and biarch structural efficiency e m max /e uit on the minimum lateral second moment of area, with respect to the R axis, I w min, as a percentage of the maximum second moment of biarch area, in the R, or depth, direction, with respect to the W axis, I d max, has been computed and illustrated in FIG. 6. Biarch 10 was assumed pinned at both ends, k=2. Results of FIG. 6 would have to be reduced by 4/9 to apply to the case of a biarch framing member with a pinned ridge connection and a fixed base connection.
Most biarch framing members with pinned-pinned ends will have I w min between two and twenty percent of I d max. Biarch applications where the base end can be considered fixed will have I w min between one and ten percent of I d max. The primary purpose for preferring that arches 20 and 30 be divided into halves and separated in the width direction by a distance LS was to make I w , equal or greater than I w min, sufficiently large that the biarch framing members would be self-resistant to excessive lateral deflections, without depending on lateral support from purlins, cladding, etc.
When internal reaction force-P.sub.Δ/ec in FIG. 3 is eccentric to axis R, it not only causes lateral deflections in the W direction, it also causes bending stresses increasing linearly from the R axis to both limits of W ba . The maximum of these stresses is,
σ.sub.ec max =P.sub.66/ec *ec.sub.max *W.sub.ba /(2*I.sub.w)
which is needed below.
9. Cross Tie Spacing
The ultimate stress capacity σ uit in tangential directions of arches 20 and 30 in FIGS. 1, 3 and 5 has four components,
σ.sub.uit =σ.sub.m max +σ.sub.n +σ.sub.ec max +σ.sub.cts max
All have been determined above except for σ cts max, the maximum arch bending stress due to cross tie spacing. Therefore,
σ.sub.cts max =σ.sub.uit -σ.sub.m max -σ.sub.n -σ.sub.ec max
Now that σ cts max has been quantified, the maximum cross tie spacings along the centroid curves 25 and 35, in FIG. 7, of outside arch 20 and inside arch 30 can be determined. Consider inside arch 30 in FIG. 7. Assume half of the segment of inside arch 30, over arc angle θ 1 , a free body acted upon by two internal reaction forces F i . These two forces are not quite collinear, by the small angle, θ i where,
θ.sub.i =S.sub.cti /2/R.sub.i
Since no rotation of the free body occurs in the biarch coplane about point 105,
F.sub.i *R.sub.i *θ.sub.i.sup.2 /2=2*M.sub.cts
where the two counterclockwise moments M cts are equal on the theory of minimum elastic strain energy.
Then,
σ.sub.ctsi =F.sub.i *S.sub.cti.sup.2 *t.sub.a /(32*R.sub.i *I.sub.a)
where:
F.sub.i =[σ.sub.m max *(1-t.sub.a /d.sub.max)+σ.sub.n ]*W.sub.a *t.sub.a ;
I a =W a *t a 3 /12, for arches of rectangular cross section.
Again, arch width W a does not include the hole diameters for cross tie bolts 46, in FIG. 5.
Combining the above three equations, the maximum cross tie spacing along inside arch 30's centroid curve 35 occurs when σ ctsi =σ cts max,
S.sub.cti max =[(8*R.sub.i *t.sub.a σ.sub.cts max)/(3*(σ.sub.m max *(1-t.sub.a d.sub.max)+σ.sub.n))].sup.0.5
A similar expression is valid for cross tie spacings along arch centroid curve 25 of outside arch 20, except the sign of σ m max will change relative to that for σ n and outside radius R a is used. One of these two spacings will limit, where cross ties 40 are kept perpendicular to biarch centroid curve 50.
Notice that the spacings of the cross ties along the arch centroid curves increase with arch radius to the 0.5 power. This is one of the major advantages of the biarch concept, keeping the number cross ties required for each framing member to a minimum and increasing the aesthetic appeal of the biarch.
10. Cross Tie Forces
Cross tie force & Arch Shear Stresses F ct is,
F.sub.ct =(|F.sub.i |*S.sub.cti /R.sub.i +|F.sub.0 |*S.sub.ct0 /R.sub.0)/2
Tangential stress σ ec does not contribute to net cross tie force. Therefore,
F.sub.i =[σ.sub.m max *(1-t.sub.a /d.sub.max)+σ.sub.n ]*W.sub.a *t.sub.a ;
F.sub.0 =[-σ.sub.m max *(1-t.sub.a /d.sub.max)+σ.sub.n ]*W.sub.a *t.sub.a.
Cross tie force F ct is resisted by shear stress τ ct on both sides of cross tie end bars 44 with a parabolic distribution which peaks at mid-thickness.
τ.sub.ct max =(3*F.sub.ct)/(4*W.sub.a *t.sub.a)
Near the biarch ends, end forces P.sub.Δ/ec have components normal to biarch centroid curve 50 which will produce shear stresses τ et in arches 20 and 30 which will add to those produced by cross ties 40 adjacent the biarch ends.
τ.sub.s max =τ.sub.ct max +τ.sub.et max | A biarch consists of two coplanar arches, curved in the same direction and radially spaced with cross ties having shear rigidity in planes perpendicular to the cross section areal center curve of the arch pair. End ties resist relative tangential arch displacements. Biarch framing members are strong, stiff, durable and economical structural members for framing aesthetically pleasing, clear span arched structures capable of withstanding hurricane winds and mountain snows. The most efficient materials for constructing biarch framing members are hardwoods, aluminum and steel. Biarch frames spanning up to fifty feet can be assembled or disassembled by one or two persons using common hand tools. | 4 |
This application is a divisional of application Ser. No. 07/907,501, filed on Jul. 1, 1992, now U.S. Pat. No. 5,347,827, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a refrigerated cabinet for storing beverage containers and other food items, and more particularly, to a cabinet for housing a plurality of readily interchangeable and independent modular elements which collectively define a refrigeration cabinet having multiple uses.
Beverage containers are displayed and sold in a variety of different types of refrigerated self-serve display cabinets and coin-operated vending machines. The sales environment in which the machine will be used most times determines the necessary attributes of a particular refrigerated cabinet. For example, a glass door merchandiser may be chosen to sell items inside a business, but would not be practical for vending items outside the business where a closed coin-operated merchandiser would be a better choice.
However, conventional refrigerated cabinets are not easily convertible from one type of merchandiser to another. For example, if a vendor purchases a closed vending machine but later discovers the need for a display type refrigerated cabinet, there is presently no way of economically and conveniently converting that machine. This is due in part to differences in the refrigeration systems provided by the two diverse types of vendors. This inability to convert merchandisers prohibits vendors from utilizing more effective methods for selling a product. Further, a vendor's purchase of a plurality of different types of cabinets causes expense and inventory problems.
SUMMARY OF THE INVENTION
It is a primary object of this invention to provide a modular refrigeration apparatus with a cabinet having a front opening and divided into refrigerated and unrefrigerated portions for housing a plurality of removable modular units, the removable modular units including one of a selected plurality of interchangeable storage units and substantially the same refrigeration unit for use with either storage unit.
It is a further object of the invention to provide a modular refrigeration apparatus in which a plurality of interchangeable storage units and a refrigeration unit can be easily removed or inserted from within a cabinet without affecting the other units.
It is a further object of the present invention to provide a modular refrigeration apparatus in which one of a plurality of interchangeable storage units includes a vending unit for storing and dispensing a plurality of containers having a front panel which attaches to and seals the front opening of the cabinet, the front panel having a product selection mechanism for enabling a customer to choose the product to be dispensed and a vending mechanism for ejecting the selected container.
It is a further object of the present invention to provide an interchangeable storage unit having a transparent door, the transparent door unit having a transparent door pivotally attached to a frame for mounting to the cabinet across the front opening for sealing the cabinet and an air distribution plenum disposed at the rear interior of the cabinet with slots to facilitate circulation of cool air for cooling the contents of the cabinet.
It is the further object of the present invention to provide a modular refrigeration apparatus having a condenser, compressor, evaporator, first fan and second fan capable of easy installation and removal from the cabinet without affecting the storage unit.
A modular refrigeration apparatus in accordance with the present invention includes a cabinet having a front opening and divided into refrigerated and unrefrigerated portions, for separately receiving a plurality of removable modular units, said removable modular units including one of a selected plurality of interchangeable storage units and a universal refrigeration unit useable with any one of the storage units. A selected one of the plurality of interchangeable storage units is positioned within the refrigerated portion of the cabinet for storing a plurality of containers. The refrigeration unit is positioned within the unrefrigerated portion of the cabinet and in communication with the refrigerated portion for cooling the entire interior of the cabinet. The cabinet is designed so that the interchangeable storage units and the universal refrigeration unit can be respectfully removed or inserted from the cabinet without affecting the other units.
Further objects, features and other aspects of the invention will be understood from the following detailed description of the preferred embodiments of the disclosed invention referring to the detailed drawings given below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of the exterior of the modular refrigeration apparatus of the present invention with a transparent door storage unit in place;
FIG. 2 is a front elevational view of the exterior of the modular refrigeration apparatus of FIG. 1;
FIG. 3 is a side elevational view of the exterior of the modular refrigeration apparatus of FIG. 1;
FIG. 4 is a cross sectional view of the interior of the modular refrigeration apparatus along line 4--4 of FIG. 2;
FIG. 5 is a cross sectional view of the interior of the modular refrigeration apparatus also along 4--4 of FIG. 2 with the modular refrigeration unit removed;
FIG. 6 is an enlarged isometric view of the refrigeration unit of FIG. 5;
FIG. 7 is a cross sectional view of the modular refrigeration unit as shown in FIG. 4 along line 7--7;
FIG. 8 is an upper cross sectional view of the modular refrigeration unit as shown in FIG. 4 along line 8--8;
FIG. 9 is a front elevational view of the modular refrigeration apparatus with the door removed showing air directing slots in the distribution plenum;
FIG. 10 is a cross sectional view of the modular refrigeration apparatus of FIG. 9 along line 10--10 of FIG. 9 highlighting a portion of the distribution plenum;
FIG. 11 is an isometric view of the exterior of the modular refrigeration apparatus of the present invention with a modular vendor unit substituted for the transparent door unit; and
FIG. 12 is a cross-sectional view of the modular refrigeration apparatus with a modular vendor unit along line 12--12 of FIG. 11.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is generally directed to a cabinet and readily interchangeable storage units and refrigeration unit in a modular refrigeration apparatus as illustrated and described below.
With reference to FIG. 1, the exterior of a first embodiment of a modular refrigeration apparatus according to the present invention is shown. This embodiment is directed to a modular refrigeration apparatus having a transparent door storage unit 2. The modular refrigeration apparatus includes a box-shaped cabinet 3 having a top, bottom, and three sides with a central front opening 4 for receiving the modular units. In this embodiment, the transparent door storage unit 2 is attached to the upper portion of the cabinet 3 and defines the front wall of the refrigeration apparatus. The transparent door storage unit 2 has a transparent panel 5 suspended in a frame 6 and pivotally mounted on a door jamb (not shown) surrounding the central front opening 4. A handle 8 is affixed to the exterior front edge of the frame 6 to facilitate easy manual opening of the door unit. A removable grill 9 completes the remaining and lower portion of the front wall.
Product is supported on spaced shelves (not shown) within storage unit 2.
FIG. 2 is a front elevational view of the modular refrigeration apparatus 1 with a transparent door storage unit 2. The panel 5 is substantially transparent for allowing customers to see the contents of the cabinet without opening the door.
FIG. 3 is a side elevational view of the modular refrigeration apparatus of FIG. 1. There the transparent door storage unit 2 is shown as abutting the edges of the central front opening 4 for creating a sealed storage unit. A compliant seal 10 is attached to entire peripheral interior edge of the casing 6 of the transparent door storage unit 2 and between the front edge of the cabinet 3 and the frame 6. When closed, the compliant seal 10 forms an air-tight seal between the periphery of the casing and the cabinet's front edge to seal the refrigerated portion of the cabinet 3.
FIG. 4 is a cross sectional view along 4--4 of FIG. 2 showing the interior of the modular refrigeration apparatus. The cabinet 3 is divided into a refrigerated portion 11 and an unrefrigerated portion 12. The refrigerated portion 11 contains the transparent door storage unit 2 and its contents. The unrefrigerated portion houses the refrigeration unit. The refrigerated portion 11 is partially divided from the unrefrigerated portion 12 by a divider 18.
The transparent door storage unit 2 includes a modular transparent door unit 2 and an air distribution system for directing the circular flow of cool air within the refrigerated portion 11 of the cabinet 3.
The air distribution system includes a vertically disposed, ventilated, false back wall 19 which is used to initiate the circular flow of cool air within the upper portion 11 of the cabinet 3, and an air deflection plate 20 extending horizontally therefrom. The ventilated false back 19 is spaced apart from, and substantially parallel to, the rear interior wall of the refrigerated portion 11 of the cabinet 3 creating an air distribution plenum 21 therebetween. The air distribution system also includes a base plate assembly 22 for supporting the false back 19 and air deflection plate 20. The base plate assembly 22 supports the false back and abuts the refrigeration unit 15 forming two distinct air flow channels to and from the refrigeration unit 15.
The refrigeration unit 15 is shown in detail FIGS. 5-8. With reference to FIG. 6, the refrigeration unit 15 includes an evaporator 23, a condenser 24, a compressor 25 and a temperature controller 26. The components of the refrigeration unit 15 are collectively arranged on a base 27. The base 27 is supported on a plurality of skids 28 affixed to the bottom of the base 27. The temperature controller 26, compressor 25, and condenser 24 are contained in the front portion of the base 27. The condenser 24 is enclosed within a condenser shroud 30 having a rear exhaust slot 30A (See FIG. 5). The front portion and rear portion of the refrigeration unit 15 are separated by a central partition 32. The evaporator 23 is contained within an evaporator tray 29, which collects condensed water from the cooled air as it passes over the evaporator 23. The condensed water drains out of evaporator pan 29 through a hole (not shown) in the bottom of the pan. The hole in the bottom of pan 29 aligns with hole 29A located in the bottom panel in the lower portion of the unit. The condensed water continues through hole 29A then drains into a shallow pan (not shown) located on the floor of condenser exhaust channel 38. Warm air from the condenser evaporates the water. A handle H assists in easily moving the refrigeration unit 15 in or out of the cabinet 3.
Air AR enters the condenser 24 through the removable front grill 9. Air AR flows through the condenser 24 passing over the coil 37 which runs throughout the condenser 24. The condenser exhaust is then pulled into the squirrel cage fan impeller 36A. The shroud 30 assists in directing the condenser exhaust into the fan 36A. The Squirrel cage fan impeller 36A then blows the condenser exhaust through slot "30A" into channel "38", then out into the atmosphere.
With particular reference to FIG. 5, the refrigeration unit 15 is shown removed from the cabinet 3. The refrigeration unit 15 is supported in the unrefrigerated portion 12 of the cabinet 3 on a plurality of the guide rails 31 which are aligned with the skids 28. The refrigeration unit 15 can be easily accessed by removing the removable grill 9 and sliding the refrigeration unit 15 out of the cabinet 3 on the guide rails. This enables the refrigeration unit 15 to be easily repaired or replaced without disturbing the remaining portions of the cabinet 3 or storage modules. The central partition 32 includes a second compliant seal 33 on the evaporator side of the partition that abuts a shelf in the cabinet 3 for sealing the refrigeration unit 3 in communication with the refrigerated portion 11 of the cabinet 3.
FIG. 7 is a cross sectional view along line 7--7 of FIG. 4 of the refrigeration unit 15. The refrigeration unit 15 also contains an evaporator fan 35 for circulating air within the interior of the apparatus, and a condenser fan with a motor 36 and a squirrel cage impeller 36A for exhausting warm air from cooling coils 37 of the condenser 24 through rear exhaust slot 30A.
FIG. 8 shows a cross section of the apparatus along line 8--8 of FIG. 4. The condenser fan including motor 36 and squirrel cage impeller 36A exhausts the warm air WA via a condenser exhaust channel. 38. The condenser fan squirrel cage impeller draws air from around coil 37 and through exhaust slot 24C and condenser exhaust channel 38. The air WA rapidly moving through the right side of the channel 38 creates an aspiration effect drawing air AA into the left portion of the channel. The air AA drawn into the left portion flows past the compressor 25, providing cooling which prevents the compressor from overheating. The squirrel cage impeller 36A creates this rapid air flow.
A front elevational view of the ventilated false back 19 is shown in FIG. 9. The ventilated false back 19 includes a plurality of slots 39 vertically disposed in horizontally spaced columns. These slots 39 direct a portion of the air flow through the air distribution plenum 21 into the interior of the cabinet 3. A space exists between the upper edge 19A of the false back 19 and the upper interior wall of the cabinet 3 for allowing any residual air flow not directed through the slots 39 to flow into the central portion of cabinet 3.
As shown in FIG. 10, slots 39 are separated by curved air directors or baffles 40 positioned adjacent thereto for directing a portion of the air flow through the air distribution plenum 21 into the interior of the cabinet 3 while the remainder of the air flow continues through the air distribution plenum 21. Each air director 40 is curved so as to direct air flow AH toward the front of the cabinet 3 (See FIG. 4).
The airflow circulation within the cabinet 3 is illustrated in FIG. 4. The airflow begins with the evaporator fans 35 (FIG. 7) pushing cool air from the evaporator 23 up the back interior wall of the cabinet 3 into the air distribution plenum 21 (See arrow AV). Air AV traveling into the air distribution plenum 21 is directed by the air directors 40 through the slots 39 and enters the interior of the cabinet creating a plurality of air currents AH. These air currents AH flow over products supported on shelves (not shown) to cool the same to the desired storage temperature. Any residual cool air enters the cabinet from the air distribution plenum 21 through the space between the top edge 19A of the false back 19 and the upper interior wall of the cabinet 3. The air flow along the upper interior surface of the cabinet 3 is directed down along the interior surface of the transparent panel 5 by an air deflector 41. As the cool air contacts the interior of the transparent panel 5, it is directed downward (See arrows AD) through an intake 42 defined between the transparent door storage unit 2 and the front end of the air deflection plate 20. Any air not entering the intake 42 is redirected by the air deflection plate 20 back into the interior of the upper portion 11. Air ingested through the intake 42 is recycled in the refrigeration unit 15 through an evaporator inlet 43 and into the evaporator 23. The air is cooled while in the refrigeration unit by the evaporator 23. Once cooled, the evaporator fan 35 draws the air up and back into plenum 21 of cabinet 3.
FIG. 11 shows a modular refrigeration apparatus 1 with a cabinet 3 and a modular vending unit 44. Similar to the transparent door storage unit 2, the modular vending unit 44 includes the ventilated false back 19. However, the air deflection plate 20 may be removed. Unit 44 is positioned within the refrigerated portion 11 and against the front central opening of the cabinet 3.
The modular vending unit 44 differs from the transparent door storage unit 2 in that the front is opaque or translucent. The modular vending unit 44 is composed of a front panel 45, a plurality of storage racks 46, a product selection device 47 attached to the front panel 45, and a vending mechanism 48 for causing a container to be ejected from a selected one of the storage racks 46 and out an aperture 49 in front of the panel 45.
As illustrated in FIG. 12, storage racks 41 may comprise slant shelves defining side-by-side serpentine paths as are known in the art. Each serpentine path is disposed in adjacent vertical columns viewed from the front of the machine. Other types of vending machine storage racks known in the art may be utilized without departing from the spirit of the present invention.
The front panel 45 is connected to the cabinet 3 at contact points 50. The front panel 45 is disposed adjacent to the edges of the front opening for sealing the interior portion of the cabinet 3. The lower portion of the front panel 45 is connected to a dividing partition 51 which separates the unrefrigerated and refrigerated portions of the cabinet 3. The front panel includes a product selection device 47. The product selection device includes a plurality of selection buttons 52. The front panel also includes a pivotally mounted door 53 over an aperture 49 through which the storage containers are ejected.
The plurality of containers are stored there until a product selection is made causing the vending mechanism 48 to release a container from a selected one of the storage columns 46 and out of the opening 49. Air flow is created in essentially the same manner as with the transparent door storage unit 2.
The invention having been described in detail in connection with the preferred embodiments is to be taken as an example only, not to be restricted thereto. It will be easily understood by those of ordinary skill in the art that other variations and modifications can be easily made within the scope of this invention as defined in the appended claims. | A modular refrigeration apparatus containing a cabinet with a front opening and divided into lower and upper portions, for separately receiving a plurality of removable modular units, said removable modular units including one of a selected plurality of interchangeable storage units and a universal refrigeration unit. A selected one of the plurality of interchangeable storage units is positioned within the upper portion of the cabinet for storing a plurality of containers. The refrigeration unit is positioned within the lower portion of the cabinet and in communication with the upper portion for cooling the entire interior of the cabinet. The cabinet is designed so that the interchangeable storage units and refrigeration unit can be respectfully removed or inserted from the cabinet without affecting the other units. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit to U.S. Provisional Application Ser. No. 61/127,883, filed May 16, 2008, and U.S. Provisional Application Ser. No. 61/212,072, filed Apr. 7, 2009, the contents of which are incorporated herein by reference in their entirety.
BACKGROUND
[0002] According to the World Health Organization, there are five million people dying from cancer every year. Drug treatment is one of the three major therapies for cancer. At present, the anticancer directions are as follows: Interfere with or inhibit cell division, Regulate cell generation cycle, Promote tumor cell to apoptosis, Inhibit angiogenesis, Inhibit oncogene, Promote tumor suppressing gene, Tumor antigen, Inhibitor of telomerase and Interfere with information transfer of tumor cells.
[0003] In view of the high mortality rates associated with abnormal proliferative diseases including cancer, there exists a need in the art for an effective treatment for benign proliferative diseases as well as cancer.
SUMMARY
[0004] This invention is based on the discovery that a combination of certain known drugs is effective in treating hyperproliferative diseases including cancer.
[0005] In one aspect, the invention features a composition that includes (A) a first agent that possesses anti-inflammatory activity or acetaminophen, phenacetin, tramadol and the like, a second agent (B) that can be an oxidative phosphorylation inhibitor, an ionophore, or an adenosine 5′-monophosphate-activated Protein kinase (AMPK) activator, and a third agent (C) that possesses or maintains serotonin activity.
[0006] The first agent can be any suitable anti-inflammatory compound (e.g., non-steroidal anti-inflammatory compounds) or acetaminophen, phenacetin, tramadol and the like. Examples include aspirin, diclofenac (e.g., diclofenac potassium or diclofenac sodium), ibuprofen (e.g., dexibuprofen or dexibuprofen lysine), indomethacin, nimesulide, and a COX-2 inhibitor (e.g., a nitric oxide-based COX-2 inhibitor or Celebrex® (4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl] benzenesulfonamide)). Other examples of the first agent include Aspirin-arginine, Alxiling, L-arginine acetylsalicylic; Aspirin-DL-lysine; Bismuth Salicylate Basic; Bismuth salicylate; Magnesium Salicylate; Diethylamine Salicylate; Salicylic acid, sodium salt; imidazole salicylate; Sodium Aminosalicylate; Isoniazid Aminosalicylate; Physostigmine Salicylate; Pregnenolone Acetylsalicylate; Choline Magnesium Trisalycylate (Trilisate); Salicylic Acid Zinc Oxide; Sodium Salicylate and Sodium Iodide; Salicylic Acid and Acetic Acid Glacial Solution; and Methyl Salicylate.
[0007] The second agent is an oxidative phosphorylation inhibitor, ionophore or AMPK activator). The term “oxidative phosphorylation inhibitor” refers to any suitable agents that inhibit oxidative phosphorylation, such as oxidative phosphorylation uncouplers. An ionophore is a lipid-soluble molecule capable of transporting an ion across the lipid bilayer of cell membranes; and an AMPK activator is an agent that activates AMPK to phosphorylate its substrates, e.g., acetyl-CoA carboxylase and malonyl-CoA decarboxylase. Examples of the second agent include metformin (e.g., metformin chloride), phenformin and buformin.
[0008] The third agent can be a compound possessing or maintaining at least one of the serotonin's activities and, when used in combination with the first and second agents, effectively treats one or more of the target diseases of this invention. Examples include serotonin (e.g., serotonin sulfate, serotonin creatinine sulfate complex, or serotonin hydrochloride) and a serotonin re-uptake inhibitor.
[0009] A preferred composition of the present invention contains aspirin, metformin hydrochloride, and serotonin creatinine sulfate complex.
[0010] In another aspect, the invention features a composition consisting essentially of a first agent that possesses anti-inflammatory activity or acetaminophen, phenacetin, tramadol and the like, a second agent that can be an oxidative phosphorylation inhibitor, an ionophore, or an AMPK activator, and a third agent that possesses serotonin activity. The term “consisting essentially of” used herein limits a composition to the three specified agents and those that do not materially affect its basic and novel characteristics, i.e., the efficacy in treating a target disease described herein. An example of such a composition contains the above-mentioned three agents and a pharmaceutically acceptable carrier. The compositions described above can contain 5-5,000 mg (e.g., 5-3,000 mg, 5-1,500 mg or 5-1,000 mg) of the first agent, 1-5,000 mg (e.g., 1-3000 mg, 1-1,000 mg, 1-500 mg, or 1-100 mg) of the second agent, and 0.1-1,000 mg (e.g., 0.1-100 mg, 0.1-50 mg, or 0.1-30 mg) of the third agent, or in quantities of the same ratio as that calculated based on the above amounts.
[0011] In still another aspect, the invention features a method for treating hyperproliferative diseases. The method includes administering to a subject in need thereof an effective amount of one or more of the compositions described above. The diseases mentioned above also include their associated disorders.
[0012] The term “treating” or “treatment” used herein refers to administering one or more above-described compositions to a subject, who has a disease described above, a symptom of such a disease, or a predisposition toward such a disease, with the purpose to confer a therapeutic effect, e.g., to cure, relieve, alter, affect, ameliorate, or prevent the disease, the symptom of it, or the predisposition toward it.
[0013] The composition described above can be in form suitable for any route of administration. For example, when the composition is orally administered, the present invention in certain embodiments may be administered by any pharmaceutically acceptable oral dosage form including, solids (e.g., tablets, capsules), liquids (e.g., syrups, solutions and suspensions), orally dissolving dosage forms (e.g., orally disintegrating dosage forms, lozenges and troches), powders or granules.
[0014] The compositions may also be prepared for parenteral administration as a solution, or suspension. The compositions may also be in dry form ready for reconstitution (e.g., with the additional of sterile water for injection), prior to parenteral administration. Parenteral administration includes administration into any body space or tissue, for example intravenous, intra-arterial, intramuscular and subcutaneous. Where the intended cite of action is a solid tumor, in certain embodiments the composition may be injected directly into the tumor.
[0015] In certain other embodiments of the invention, one or more active compounds of the present invention are associated with a carrier substance such as a compound or molecule (e.g., an antibody), to facilitate the transport of the one or more active compounds to the intended cite of action. In certain preferred embodiments, active compound B (useful for treating a hyperproliferating tissue), is covalently bonded to an antibody that corresponds to a marker located on the hyperproliferative tissue. According to this aspect of the invention, it is contemplated that toxicity and adverse effects can be reduced because lower levels of the active agent are capable of providing the desired therapeutic effect relative to administration of the active agent that is not associated with a carrier substance.
[0016] The first, second, and third agents described above include active compounds, as well as any pharmaceutically acceptable derivatives such as their salts, pro-drugs, and solvates, if applicable. A salt, for example, can be formed between an anion and a positively charged group (e.g., amino) on an agent. Examples of suitable anions include chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, chlorophenyoxyacetate, malate, tosylate, tartrate, fumarate, glutamate, glucuronate, lactate, glutarate, benzoate, embonate, glycolate, pamoate, aspartate, parachlorophenoxyisobutyrate, formate, succinate, cyclohexanecarboxylate, hexanoate, octonoate, decanoate, hexadecanoate, octodecanoate, benzenesulphonate, trimethoxybenzoate, paratoluenesulphonate, adamantanecarboxylate, glycoxylate, pyrrolidonecarboxylate, naphthalenesulphonate, 1-glucosephosphate, sulphite, dithionate, and maleate. Likewise, a salt can also be formed between a cation and a negatively charged group (e.g., carboxylate) on an agent. Examples of suitable cations include sodium ion, potassium ion, magnesium ion, calcium ion, and an ammonium cation such as tetramethylammonium ion. In certain embodiments, the agents also include salts containing quaternary nitrogen atoms. Examples of pro-drugs include esters and other pharmaceutically acceptable derivatives, which, upon administration to a subject, are capable of providing active compounds. A solvate refers to a complex formed between an active compound and a pharmaceutically acceptable solvent. Examples of pharmaceutically acceptable solvents include water, ethanol, isopropanol, ethyl acetate, acetic acid, and ethanolamine.
[0017] Other examples of the salts include arginine, L-arginine; DL-lysine; Bismuth Salicylate Basic; Bismuth salicylate; Magnesium; Diethylamine; sodium salt; imidazole; Sodium Aminosalicylate; Isoniazid Aminosalicylate; Physostigmine; Pregnenolone Acetylsalicylate; Choline Magnesium Trisalycylate (Trilisate); Zinc Oxide; Iodide; Acetic Acid Glacial Solution and Methyl.
[0018] Also within the scope of this invention is one or more compositions described above for use in treating a disease described herein, and the use of such a composition for the manufacture of a medicament for the treatment of a disease described herein.
[0019] The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
DETAILED DESCRIPTION
[0020] In certain embodiments, a composition of this invention can include three agents.
[0021] Examples of the first agent can include steroidal anti-inflammatory drugs and non-steroidal anti-inflammatory drugs. Examples of steroidal anti-inflammatory drugs include glucocorticoids, hydrocortisone, cortisone, beclomethasone, dipropionate, betamethasone, dexamethasone, prednisone, methylprednisolone, triamcinolone, fluocinolone acetonide, fludrocortisone, and beclometasone propionate.
[0022] Examples of non-steroidal anti-inflammatory drugs (NSAIDs) include A183827, ABT963, aceclofenac, acemetacin, acetyl salicylic acid, AHR10037, alclofenac, alminoprofen, ampiroxicam, amtolmetin guacil, apazone, atliprofen methyl ester, AU8001, benoxaprofen, benzydamine flufenamate, bermoprofen, bezpiperylon, BF388, BF389, BIRL790, BMS347070, bromfenac, bucloxic acid, butibufen, BW755C, C53, C73, C85, carprofen, CBS1108, celecoxib, CHF2003, chlorobiphenyl, choline magnesium trisalicylate, CHX108, cimicoxib, cinnoxicam, clidanac, CLX1205, COX-2 inhibitors, CP331, CS502, CS706, D1367, darbufelone, deracoxib, dexketoprofen, DFP, DFU, diclofenac potassium, diclofenac sodium, diclofenac sodium misoprostol, diflunisal, DP155, DRF4367, E5110, E6087, eltenac, ER34122, esflurbiprofen, etoricoxib, etodolac, F025, felbinac ethyl, fenbufen, fenclofenac, fenclozic acid, fenclozine, fenoprofen, fentiazac, feprazone, filenadol, flobufen, florifenine, flosulide, flubichin methanesulfonate, flufenamic acid, fluprofen, flurbiprofen, FPL62064, FR122047, FR123826, FR140423, FR188582, FS205397, furofenac, GR253035, GW406381, HAI105, HAI106, HCT2035, HCT6015, HGP12, HN3392, HP977, HX0835. HYAL AT2101, ibufenac, ibuproxam-beta-cyclodextrin, icodulinum, IDEA070, iguratimod, imrecoxib, indoprofen, IP751, isoxepac, isoxicam, KC764, ketoprofen, L652343, L745337, L748731, L752860, L761066, L768277, L776967, L783003, L784520, L791456, L804600, L818571, LAS33815, LAS34475, licofelone, LM 4108, lobuprofen, lomoxicam, lumiracoxib, mabuprofen, meclofenamic acid, meclofenamate sodium, mefenamic acid, meloxicam, mercaptoethylguanidine, mesoporphyrin, metoxibutropate, miroprofen, mofebutazone, mofezolac, MX1094, nabumetone, naproxen sodium, naproxen-sodium/metoclopramide, NCX1101, NCX284, NCX285, NCX4016, NCX4215, NCX530, niflumic acid, nimesulide, nitric oxide-based NSAIDs (NitroMed, Lexington, Mass.), nitrofenac, nitroflurbiprofen, nitronaproxen, NS398, ocimum sanctum oil, ONO3144, orpanoxin, oxaprozin, oxindanac, oxpinac, oxycodone/ibuprofen, oxyphenbutazone, P10294, P54, P8892, pamicogrel, parcetasal, parecoxib, PD138387, PD145246, PD164387, pelubiprofen, pemedolac, phenylbutazone, pirazolac, piroxicam, piroxicam beta-cyclodextrin, piroxicam pivalate, pirprofen, pranoprofen, resveratrol, R-ketoprofen, R-ketorolac, rofecoxib, RP66364, RU43526, RU54808, RWJ63556, S19812, S2474, S33516, salicylsalicylic acid, salsalate, satigrel, SC236, SC57666, SC58125, SC58451, SFPP, SKF105809, SKF86002, sodium salicylate, sudoxicam, sulfasalazine, sulindac, suprofen, SVT2016, T3788, TA60, talmetacin, talniflumate, tazofelone, tebufelone, tenidap, tenoxican, tepoxalin, tiaprofenic acid, tilmacoxib, tilnoprofen arbamel, tinoridine, tiopinac, tioxaprofen, tolfenamic acid, tolmetin, triflusal, tropesin, TY10222, TY10246, TY10474, UR8962, ursolic acid, valdecoxib, WAY120739, WY28342, WY41770, ximoprofen, YS134, zaltoprofen, zidometacin, and zomepirac. Other examples of the first agent include acetaminophen, phenacetin, tramadol and the like.
[0023] Still other examples of the first agent include Aspirin-arginine, Alxiling, L-arginine acetylsalicylic; Aspirin-DL-lysine; Bismuth Salicylate Basic; Bismuth salicylate; Magnesium Salicylate; Diethylamine Salicylate; Salicylic acid, sodium salt; imidazole salicylate; Sodium Aminosalicylate; Isoniazid Aminosalicylate; Physostigmine Salicylate; Pregnenolone Acetylsalicylate; Choline Magnesium Trisalycylate (Trilisate); Salicylic Acid Zinc Oxide; Sodium Salicylate and Sodium Iodide; Salicylic Acid and Acetic Acid Glacial Solution; and Methyl Salicylate.
[0024] Examples of the second agent can include, in addition to those described above, 4,6-dinitro-ocresol, uncoupling proteins (e.g., UCP1, UCP2, or UCP3), carbonyl cyanide p(trifluoromethoxy)phenyl-hydrazone, carbonyl cyanide m-chlorophenyl-hydrazone, C5 gene products, dinitrophenol (e.g., 2,4-dinitrophenol), efrapeptin (A23871), guanethidine, chlorpromazine, amytal, secobarbital, rotenone, progesterone, antimycin A, naphthoquinone, 8-hydroxyquinoline, carbon monoxide, cyanides, azides (e.g., NaN3), dicoumarin, bilirubin, bile pigment, ephedrine, hydrogen sulfide, tetraiodothyronine, quercetin, 2,4-bis(p-chloroanilino)pyrimidine, glyceraldehyde-3 phosphate dehydrogenase, oligomycin, tributyltin chloride, aurovertin, rutamycin, venturicidin, mercurials, dicyclohexylcarbdiimide, Dio-9, m-chlorophenyl-hydrazone mesoxalonitrile, ionomycin, calcium ionophores (e.g., A23187, NMDA, CA 1001, or enniatin B), compounds that increase the Ca+2 concentration in mitochondria (e.g., atractyloside, bongkrekic acid, thapsigargin, amino acid neurotransmitters, glutamate, N-methyl-D-aspartic acid, carbachol, ionophores, inducers of potassium depolarization), apoptogens (i.e., compounds that induce apoptosis), valinomycin, gramicidin, nonactin, nigericin, lasalocid, and monensin. The second agent can be an AMPK activator (e.g., metformin or phenformin, buformin, AICAR, thienopyridones, resveratrol, nootkatone, thiazole, adiponectin, thiazolidinediones, rosiglitazone, pioglitazone or dithiolethiones).
[0025] The third agent includes serotonin and its functional equivalents. Examples of the functional equivalents of serotonin include:
[0026] Serotonin 1A agonists such as: (e.g., arylpiperazine compounds, azaheterocyclylmethyl derivatives of heterocycle-fused benzodioxans, or buspirone, 3-amino-dihydro-[1]-benzopyrans and benzothiopyrans, (S)-4-[[3-[2-(dimethylamino)ethyl]-1H-indol-5-yl]methyl]-2-oxazolidinone—311C90) and 8-OH-DPAT), 5-Carboxamidotyptamine hemiethanolate maleate salt, N,N-Dipropyl-5-carboxamidotryptamine maleate salt, R(+)-UH-301 HCl, S15535, gepirone, psilocybin, xaliproden HCl and tandospirone;
[0027] Serotonin 1B agonists such as: CGS-12066a, N-Methylquipazine dimaleate salt, rizatriptan and naratriptan;
[0028] Serotonin 1C agonists such as: dexnorfenfluramine;
[0029] Serotonin 1A, 1B, 1D and 1F agonists such as Sumatriptan and 5-Carboxamidotryptamine hemiethanolate maleate salt;
[0030] Serotonin 1B and 1D agonists such as: dihydroergotamine and GR46611;
[0031] Serotonin 1A and 1D agonists such as: LY-165,163;
[0032] Serotonin 1A and 1E agonists such as: ergonovine and BRL 54443 maleate salt;
[0033] 5-HT 2A/2C agonists such as: DOI (2,5-dimethoxy-4-iodoamphetamine), mCPP (m-chlorophenyl-piperazine), TFMPP (3-Trifluoromethylphenylpiperazine), mescaline, DMT, psilocin, 2C-B, lorcaserin, methylserotonin laleaste salt and 1-(3-Chlorophenyl)piperazine HCl;
[0034] Serotonin 2B agonist such as: BW 723C86;
[0035] Serotonin receptor 2C modulators such as: (e.g., BVT933, DPCA37215, IK264, PNU22394, WAY161503, R-1065, YM348, VER-3323 hemifumarate and those disclosed in U.S. Pat. No. 3,914,250, WO 01/66548, WO 02/10169, WO 02/36596, WO 02/40456, and WO02/40457, WO 02/44152, WO 02/48124, WO 02/51844, and WO 03/033479), the disclosures of which are incorporated by reference in their entireties;
[0036] 5-HT 3 agonists such as Phenylbiguanide, O-Methylserotonin HCl, SR 57227A and 1-(3-Chlorophenyl)biguanide HCl;
[0037] 5-HT 4 agonist such as cisapride, mosapride citrate duhydrate and ML 10302;
[0038] 5HT7 receptor agonist such as: 4-(2-pyridyl) piperazines, LP 12 hydrochloride hydrate, LP44 and quinoline derivatives;
[0039] Serotonin transporter inhibitors such as: imipramine;
[0040] Serotonin reuptake inhibitors such as (e.g., arylpyrrolidine compounds, phenylpiperazine compounds, benzylpiperidine compounds, piperidine compounds, tricyclic gamma-carbolines duloxetine compounds, pyrazinoquinoxaline compounds, pyridoindole compounds, piperidyindole compounds, milnacipran, citalopram, sertraline metabolite, demethylsertraline, norfluoxetine, desmethylcitalopram, escitalopram, 1-fenfluramine, femoxetine, ifoxetine, cyanodothiepin, litoxetine, dapoxetine, nefazodone, cericlamine, trazodone, mirtazapine, fluvoxamine, indalpine, indeloxazine, milnacipran, paroxetine, sibutramine, zimeldine, trazodone hydrochloride, dexfenfluramine, bicifadine, vilazodone, desvenlafaxine, duloxetine, amitriptyline, butriptyline, desipramine, dosulepin, doxepin, lofepramine, nortriptyline, protriptyline, trimipramine, amoxapnie, maprotiline, adhyperforin, bromopheniramine, chlorpheniramine, dextromethorphan, diphenhydramine, hyperforin, ketamine, nefazodone, pethidine, phencyclidine, pheniramine, propoxyphene and those in U.S. Pat. No. 6,365,633, WO 01/27060, and WO 01/162341), the disclosures of which are hereby incorporated by reference in their entireties, EPTI, 8-OH-DPAT, Prozac® (fluoxetine hydrochloride) and Zoloft® (Sertraline hydrochloride);
[0041] Serotonin and noradrenaline reuptake inhibitors such as: (e.g., venlafaxine, venlafaxine metabolite O-desmethylvenlafaxine, clomipramine, and clomipramine metabolite desmethylclomipramine);
[0042] Monoamine re-uptake inhibitors such as: (e.g., amides);
[0043] Pyridazinone aldose reductase inhibitors such as: (e.g., pyridazinone compounds);
[0044] Serotonergic agents, which are also stimulants of serotonin receptors, such as: (e.g., ergoloid mesylate or pergolide mesylate);
[0045] Stimulants of serotonin synthesis such as: (e.g., vitamin B1, vitamin B3, vitamin B6, biotin, Sadenosylmethionine, folic acid, ascorbic acid, magnesium, coenzyme Q10, or piracetam);
[0046] Serotonin receptor agonists such as: Rauwolscine, Yohimbine, .alpha.-Methyl-5-hydroxytryptamine, 1-(1-Naphthyl)piperazine, metoclopramide, HTF-919, R-093877, Zolmitriptan, 5-Methoxy-N,N-dimethyltryptamine, 5-MEO-DIPT hydrochloride hydrate and lysergic acid diethylamide;
[0047] Serotonin precursors such as tryptophan;
[0048] Agents that promote serotonin release from nerve terminals such as: fenfluramine, and norfenfluramine;
[0049] All of the compounds mentioned above are known drugs and are readily available to the public. Some of the drugs can be purchased from chemical companies, such as Sigma-Aldrich, St. Louis, Mo. Where the drugs are not readily available, in certain embodiments, one of ordinary skill in art will appreciate that the compounds can be organically manufactured and identified according to accepted standards such as those found in the Merck Index, Remington's Pharmaceutical Sciences, USP/NF, and foreign publications. In certain embodiments, regimens for administering these drug compounds are well known and, if necessary, can be easily re-established by an ordinary skilled clinician. Effective doses will vary, as recognized by those skilled in the art, depending on the type or degree of the disease to be treated; the subject's size, weight, age, and sex; the route of administration; the excipient usage; rate of metabolism, rate of excretion, and the possible co-usage with other therapeutic treatment. In certain embodiments, coadministration of other drugs can lead to increased or decreased metabolism and or excretion requiring an adjustment in dose. In certain other embodiments, where one or more of the active agents are bound to plasma proteins, coadministration of other drugs that effect the extent of binding may also require an adjustment of dose. The daily dose of the compositions described above can be 5-10,000 mg (e.g., 10-5000 or 10-3,000 mg) of the first agent, 1-5,000 mg (e.g., 2-1,000 or 2-3,000 mg) of the second agent, and 0.1-1,000 mg (e.g., 1-50 mg) of the third agent.
[0050] In certain preferred embodiments the human dose of the composition of the present invention is about 5-5,000 mg of metformin, about 1-5,000 mg aspirin and about 0.1-1,000 mg serotonin creatinine complex. In certain more preferred embodiments, the human dose of the composition is about 1000 mg of metformin, about 400 mg aspirin and about 4 mg serotonin creatinine complex administered as multiple daily doses. In certain further preferred embodiments, this dose is administered three times a day.
[0051] One aspect of this invention features a method of administering an effective amount of one or more of the above-mentioned compositions to a subject for treating a disease described herein. Such a subject can be identified by a health care professional such as a clinician based on results from any suitable diagnostic method. “An effective amount” refers to the amount of one or more compositions described herein that is required to confer a therapeutic effect on a treated subject.
[0052] To practice the method of the present invention, in certain embodiments, one or more of the above-described compositions can be administered parenterally, orally, nasally, rectally, topically, or buccally. The term “parenteral” as used herein refers to subcutaneous, intracutaneous, intravenous, intramuscular, intraarticular, intraarterial, intrasynovial, intrasternal, intrathecal, intralesional, or intracranial injection, as well as any suitable infusion or injection technique.
[0053] A sterile injectable composition can be a solution or suspension in a non-toxic parenterally acceptable diluent or solvent, such as a solution in 1,3-butanediol. Examples of the acceptable vehicles and solvents that can be employed are mannitol, water, Ringer's solution, and isotonic sodium chloride solution. In addition, fixed oils are conventionally employed as a solvent or suspending medium (e.g., synthetic mono- or diglycerides). Fatty acid, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions.
[0054] These oil solutions or suspensions can also contain a long chain alcohol diluent or dispersant, carboxymethyl cellulose, or similar dispersing agents. Other commonly used surfactants such as Tweens or Spans or other similar emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid, liquid, or other dosage forms can also be used for the purpose of formulation.
[0055] A composition for oral administration can be any orally acceptable dosage form including capsules, tablets, emulsions and aqueous suspensions, dispersions, and solutions. In the case of tablets, commonly used carriers include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried corn starch. When aqueous suspensions or emulsions are administered orally, the active ingredient can be suspended or dissolved in an oily phase combined with emulsifying or suspending agents. If desired, certain sweetening, flavoring, or coloring agents can be added.
[0056] A nasal aerosol or inhalation composition can be prepared according to techniques well known in the art of pharmaceutical formulation. For example, such a composition can be prepared as a solution in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other solubilizing or dispersing agents known in the art.
[0057] A composition for topical administration can be prepared in form of an ointment, a gel, a plaster, an emulsion, a lotion, a foam, a cream of a mixed phase or amphiphilic emulsion system (oil/water-water/oil mixed phase), a liposome, a transfersome, a paste, or a powder.
[0058] Any of the compositions described above can also be administered in the form of suppositories for rectal administration. It also can be designed such that the composition is released in the intestine. For example, the composition is confined in a solid sub-unit or a capsule compartment that has respectively a matrix or a wall or a closure comprising an enteric polymer which dissolves or disperses at the pH of the small or large intestine to release the drug substance in the intestine. Suitable such polymers have been described above, for example with reference to U.S. Pat. No. 5,705,189.
[0059] In certain embodiments, the carrier in the pharmaceutical composition must be “acceptable” in the sense that it is compatible with the active ingredient of the composition (and preferably, capable of stabilizing the active ingredient) and not deleterious to the subject to be treated. One or more solubilizing agents can be utilized as pharmaceutical excipients for delivery of an active compound. Examples of other carriers include colloidal silicon oxide, magnesium stearate, cellulose, sodium lauryl sulfate, and D&C Yellow # 10.
Benign Tumors
[0060] The compounds and methods of the present invention are also suitable for treatment of variety of benign tumors. Exemplary benign tumors include: Adrenal tumors such as adenoma, Adrenal Pheochromocytoma and Adrenal Ganglioneuroma; Brain tumors such as Meningioma and Adenoma; Peripherial Nerve tumors such as Neurofibroma and Schwannoma; Liver tumors such as Adenoma; Thyroid tumors such as Follicular Adenoma; Parathyroid tumors such as Adenoma; Thymus tumors such as Thymoma; Salivary Gland tumors such as Pleomorphic Adenoma; Small Intestine tumor such as Villous Adenoma; Colon tumors such as Tubulovillous Adenoma, Adenomatous Polyp of Colon and Polyposis Coli; Pancreas tumors such as Serous Cystadenoma; Islet tumors such as Pancreatic Islet Cell Tumor; Nasopharyngyl tumors such as Nasal Angiofibroma; Ovary tumors such as: Atypical Proliferating Mucinous Neoplasm, Brenner Tumor of Ovary, Mucinous Cystadenoma, Papillary cystadenoma, Dermoid Cyst of Ovary, Ovarian Teratoma, Ovarian Fibroma, Luteoma and Struma ovarii; Uterus tumors such as Uterine Cellular Leiomyoma and Leiomyoma; Placenta tumors such as Chorioangioma, Partial hydatidiform mole, Complete Hydatidiform and Mole; Bone tumors such as Cavernous Hemangioma and Giant Cell Tumor; Soft Tissue tumors such as Cavernous hemangioma, Desmoid Tumor, lipoma, Myelolipoma and osteochondroma; Joint tumors such as Synovial Chondromatosis; Lung tumors such as Carcinoid Tumor, Granular Cell Tumor and Hemangioma; Myocardium tumors such as Atrial Myxoma; Breast tumors such as Fibroadenoma, Intraductal Papilloma and Schwannoma; Kidney tumors such as Congenital Mesoblastic Nephroma; and Skin tumors such as Giant Congenital Intradermal Nevus; Kidney tumors such as Congenital Mesoblastic Nephroma.
[0061] The present composition can be administered for the treatment of hyperproliferative disorders. The term “hyperproliferative disorders” refers to excess cell proliferation that is not governed by the usual limitation of normal growth. The term denotes malignant as well as nonmalignant cell populations. The excess cell proliferation can be determined by reference to the general population and/or by reference to a particular patient, e.g. at an earlier point in the patient's life. Hyperproliferative cell disorders can occur in different types of animals and in humans, and produce different physical manifestations depending upon the affected cells.
[0062] Hyperproliferative cell disorders include tumors as well as nontumors. A “tumor” here refers to an abnormal mass of tissue that results from excessive cell division that is uncontrolled and progressive, also called a neoplasm.
[0063] Examples of tumors include a variety of solid tumor such as laryngeal tumors, brain tumors, other tumors of the head and neck; colon, rectal and prostate tumors; breast and thoracic solid tumors; ovarian and uterine tumors; tumors of the esophagus, stomach, pancreas and liver; bladder and gall bladder tumors; skin tumors such as melanomas; and the like, and a fluid tumor such as leukemia.
[0064] A “solid tumor”, as used herein, refers to an abnormal mass of tissue that usually does not contain cysts or liquid areas. Solid tumors may be benign (not cancerous), or malignant (cancerous). Solid tumors have a distinct structure that mimics that of normal tissues and comprises two distinct but interdependent compartments: the parenchyma (neoplastic cells) and the stroma that the neoplastic cells induce and in which they are dispersed. Different types of solid tumors are named for the type of cells that form them. Examples of solid tumors are sarcomas, carcinomas, and lymphomas.
[0065] “Solid tumor” means a locus of tumor cells where the majority of the cells are tumor cells or tumor-associated cells.
[0066] More particularly, tumor here refers to either benign (not cancerous) or malignant tumors.
Malignant Tumors
[0067] Examples of malignant tumors include but not limited to: Breast cancer:
[0000] 1. Ductal carcinoma: A1. Ductal Carcinoma In Situ (DCIS): Comedocarcinoma, Cribriform, Papillary, Micropapillary; A2. Infiltrating Ductal Carcinoma (IDC): Tubular Carcinoma, Mucinous (Colloid) Carcinoma, Medullary Carcinoma, Papillary Carcinoma, Metaplastic Carcinoma, Inflammatory Carcinoma
2. Lobular Carcinoma: B1. Lobular Carcinoma In Situ (LCIS); B2. Invasive lobular carcinoma
3. Paget's Disease of the Nipple
[0068] Female Reproductive System
[0069] CERVIX UTERI: Cervical intraepithelial neoplasia, grade I, Cervical intraepithelial neoplasia, grade II, Cervical intraepithelial neoplasia, grade III (Squamous cell carcinoma in situ), Keratinizing Squamous Cell Carcinoma, Nonkeratinizing Squamous Cell Carcinoma, Verrucous Carcinoma, Adenocarcinoma in situ, Adenocarcinoma in situ, endocervical type, Endometrioid adenocarcinoma, Clear cell adenocarcinoma, Adenosquamous carcinoma, Adenoid cystic carcinoma, Small cell carcinoma, Undifferentiated carcinoma
[0070] CORPUS UTERI: Endometrioid carcinoma, Adenocarcinoma, Adenocanthoma (adenocarcinoma with squamous metaplasia), Adenosquamous carcinoma (mixed adenocarcinoma and squamous cell carcinoma, Mucinous adenocarcinoma, Serous adenocarcinoma, Clear cell adenocarcinoma, Squamous cell adenocarcino, Undifferentiated adenocarcinoma
[0071] OVARY: Serous cystadenoma, Serous cystadenocarcinoma, Mucinous cystadenoma, Mucinous cystadenocarcinoma, Endometrioid tumor, Endometrioid adenocarcinoma, Clear cell tumor, Clear cell cystadenocarcinoma, Unclassified tumor
[0072] VAGINA: Squamous cell carcinoma, Adenocarcinoma
[0073] VULVA: Vulvar intraepithelial neoplasia, grade I, Vulvar intraipithelial neoplasia, grade II, Vulvar intraepithelial neoplasia, grade III (squamous cell carcinoma in situ), Squamous Cell Carcinoma, Verrucous carcinoma, Padget's disease of the vulva, Adenocarcinoma, NOS, Basal cell carcinoma, NOS, Bartholin's gland carcinoma
[0074] Male Reproductive System
[0075] PENIS: Squamous Cell Carcinoma
[0076] PROSTATE: Adenocarcinoma, Sarcoma, Transitional cell carcinoma of the prostate
[0077] TESTIS: Seminomatous tumor, Nonseminomatous tumor, Teratoma, Embryonal carcinoma, Yolk sac tumor, Choriocarcinoma
[0078] CARDIAC: sarcoma (angiosarcoma, fibrosarcoma, rhabdomyosarcoma, liposarcoma), myxoma, rhabdomyoma, fibroma, lipoma and teratoma
[0079] Respiratory System
[0080] LARYNX: Squamous cell carcinoma
[0081] PLEURAL MESOTHELIOMA: Primary pleural mesothelioma
[0082] PHARYNX: Squamous cell carcinoma
[0083] Lung
[0084] 1. Squamous cell carcinoma (epidermoid carcinoma), Variant: Spindle cell;
[0085] 2. Small cell carcinoma, Other cell carcinoma, Intermediate cell type, Combined oat cell carcinoma;
[0086] 3. Adenocarcinoma: Acinar adenocarcinoma, Papillary adenocarcimoma, Bronchiolo-alveolar carcinoma, Solid carcinoma with mucus formation;
[0087] 4. Large cell carcinoma: Giant cell carcinoma, Clear cell carcinoma, Sarcoma;
[0088] Gastrointestinal Tract
[0089] AMPULLA OF VATER: Primary adenocarcinoma, Carcinoid tumor, Lymphoma
[0090] ANAL CANAL: Adenocarcinoma, Squamous cell carcinoma, Melanoma
[0091] EXTRAHEPATIC BILE DUCTS: Carcinoma in situ, Adenocarcinoma, Papillary adenocarcinoma, Adenocarcinoma, intestinal type, Mucinous adenocarcinoma, Clear cell adenocarcinom, Segnet-ring cell carcinoma, Adenosquamous carcinoma, Squamous cell carcinoma, Small cell (oat) carcinoma, Undifferentiated carcinoma, Carcinoma, NOS, Sarcoma, Carcinoid tumor
[0092] COLON AND RECTUM: Adenocarcinoma in situ, Adenocarcinoma, Mucinous adenocarcinoma (colloid type; greater than 50% mucinous carcinoma), Signet ring cell carcinoma (greater than 50% signet ring cell), Squamous cell (epidermoid) carcinoma, Adenosquamous carcinoma, Small cell (oat cell) carcinoma, Undifferentiated carcinoma, Carcinoma, NOS, Sarcoma, Lymphoma, Carcinoid tumor
[0093] ESOPHAGUS: squamous cell carcinoma, adenocarcinoma, leiomyosarcoma lymphoma
[0094] GALLBLADDER: Adenocarcinoma, Adenocarcinoma, intestinal type, Adenosquamous carcinoma, Carcinoma in situ, Carcinoma, NOS, Clear cell adenocarcinoma, Mucinous adenocarcinoma, Papillary adenocarcinoma, Signet-ring cell carcinoma, Small cell (oat cell) carcinoma, Squamous cell carcinoma, Undifferentiated carcinoma
[0095] LIP AND ORAL CAVITY: Squamous cell carcinoma
[0096] LIVER: hepatoma (hepatocellular carcinoma), cholangiocarcinoma, hepatoblastoma, angiosarcoma, hepatocellular adenoma, hemangioma
[0097] EXOCRINE PANCREAS: Duct cell carcinoma, Pleomorphic giant cell carcinoma, Giant cell carcinoma, osteoclastoid type, Adenocarcinoma, Adenosquamous carcinoma, Mucinous (colloid) carcinoma, Cystadenocarcinoma, Acinar cell carcinoma, Papillary carcinoma, Small cell (oat cell) carcinoma, Mixed cell typed, Carcinoma, NOS, Undifferentiated carcinoma, Endocrine cell tumors arising in the islets of Langerhans, Carcinoid
[0098] SALIVARY GLANDS: Acinic (acinar) cell carcinoma, Adenoid cystic carcinoma (cylindroma), Adenocarcinoma, Squamous cell carcinoma, Carcinoma in pleomorphic adenoma (malignant mixed tumor), Mucoepidermoid carcinoma, Well differentiated (low grade), Poorly differentiated (high grade)
[0099] STOMACH: Adenocarcinoma, Papillary adenocarcinoma, Tubular adenocarcinoma, Mucinous adenocarcinoma, Signet ring cell carcinoma, Adenosquamous carcinoma, Squamous cell carcinoma, Small cell carcinoma, Undifferentiated carcinoma, Lymphoma, Sarcoma, Carcinoid tumor
[0100] SMALL INTESTINE: adenocarcinoma, lymphoma, carcinoid tumors, Karposi's sarcoma, leiomyoma, hemangioma, lipoma, neurofibroma, fibroma
[0101] Urinary System
[0102] KIDNEY: Renal cell carcinoma, Carcinoma of Bellini's collecting ducts, Adenocarcinoma, Papillary, Tubular carcinoma, Granular cell carcinoma, Clear cell carcinoma (hypemephroma), Sarcoma of the kidney, Nephroblastoma, Nephroblastoma
[0103] RENAL PELVIS AND URETER: Transitional cell carcinoma, Papillary transitional cell carcinoma carcinoma, Squamous cell carcinoma, Adenomcarcinoma
[0104] URETHRA: Transitional cell carcinoma, Squamous cell carcinoma, Adenocarcinoma
[0105] URINARY BLADDER: Carcinoma in situ, Transitional urothelial cell carcinoma, Papillary transitional cell carcinoma, Squamous cell carcinoma, Adenocarcinoma, Undifferentiated
[0106] Muscle, Bone, and Soft Tissue
[0000] BONE: A. Bone-forming: Osteosarcoma; B. Cartilage-forming: Chondrosarcoma, Mesenchymal chondrosarcoma, C. Giant cell tumor, malignant, D. Ewing's sarcoma, E. Vascular tumors: Hemangioendothelioma, Hemangiopericytoma, Angiosarcoma; F. Connective tissue tumors: Fibrosarcoma, Liposarcoma, Malignant mesenchymoma, Undifferentiated sarcoma; G. Other tumors: Chordoma, Adamantinoma of long bones
[0107] SOFT TISSUES: Alveolar soft-part sarcoma, Angiosarcoma, Epithelioid sarcoma, Extraskeletal chondrosarcoma, Fibrosarcoma, Leiomyosarcoma, Liposarcoma, Malignant fibrous histiocytoma, Malignant hemangiopericytoma, Malignant mesenchymoma, Malignant schwannoma, Rhabdomyosarcoma, Synovial sarcoma, Sarcoma, NOS
[0108] NERVOUS SYSTEM: skull (osteoma, hemangioma, granuloma, xanthoma, osteitis deformans), meninges (meningioma, meningiosarcoma, gliomatosis), brain (astrocytoma, medulloblastoma, glioma, ependymoma, germinoma (pilealoma), glioblastoma multiform, oligodendroglioma, schwannoma, retinoblastoma, congenital tumors), spinal cord neurofibroma, meningioma, glioma, sarcoma)
[0109] HEMATOLOGY: blood (myeloid leukemia (acute and chronic), acute lymphloblastic leukemia, chronic lymphocytic leukemia, myeloproliferative diseases, multiple myeloma, myelodysplastic syndrome), Hodgkin's disease, non-Hodgkin's lymphoma (malignant lymphonoma);
[0110] Endocrine System
[0000] THYROID GLAND: Papillary carcinoma (including those with follicular foci), Follicular carcinoma, Medullary carcinoma, Undifferentiated (anaplastic) carcinoma
NEUROBLASTOMA: Sympathicoblastoma, Sympathicogonioma, Malignant ganglioneuroma, Gangliosympathicoblastma, Ganglioneuroma
[0111] Skin
[0000] Squamous cell carcinoma, Spindle cell variant of squamous cell carcinoma, Basal cell carcinoma, Adenocarcinoma developing from sweat or sebaceous gland, Malignant Melanoma
[0112] Eye
[0113] THE CONJUNCTIVA: Carcinoma of the conjunctiva;
[0114] THE EYELID: Basal cell carcinoma, Squamous cell carcinoma, Sebaceous cell carcinoma;
[0115] THE LACRIMAL GLAND: Adenocarcinoma, Adenoid cystic carcinoma, Carcinoma in pleomorphic adenoma, Mucoepidermoid carcinoma, Squamous cell carcinoma;
[0116] THE EYELID: Melanoma of the eyelid
[0117] THE UVEA: Spindle cell melanoma, Mixed cell melanoma, Epithelioid cell melanoma
[0118] SARCOMA OF THE ORBIT: Soft tissue tumor, Sarcoma of bone
[0119] RETINOBLASTOMA: Retinoblastoma
[0120] Examples of nontumor hyperproliferative disorders include but not limited to myelodysplastic disorders; cervical carcinoma-in-situ; familial intestinal polyposes such as Gardner syndrome; oral leukoplakias; histiocytoses; keloids; hemangiomas; inflammatory arthritis; hyperkeratoses and papulosquamous eruptions including arthritis. Also included are viral induced hyperproliferative diseases such as warts and EBV induced disease (i.e., infectious mononucleosis), scar formation, blood vessel proliferative disorders such as restenosis, atherosclerosis, in-stent stenosis, vascular graft restenosis, etc.; fibrotic disorders; psoriasis; glomerular nephritis; macular degenerative disorders; benign growth disorders such as prostate enlargement and lipomas; autoimmune disorders and the like.
[0121] The present composition can also be administered for the treatment of Cardiac dysrhythmias, including but not limited to the Wolff-Parkinson-White syndrome and atrioventricular nodal reentrant tachycardia ventricular tachycardia (VT), atrial tachycardias, atrial flutter and atrial fibrillationsupraventricular tachycardias.
[0122] The present composition can also be administered for the treatment of Endometriosis, uterine fibroid (Uterine leiomyomata) menorrhagia, cervical erosion, cervical polyp, and the like.
[0123] The present composition can also be administered for the treatment of the defects or disorders of intervertebral discs include but not limited to annular fissures, fragmentation of the nucleus pulposus, and contained herniation a herniated intervertebral disc, degenerative intervertebral discs.
[0124] The compositions described above can be preliminarily screened for their efficacy in treating above-described diseases by an in vitro assay and then confirmed by animal experiments (See Examples 1-9 below) and clinic trials. Having the information set forth in the present invention, other methods will also be apparent to those of ordinary skill in the art.
[0125] The specific examples below are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. All of the publications cited herein are incorporated by reference in their entirety.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0126] Cells can exist in different periods of a cell cycle such as: G1 phase cells, S phase cells, (indicating synthesis and doubling of DNA), and G2 phase cells. Comparing cancer cells to normal cells, one finds a decrease in the proportion of G1 phase cells in cancer, an increase in the proportion of cells in synthesis in cancer and an increase in the proportion of cells in G2 phase and S phase.
Example 1
[0127] In Example 1, B20L (Metformin 1 mM+aspirin 0.4 mM+serotonin creatinine sulfate complex 0.002 mM) and B20H (Metformin 10 mM+aspirin 4 mM+serotonin creatinine sulfate complex 0.02 mM) were tested to determine the effect on the cell cycle of pancreatic cancer cells after 24 hours. Each of the cell samples were then tested in a flow cytometer. The testing methodology and equipment used are set forth as follows. Cells were harvested and washed twice with phosphate buffered saline, (PBS) and fixed in 70% cold ethanol at 4° C. overnight. Before analysis, cells were washed twice with PBS, containing 1% bovine serum albumin (BSA), then resuspended with 400 μl PBS and treated with 100 μg/ml RNase A (Roche Diagnostics) and 50 μg/ml propidium iodide (PI) (Sigma). After incubation for 30 min at 37° C., the cells were subjected to DNA content analysis. propidium iodide, (PI) fluorescence was analyzed with a FACS calibur flowcytometer, (Becton Dickinson). Data from at least 10,000 cells were analyzed with software. The results of a control group as well as the two active treatment groups are set forth in Table 1 below.
[0000]
TABLE 1
Effect of B20L Metformin + aspirin + serotonin creatinine sulfate complex
and B20H Metformin + aspirin + serotonin creatinine sulfate complex
on Pancreatic Cancer Cells after 24 Hours
Group
G1
S
G2
Control
63%
35.5%
1.5%
B20L Metformin
87.30%
9.40%
3.30%
1 mM + aspirin
0.4 mM + serotonin
creatinine sulfate
complex 0.002 mM
Metformin 10 mM +
88.70%
7.80%
3.40%
aspirin 4 mM +
serotonin creatinine
sulfate complex
0.02 mM
[0128] The results indicate that Metformin+aspirin+serotonin creatinine sulfate complex can block pancreatic cancer cells in G1 phase from progressing into S phase and G2 phase after 24 hours as the two treatment groups have a higher proportion of cancer cells in the G1 phase.
Example 2
[0129] In Example 2, the testing procedure according to Example 1 above was carried out for 48 and 72 hours comparing the control group to a B20L treatment group. The results are provided in Table 2 below.
[0000]
TABLE 2
Effect of B20L Metformin + aspirin + serotonin creatinine sulfate complex
on Pancreatic Cancer Cells after 48 and 72 Hours
Group
G1
S
G2
The effect of B20L on cell cycle in 48 hours
Control
47%
46.20%
6.60%
Metformin 1 mM +
71.70%
25.40%
2.90%
aspirin 0.4 mM +
serotonin creatinine
sulfate complex
0.002 mM
The effect of B20L on cell cycle in 72 hours
Control
57%
37.40%
5.80%
Metformin 1 mM +
63.80%
31.50%
4.60%
aspirin 0.4 mM +
serotonin creatinine
sulfate complex
0.002 mM
[0130] The results indicate that Metformin+aspirin+serotonin creatinine sulfate complex can block pancreatic cancer cells in G1 phase from progressing into S phase and G2 phase after 24, 48 and 72 hours as the two treatment groups have a higher proportion of cancer cells in the G1 phase.
Example 3
[0131] In Example 3, different dosages of Metformin+aspirin+serotonin creatinine sulfate complex were tested to determine the effect on the cell cycle of breast cancer cells after 24 hours. Each of the cell samples were then tested in a flow cytometer according to the procedures set forth in Example 1 above. The results of a control group as well as the two active treatment groups are set forth in Table 3 below.
[0000]
TABLE 3
Effect of different dosages of Metformin + aspirin + serotonin creatinine
sulfate complex on Breast Cancer Cells after 24 Hours
Group
G1
S
G2
Control
43%
46.10%
10.6%
(Metformin 1 mM +
59.60%
36.30%
4.10%
aspirin 0.4 mM +
serotonin creatinine
sulfate complex
0.002 mM)
Metformin 10 mM +
73.80%
20.00%
6.20%
aspirin 4 mM +
serotonin creatinine
sulfate complex
0.02 mM
[0132] The results indicate that B20 different dosages of Metformin+aspirin+serotonin creatinine sulfate complex can block breast cancer cells in G1 phase from progressing into S phase cells after 24 hours as the two treatment groups have a lower proportion of cancer S phase cells.
Example 4
[0133] In Example 4, different dosages of Metformin+aspirin+serotonin creatinine sulfate complex were tested to determine the effect on proliferation speed of pancreatic cancer cells after 24, 48 and 72 hours. The testing methodology and equipment used are set forth as follows. Pancreatic cancer cells were subcultured into 96-well plates at approximately 4×10 4 cells per ml and allowed to adhere for 24 h at 37° C. before being treated with the drug. Cell viability was assessed using the Dojindo Cell Counting Kit-8. The cell viability was in direct proportion to the absorbance at 450 nm. Accordingly, the cell viability was expressed as the absorbance at 450 nm. All experiments were performed in triplicate on three separate occasions. The results of a control group as well as the two active treatment groups are set forth in Table 4 below.
[0000]
TABLE 4
Effect of different dosages of Metformin + aspirin + serotonin creatinine
sulfate complex on Proliferation Speed of Pancreatic Cancer Cells after
24, 48 and 72 Hours
Group
24 H
48 H
72 H
Control
0.40 ± 0.023
0.89 ± 0.053
1.805 ± 0.033
Metformin 1
0.335 ± 0.021*
0.725 ± 0.047**
0.787 ± 0.066**
mM + aspirin
0.4 mM +
serotonin
creatinine
sulfate complex
0.002 mM
Metformin 10
0.296 ± 0.017**
0.491 ± 0.034**
0.565 ± 0.060**
mM + aspirin
4 mM +
serotonin
creatinine
sulfate complex
0.02 mM
*p < 0.05,
**p < 0.01
[0134] The results indicate that different dosage of Metformin+aspirin+serotonin creatinine sulfate complex can inhibit pancreatic cancer cell proliferation and the effects are time and dose dependent.
Example 5
[0135] In Example 5, Metformin 5 mM; Metformin 5 mM+aspirin 2 mM; and Metformin 5 mM+aspirin 2 mM+serotonin creatinine sulfate complex 0.001 mM were tested to determine the effect on cell cycle on B16 (mice melanoma cells) during the G1, S and G2 cell phases. The procedure for testing using the flow cytometer was carried out as set forth in Example 1 above. The results are set forth in Table 5 below.
[0000]
TABLE 5
Effect of Metformin 5 mM, Metformin 5 mM + aspirin 2 mM, and
Metformin 5 mM + aspirin 2 mM + serotonin creatinine
sulfate complex 0.01 mM on B16 mice melanoma cells during G1,
S and G2 cell phases.
Group
G1
S
G2
Control
64
12.8
23.1
Metformin 5 mM
71.8
4.6
23.6
Metformin 5 mM +
82.4
6.0
11.6
aspirin 2 mM
Metformin 5 mM +
85.1
6.9
8.0
aspirin 2 mM +
serotonin creatinine
sulfate complex
0.01 mM
[0136] The results indicate that metformin was effective. Metformin+aspirin had better effect metformin alone, while metformin+aspirin+serotonin creatinine sulfate complex is better than metformin+aspirin.
Example 6
[0137] In Example 6, Metformin 50 mM; Metformin 100 mM, Metformin 150 mM; and metformin 200 mM were tested to determine the kill effect on breast cancer cells after 3, 12 and 24 hours. The testing methodology and equipment used are set forth as follows. Breast cancer cells were subcultured into 96-well plates at approximately 4×10 4 cells per ml and allowed to adhere for 24 h at 37° C. before being treated with the drug. Cell viability was assessed using the Dojindo Cell Counting Kit-8. The cell viability was in direct proportion to the absorbance at 450 nm. Accordingly, the cell viability was expressed as the absorbance at 450 nm. All experiments were performed in triplicate on three separate occasions. The results are set forth in Table 6 below showing the kill ratio (compared to control group) of different concentrations and different action times of metformin on MCF-7 cells (breast cancer cells).
[0000]
TABLE 6
Effect of metformin on MCF-7 kill ratio of Breast Cancer
Cells after 3, 12 and 24 Hours
Time
Concentration
3 h (%)
12 h (%)
24 h (%)
Metformin
0.139 ± 0.041**
0.397 ± 0.042**
0.404 ± 0.061**
50 mM
Metformin
0.123 ± 0.057**
0.353 ± 0.083**
0.542 ± 0.095**
100 mM
Metformin
0.318 ± 0.032**
0.488 ± 0.036**
0.887 ± 0.068**
150 mM
Metformin
0.321 ± 0.07**
0.769 ± 0.088**
0.983 ± 0.018**
200 mM
*p < 0.05,
**p < 0.01
[0138] The results indicate that Metformin was effective, can kill breast cancer cell and the effects are time and dose dependent.
Example 7
[0139] In Example 7, Metformin+serotonin creatinine sulfate complex+different compounds with anti-inflammatory activity or acetaminophen or tramadol (different first agent), were tested to determine the kill effect on liver cancer cells after 24 and 48 hours. The testing methodology and equipment was carried out as set forth in Example 6 above. The results are set forth in Table 7 below showing the kill ratio (compared to the control group), of different compositions and different action times on HepG-2 cells (liver cancer cells).
[0000]
TABLE 7
The kill ratio of different compositions and different
action times on HepG-2 cells
24 hr (%)
48 hr (%)
Metformin
0.975 ± 0.004**
0.995 ± 0.004**
100 mM + aspirin 40 mM +
serotonin
creatinine sulfate
complex 0.2 mM
Metformin 100 mM +
0.953 ± 0.010**
0.985 ± 0.008**
indomethacin 30 mM +
serotonin creatinine
sulfate complex 0.2 mM
Metformin 100 mM +
0.935 ± 0.022**
0.974 ± 0.007**
nimesulide 30 mM +
serotonin creatinine
sulfate complex 0.2 mM
Metformin 100 mM +
0.925 ± 0.027**
0.971 ± 0.005**
celebrex 30 mM +
serotonin creatinine
sulfate complex 0.2 mM
Metformin 100 mM +
0.957 ± 0.015**
0.975 ± 0.009**
Piroxicam33 mM +
serotonin creatinine
sulfate complex 0.2 mM
Metformin 100 mM +
0.964 ± 0.016**
0.981 ± 0.007**
diclofenac25 mM +
serotonin creatinine
sulfate complex 0.2 mM
Metformin 100 mM +
0.757 ± 0.115**
0.969 ± 0.014**
acetaminophen
17 mM + serotonin
creatinine sulfate
complex 0.2 mM
Metformin 100 mM +
0.884 ± 0.015**
0.978 ± 0.008**
Tramadol
hydrochloride 17 mM +
serotonin creatinine
sulfate complex 0.2 mM
(*p < 0.05, **p < 0.01)
[0140] The results indicate that Metformin+serotonin creatinine sulfate complex+different compounds with anti-inflammatory activity, acetaminophen, and tramadol (different first agent), can kill the live cancer cells well, and the effect is better than metformin only.
Example 8
[0141] In Example 8, phenformin (different second agent)+serotonin creatinine sulfate complex+different compounds with anti-inflammatory activity or acetaminophen, or tramadol, were tested to determine the kill effect on liver cancer cells after 24 and 48 hours. The testing methodology and equipment was carried out as set forth in Example 6 above. The results are set forth in Table 8 below showing the kill ratio (compared to control group) of different compositions and different action times on HepG-2 cells.
[0000]
TABLE 8
The kill ratio of different compositions and different
actions time on HepG-2 cells
24 hours (%)
48 hours (%)
Phenformin
0.936 ± 0.016**
0.991 ± 0.006**
2 mM + aspirin 40 mM +
serotonin
creatinine sulfate
complex 0.2 mM
Phenformin 2 mM +
0.762 ± 0.032**
0.920 ± 0.02**
indomethacin
30 mM + serotonin
creatinine sulfate
complex 0.2 mM
Phenformin 2 mM +
0.789 ± 0.039**
0.956 ± 0.012**
nimesulide 30 mM +
serotonin creatinine
sulfate complex 0.2 mM
Phenformin 2 mM +
0.817 ± 0.028**
0.957 ± 0.002**
celebrex 30 mM +
serotonin creatinine
sulfate complex 0.2 mM
Phenformin 2 mM +
0.973 ± 0.004**
0.994 ± 0.007**
Piroxicam33 mM +
serotonin creatinine
sulfate complex 0.2 mM
Phenformin 2 mM +
0.965 ± 0.006**
0.992 ± 0.005**
diclofenac25 mM +
serotonin creatinine
sulfate complex 0.2 mM
Phenformin 2 mM +
0.940 ± 0.022**
0.991 ± 0.005**
acetaminophen
17 mM + serotonin
creatinine sulfate
complex 0.2 mM
Phenformin 2 mM +
0.721 ± 0.027**
0.940 ± 0.004**
tramadol
hydrochloride
17 mM + serotonin
creatinine sulfate
complex 0.2 mM
(*p < 0.05, **p < 0.01)
[0142] The results indicate that phenformin (different second agent)+serotonin creatinine sulfate complex+compounds with different anti-inflammatory activity or acetaminophen, tramadol, can kill the live cancer cell well and the effect is better than metformin only.
Example 9
[0143] In Example 9, the effect of B10 (Metformin 50 mg/kg+aspirin 40 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg) was tested to determine the effect on volume of hepatoma in Strain Kunming Mice (KM) relative to a 10% glucose saline (GS) group. The drugs were administered by intratumor injection, twice a day for 3 days. Volume was measured before and after treatment for each group. The results including the change in volume are set forth in Table 6 below.
[0000]
TABLE 9
The effect of B10 Metformin 50 mg/kg + aspirin 40 mg/kg +
serotonin creatinine sulfate complex 0.4 mg/kg on the volume
of hepatoma in KM mice
Group
Before Drug
After Drug
10% G.S. (glucose saline)
321 ± 54
388 ± 275
Metformin 50 mg/kg + aspirin 40 mg/kg +
219 ± 68
13 ± 6**
serotonin creatinine sulfate complex
0.4 mg/kg
(n = 4, *p < 0.05, **p < 0.01)
[0144] The results indicate that B10 Metformin 50 mg/kg+aspirin 40 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg can eliminate hepatoma volume in KM mice at the rate of 94.1%.
Example 10
[0145] In Example 10, the effect of B10 Metformin 50 mg/kg+aspirin 40 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg was tested to determine the effect on the weight and volume of transplanted human hepatoma in hairless mice relative to a 10% GS group and a dehydration alcohol group. The procedures for performing this test were as follows. Hep G2 cells were prepared at 25*10 6 cells/ml and 0.2 ml of the cell suspension (5*10 6 cells) was injected in an exposed mouse mammary fat pad. When tumors achieved the required size (0.5 cm 3 ), animals would be treated with 50 μl of B10, dehydrated alcohol or 10% glucose solution once daily for 6 days. During 12 days after the last injection, tumor volume will be assessed by measuring tumor dimensions (long (L) and short (S)) and estimated it as V=0.52*L*S 2 . 12 days after the last injection, mice would be sacrificed and tumors would be dissected, weighed and stored in a formaline solution for further evaluation.). Volume was measured before and after treatment for each group. The results including the change in volume are set forth in Table 7 below.
[0000]
TABLE 10
The effect of B10 on the weight and volume of hepatoma in KM mice
Volume
Before
After
Group
Treatment
Treatment
Changes
10% G.S.
172 ± 65.5
444 ± 199
↑158%
Dehydration ethanol
188 ± 119
89 ± 120**
↓52.7%
Metformin 50 mg/kg +
180 ± 128
1.05 ± 2.09**
↓199.4%
aspirin 40 mg/kg +
serotonin creatinine sulfate
complex 0.4 mg/kg
(n = 4, *p < 0.05, **p < 0.01)
[0146] The results indicate that B10 can eliminate hepatoma volume in hairless mice at the rate 99.4%, compared to the dehydration ethanol group rate of 52.7%.
Example 11
[0147] In Example 11, the effect of B3 (Metformin 50 mg/kg+celebrex 10 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg) was tested to determine the effect on metastasis of hepatoma carcinoma H22 cells. Fifty thousand (50,000) mice hepatoma carcinoma H22 cells were injected into the abdominal cavity of KM mice, and then administered 10% G.S. in the control group, or Metformin 50 mg/kg+celebrex 10 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg two times a day for only the first 30 days in the active treatment group. After treatment was stopped, survival time was observed. The results of the active treatment group and the 10% G.S. group are set forth in Table 8 below.
[0000]
TABLE 11
Survival Data of KM Mice Treated with Metformin 50 mg/kg + celebrex
10 mg/kg + serotonin creatinine sulfate complex 0.4 mg/kg three
times a day for 30 days
Number Surviving
Group
120 Days
Survival Time
10% G.S.
2/12
64.8 ± 27.8
Metformin 50 mg/kg + celebrex
9/12
95 ± 37.9*
10 mg/kg + serotonin creatinine
sulfate complex 0.4 mg/kg
(n = 12, *p < 0.05, **p < 0.01)
[0148] The results indicate that the metformin 50 mg/kg+celebrex 10 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg group, 9 mice survived 120 days, and in the control group only 2 mice survived. The active drug group survival time was also better than control group indicating that this drug therapy can extend mice survival time and reduce cancer cell transplantation rate.
Example 12
[0149] In Example 12, the effect of B3 and B10 was tested to determine the effect on oncogenesis rate of hepatoma carcinoma H22 cells in KM mice. Fifty thousand (50,000) mice hepatoma carcinoma H22 cells were injected subcutaneously into KM mice. Treatment groups consisted of B3 and B10, administered three times a day for 30 days. After the drug was stopped, the mice were observed for the presence of tumor tissue to determine whether oncogenesis has occurred. The results of the B10 and B3 treatment groups and the G.S. group are set forth in Table 9 below.
[0000]
TABLE 12
Oncogenesis Rate for Weeks 1, 2, 3, 4, 6 and 8 After Inoculation and
Treatment with B10 (Metformin 50 mg/kg + aspirin 40 mg/kg +
serotonin creatinine sulfate complex 0.4 mg/kg) and B3
(Metformin 50 mg/kg + celebrex 10 mg/kg +
serotonin creatinine sulfate complex 0.4 mg/kg)
Time after administration
of drug and Oncogenesis Rate
Group
1 w
2 w
3 w
4 w
6 w
8 w
GS
60
70
70
80
90
90
Metformin 50 mg/kg +
10
20
20
20
20
20
aspirin40 mg/kg +
serotonin
creatinine
sulfate complex
0.4 mg/kg
Metformin 50 mg/kg +
30
50
50
50
50
50
celebrex 10 mg/kg +
serotonin
creatinine
sulfate complex
0.4 mg/kg
[0150] The results indicate that 8 weeks after the drugs were administered, the Metformin 50 mg/kg+aspirin 40 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg group only had a 20% oncogenesis rate. The Metformin 50 mg/kg+celebrex 10 mg/kg+serotonin creatinine sulfate complex 0.4 mg/kg only had a 50% oncogenesis rate. Both active drug groups had a lower oncogenesis rate than the control group (90%). Therefore, these drugs can decrease the rate of transplantation of tumor cells.
Other Embodiments
[0151] All of the features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features. From the above description, one skilled in the art can easily ascertain the essential characteristics of the present 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. Thus, other embodiments are also within the scope of the following claims. | The invention relates to a composition that includes a first agent selected including an agent that possesses anti-inflammatory activity or acetaminophen, phenacetin, tramadol and the like; a second agent selected from the group consisting of an oxidative phosphorylation inhibitor, an ionophore, and an adenosine 5-monophosphate-activated Protein kinase (AMPK) activator; a third agent that possesses or maintains serotonin activity. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to papermaking, and relates more specifically to multilayer fabrics employed in papermaking. The invention also relates to the binding of multilayered forming fabric with warp yarns. The present invention also relates to. multilayer papermaker's fabrics that utilizes warp yarns to bind top and bottom layers such without disrupting the top fabric surface. The invention also provides for a fabric which utilizes a condensed sequence of warp knuckles in a weft float dominate structure in order to provide space in the weave for the binding warps to smoothly transition from the top layer to the bottom layer. The invention also provides for a fabric wherein the warp knuckles of several repeats of a weft float dominate pattern are condensed into a plain weave sequence that allows space for warps to float under the wefts for a distance.
[0003] 2. Discussion of Background Information
[0004] In the conventional fourdrinier papermaking process, a water slurry, or suspension, of cellulosic fibers (known as the paper “stock”) is fed onto the top of the upper run of an endless belt of woven wire and/or synthetic material that travels between two or more rolls. The belt, often referred to as a “forming fabric,” provides a papermaking surface on the upper surface of its upper run which operates as a filter to separate the cellulosic fibers of the paper stock from the aqueous medium, thereby forming a wet paper web. The aqueous medium drains through mesh openings of the forming fabric, known as drainage holes, by gravity or vacuum located on the lower surface of the upper run (i.e., the “machine side”) of the fabric.
[0005] After leaving the forming section, the paper web is transferred to a press section of the paper machine, where it is passed through the nips of one or more pairs of pressure rollers covered with another fabric, typically referred to as a “press felt.” Pressure from the rollers removes additional moisture from the web; the moisture removal is often enhanced by the presence of a “balt” layer of the press felt. The paper is then transferred to a dryer section for further moisture removal. After drying, the paper is ready for secondary processing and packaging.
[0006] Typically, papermaker's fabrics are manufactured as endless belts by one of two basic weaving techniques. In the first of these techniques, fabrics are flat woven by a flat weaving process, with their ends being joined to form an endless belt by any one of a number of well-known joining methods, such as dismantling and reweaving the ends together (commonly known as splicing), or sewing on a pin-seamable flap or a special foldback on each end, then reweaving these into pin-seamable loops. A number of auto-joining machines are available, which for certain fabrics may be used to automate at least part of the joining process. In a flat woven papermaker's fabric, the warp yarns extend in the machine direction and the filling yarns or weft yarns extend in the cross machine direction.
[0007] In the second basic weaving technique, fabrics are woven directly in the form of a continuous belt with an endless weaving process. In the endless weaving process, the warp yarns extend in the cross machine direction and the filling yarns or weft yarns extend in the machine direction. Both weaving methods described hereinabove are well known in the art, and the term “endless belt” as used herein refers to belts made by either method.
[0008] Effective sheet and fiber support are important considerations in papermaking, especially for the forming section of the papermaking machine, where the wet web is initially formed. Additionally, the forming fabrics should exhibit good stability when they are run at high speeds on the papermaking machines, and preferably are highly permeable to reduce the amount of water retained in the web when it is transferred to the press section of the paper machine. In both tissue and fine paper applications (i.e., paper for use in quality printing, carbonizing, cigarettes, electrical condensers, and like) the papermaking surface comprises a very finely woven or fine wire mesh structure.
[0009] In prior art fabrics, there is typically not enough space within the weave pattern for top warps to bind to the bottom wefts without disrupting the top fabric surface. Such fabrics also do not typically provide space in the weave for the top warps to smoothly transition from the top layer to the bottom layer. Such fabrics also do not typically provide space for warps to float under the wefts for a distance.
SUMMARY OF THE INVENTION
[0010] The fabric of the present invention may be made using the prior art methods described above. The invention also provides for a multilayer fabric employed in papermaking. The invention further also provides for the binding of multilayered forming fabric using warp yarns such as warp yarns that weave in the top layer. The present invention also relates to multilayer papermaker's fabrics that utilizes warp yarns to bind top and bottom layers such without disrupting the top fabric surface.
[0011] The present invention also recognizes that it is better for a warp yarn weaving in the top layer to pass between a top and bottom weft yarn before weaving or binding with one or more bottom weft yarns than for the warp yarn to pass from over a top weft yarn to directly over a bottom weft yarn without first passing between top and bottom weft yarns.
[0012] By way of non-limiting example, the present invention provides for a forming fabric having a 5 shed/5 shed warp bound 3:2 weft ratio.
[0013] The invention also provides for a fabric which utilizes a condensed sequence of warp knuckles in a weft float dominate structure in order to provide space in the weave for the warps which weave in the top layer to smoothly transition from the top layer to the bottom layer. The invention also provides for a fabric wherein the warp knuckles of several repeats of a weft float dominate pattern are condensed into a plain weave sequence that allows space for warps to float under the wefts for a distance.
[0014] The present invention relates to a forming fabric comprising a top layer comprising top weft yarns, a bottom layer comprising bottom weft yarns, binding warp yarns weaving with the top weft yarns and binding to the bottom layer, and at least one of the binding warp yarns passing between at least one top and bottom weft yarns before passing over at least one bottom weft yarn.
[0015] The fabric may further comprise at least one of bottom warp yarns weaving with non-adjacent bottom weft yarns and bottom warp yarns weaving only in the bottom layer.
[0016] At least one of the at least one binding warp yarn may pass under at least two adjacent top weft yarns before passing over at least one bottom weft yarn and each binding warp yarn may bind to bottom layer by binding to non-adjacent bottom weft yarns. The binding warp yarns may weave with the top weft yarns and bind to different non-adjacent bottom weft yarns per pattern repeat. Each binding warp yarn may bind to at least three non-adjacent bottom weft yarns per pattern repeat. After weaving with the top weft yarns, each binding warp yarn may bind to at least two non-adjacent bottom weft yarns per pattern repeat before again weaving with the top weft yarns. The binding warp yarns may bind to at least four non-adjacent bottom weft yarns per pattern repeat. After weaving with the top weft yarns, the at least one binding warp yarn may pass under at least two adjacent top weft yarns before binding with the bottom weft yarns. After weaving with the top weft yarns, the at least one binding warp yarn may pass under at least two adjacent top weft yarns before binding to two non-adjacent bottom weft yarns. After weaving with the top weft yarns, the at least one binding warp yarn may pass under at least three adjacent top weft yarns before binding with the bottom weft yarns. After weaving with the top weft yarns, the at least one binding warp yarn may pass under at least three adjacent top weft yarns before binding to-two non-adjacent bottom weft yarns.
[0017] The top layer and bottom layer may be bound together only by the binding warp yarns and the binding warp yarns are intrinsic warp yarns. Each binding warp yarn in a pattern repeat may weave with a plain weave with top weft yarns before binding with non-adjacent bottom weft yarns. Each binding warp yarn in a pattern repeat may weave with a plain weave with top weft yarns before binding with two non-adjacent bottom weft yarns.
[0018] In a pattern repeat, each binding warp yarn may weave with a plain weave with top weft yarns, then binds with two non-adjacent bottom weft yarns, and then weaves with a plain weave with top weft yarns. In a pattern repeat, the at least one binging warp yarn may bind with first and second non-adjacent bottom weft yarns and a bottom warp yarn weaves with the first and second bottom weft yarns. In a pattern repeat, the at least one binding warp yarn may bind with first, second and third non-adjacent bottom weft yarns and a bottom warp yarn weaves with the first, second and third bottom weft yarns. In a pattern repeat, the at least one binding warp yarn may bind with only first, second and third non-adjacent bottom weft yarns and a bottom warp yarn weaves with the first, second and third bottom weft yarns. In a pattern repeat, each binding warp yarn may bind with only first, second and third non-adjacent bottom weft yarns and corresponding bottom warp yarns weave only with a same first, second and third bottom weft yarns. In a pattern repeat, the at least one binding warp yarn may bind with first, second, third and fourth non-adjacent bottom weft yarns and a bottom warp yarn weaves with the first, second, third and fourth bottom weft yarns. In a pattern repeat, the at least one binding warp yarn may bind with only first, second, third and fourth non-adjacent bottom weft yarns and a bottom warp yarns weave with the first, second, third and fourth bottom weft yarns. In a pattern repeat, each binding warp yarn may bind with only first, second, third and fourth non-adjacent bottom weft yarns and corresponding bottom warp yarns weave only with the first, second, third and fourth bottom weft yarns. In a pattern repeat, all bottom warp yarns may weave only in the bottom layer to non-adjacent bottom weft yarns.
[0019] All of the binding warp yarns may weave only with a plain weave when in the top layer. All of the binding warp yarns may bind to non-adjacent bottom weft yarns in a pattern repeat. The binding warp yarns may bind to different non-adjacent bottom weft yarns in a pattern repeat. The top layer may have a papermaking surface and the bottom has a machine side surface.
[0020] In a pattern repeat, each of the binding warp yarns may be vertically stacked with respect to bottom warp yarns. In a pattern repeat, more top weft yarns may be utilized that bottom weft yarns. In a pattern repeat, 30 top weft yarns may be utilized and 20 bottom weft yarns are utilized. In a pattern repeat, 30 top weft yarns may be utilized and 15 bottom weft yarns are utilized. In a pattern repeat, 20 top or binding warp yarns are utilized and 20 bottom warp yarns may be utilized.
[0021] At least one of the binding warp yarns per pattern repeat may differ from bottom warp yarns in at least one of the following characteristics size, modulus, and material. At least one of the top weft yarns per pattern repeat may differ from the bottom weft yarns in at least one of the following characteristics size, modulus, and material. At least one of the binding warp yarns may be smaller in size than at least one bottom warp yarn. At least one of the top layer may have a different weave pattern than the bottom layer and the top layer may utilize a plain weave and the bottom layer does not utilize a plain weave.
[0022] The invention also provides for a forming fabric comprising a top layer comprising top weft yarns, a bottom layer comprising bottom weft yarns, at least one binding warp yarn weaving with the top weft yarns and binding to at least two non-adjacent bottom weft yarns, and at least one bottom warp yarn weaving only with bottom weft yarns.
[0023] The invention also provides for a forming fabric comprising a top layer comprising top weft yarns, a bottom layer comprising bottom weft yarns, at least one binding warp yarn weaving with top weft yarns and binding to at least two non-adjacent bottom weft yarns in a pattern repeat, and at least one bottom warp yarn weaving with the at least two non-adjacent bottom weft yarns.
[0024] The invention also provides for a method of making the fabric of any of the types described above, wherein the method comprises binding together the top and bottom layers using only the binding warp yarns.
[0025] The invention also provides for a method of making the fabric of any of the types described above, wherein the method comprises binding the top and bottom layers together using the binding warp yarns, wherein each binding warp yarn binds to at least three non-adjacent bottom weft yarns per pattern repeat.
[0026] Additional aspects of the present invention include methods of manufacturing warp-stitched triple layer fabrics and methods of using the triple layer papermaker's fabric described herein for making paper.
BRIEF DESCRIPTION OF THE FIGURES
[0027] The present invention is further described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of exemplary embodiments of the present invention, in which like reference numerals, represent similar parts throughout the several views of the drawings, and wherein:
[0028] FIG. 1 shows a weave pattern repeat of a first embodiment of the present invention;
[0029] FIG. 2 a shows a cross-section view of the repeat shown in FIG. 1 and illustrates binding yarns 2 , 4 , 6 , 8 and 10 (listed from the bottom up on the left-hand side) and bottom warp yarns 1 , 3 , 5 , 7 and 9 (listed from the bottom up on the left-hand side). The top and bottom weft yarns 1 - 50 are listed right to left;
[0030] FIG. 2 b shows a cross-section view of the repeat shown in FIG. 1 and illustrates binding warp yarns 12 , 14 , 16 , 18 and 20 (listed from the bottom up on the left-hand side) and bottom warp yarns 11 , 13 , 15 , 17 and 19 (listed from the bottom up on the left-hand side). The top and bottom weft yarns 1 - 50 are again listed right to left;
[0031] FIG. 3 shows a photograph of a top side or paper facing side of an actual forming fabric utilizing the weave pattern shown in FIGS. 1-2 b;
[0032] FIG. 4 shows a photograph of a bottom side or machine side of the forming fabric shown in FIG. 3 ;
[0033] FIG. 5 shows a weave pattern repeat of a second embodiment of the present invention;
[0034] FIG. 6 a shows a cross-section view of the repeat shown in FIG. 6 and illustrates binding warp yarns 1 , 3 , 5 , 7 and 9 (listed from the top down on the left-hand side) and bottom warp yarns 2 , 4 , 6 , 8 and 10 (listed from the top down on the left-hand side). The top and bottom weft yarns 1 - 45 are listed right to left;
[0035] FIG. 6 b shows a cross-section view of the repeat shown in FIG. 6 and illustrates binding warp yarns 11 , 13 , 15 , 17 and 19 (listed from the top down on the left-hand side) and bottom warp yarns 12 , 14 , 16 , 18 and 20 (listed from the top down on the left-hand side). The top and bottom weft yarns 145 are again listed right to left;
[0036] FIG. 7 shows a photograph of a top side or paper facing side of an actual forming fabric utilizing the weave pattern shown in FIGS. 5-6 b ; and
[0037] FIG. 8 shows a photograph of a bottom side or machine side of the forming fabric shown in FIG. 7 .
DETAILED DESCRIPTION OF THE INVENTION
[0038] The particulars shown herein are by way of example and for purposes of illustrative discussion of the embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the present invention. In this regard, no attempt is made to show structural details of the present invention in more detail than is necessary for the fundamental understanding of the present invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the present invention may be embodied in practice.
[0039] FIG. 1 shows a first non-limiting embodiment of the invention and depicts a top pattern view of the top fabric layer of the multilayer fabric (i.e., a view of the papermaking surface). The numbers 1 - 20 shown on the bottom of the pattern identify the upper and lower warp yarns while the right side numbers 1 - 50 show the upper or top and lower or bottom weft yarns. The bottom warp yarns shown on the bottom of the pattern are 1 , 3 , 5 , 7 , 9 , 11 , 13 , 15 , 17 and 19 . The upper warp yarns shown on the bottom of the pattern are 2 , 4 , 6 , 8 , 10 , 12 , 14 , 16 , 18 and 20 . The upper weft yarns shown on the right side of the pattern are 1 , 3 , 5 , 6 , 8 , 10 , 11 , 13 ,: 15 , 16 , 18 , 20 , 21 , 23 , 25 , 26 , 28 , 30 , 31 , 33 , 35 , 36 , 38 , 40 , 41 , 43 , 45 , 46 , 48 and 50 . The lower weft yarns shown on the right side of the pattern are 2 , 4 , 7 , 9 , 12 , 14 , 17 , 19 , 22 , 24 , 27 , 29 , 32 , 34 , 37 , 39 , 42 , 44 , 47 and 49 .
[0040] Also in FIG. 1 , a blank cell is shown in locations where a binding warp yarn passes under a top weft yarn while a bottom warp yarn passes under a bottom weft yarn. Symbol X is shown in locations where a binding warp yarn passes over a top weft yarn while a bottom warp yarn passes under a bottom weft yarn. A shaded cell is shown in locations where a binding warp yarn passes over a bottom weft yarn while a bottom warp yarn passes over the same bottom weft yarn. As used herein, the term “over” in reference to a weave pattern of a warp yarn in the top layer means that the yarn passes vertically above a paper-side surface of the fabric and then over a top weft yarn. The term “over” in reference to a weave pattern of a warp yarn in the bottom layer means that the yarn passes vertically below a machine-side surface and then over a top weft yarn as opposed to passing between the top and bottom weft yarns.
[0041] FIGS. 2 a and 2 b depict the paths of the upper and lower warp yarns 1 - 20 as they weave through the upper and lower weft yarns 1 - 50 . The fabric of FIG. 1 thus shows a single repeat of the fabric that encompasses 50 weft yarns (yarns 1 - 50 represented horizontally in the figures) and 20 warp yarns (yarns 1 - 20 represented vertically in the figures). While FIGS. 1-2 b only show a single repeat unit of the fabric, those of skill in the art will appreciate that in commercial applications, the repeat unit shown in FIGS. 1-2 b would be repeated many times, in both the warp and weft directions, to form a large fabric suitable for use on a papermaking machine.
[0042] As seen in FIG. 2 a , bottom warp yarn 1 passes under bottom weft yarns 2 , 4 , 7 , 9 , 12 and 14 , then passes over bottom weft yarn 17 , then passes under bottom weft yarns 19 and 22 , then passes over bottom weft yarn 24 , then passes under bottom weft yarns 27 , 29 , 32 , 34 , 37 and 39 , then passes over bottom weft yarn 42 , then passes under bottom weft yarns 44 and 47 , and then passes over bottom weft yarn 49 . The bottom warp yarn 1 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 17 , 24 , 42 and 49 .
[0043] Also seen in FIG. 2 a , binding warp yarn 2 passes from the bottom layer to the top layer by passing under top weft yarns 1 and 3 , then weaves with the top layer weft yarns 5 , 6 , 8 , 10 and 11 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 13 and 15 , then passes over bottom weft yarn 17 , then passes under bottom weft yarns 19 and 22 , then passes over bottom weft yarn 24 , then passes from the bottom layer to the top layer by passing under top weft yarns 25 , 26 , and 28 , then weaves with the top weft yarns 30 , 31 , 33 , 35 and 36 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 38 and 40 , then passes over bottom weft yarn 42 , then passes under bottom weft yarns 44 and 47 , then passes over bottom weft yarn 49 , and then begins to pass back to the top layer. The binding warp yarn 2 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 1 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 17 , 24 , 42 and 49 .
[0044] FIG. 2 a also illustrates bottom warp yarn 3 passing over bottom weft yarn 2 , then passes under bottom weft yarns 4 and 7 , then passes over bottom weft yarn 9 , then passes under bottom weft yarns 12 , 14 , 17 , 19 , 22 and 24 , then passes over bottom weft yarn 27 , then passes under bottom weft yarns 29 and 32 , then passes over bottom weft yarn 34 , and then passes under bottom weft yarns 37 , 39 , 42 , 44 , 47 and 49 . The bottom warp yarn 3 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 2 , 9 , 27 and 34 . The pattern formed by bottom warp yarn 3 is the same as that of bottom warp yarn 1 except that it is shifted sideways by six bottom weft yarns.
[0045] Also seen in FIG. 2 a , binding warp yarn 4 passes over bottom weft yarn 2 , then passes under bottom weft yarns 4 and 7 , then passes over bottom weft yarn 9 , then passes from the bottom layer to the top layer by passing under top weft yarns 10 , 11 and 13 , then weaves with the top layer weft yarns 15 , 16 , 18 , 20 and 21 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 23 and 25 , then passes over bottom weft yarn 27 , then passes under bottom weft yarns 29 and 32 , then passes over bottom weft yarn 34 , then passes from the bottom layer to the top layer by passing under top weft yarns 35 , 36 , and 38 , then weaves with the top weft yarns 40 , 41 , 43 , 45 and 46 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 48 and 50 . The binding warp yarn 4 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 3 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 2 , 9 , 27 and 34 . The pattern formed by binding warp yarn 4 is the same as that of binding warp yarn 2 except that it is shifted sideways by six top weft yarns.
[0046] FIG. 2 a additionally shows bottom warp yarn 5 passing under bottom weft yarns 2 , 4 , 7 and 9 , then passes over bottom weft yarn 12 , then passes under bottom weft yarns 14 and 17 , then passes over bottom weft yarn 19 , then passes under bottom weft yarns 22 , 24 , 27 , 29 , 32 and 34 , then passes over bottom weft yarn 37 , then passes under bottom weft yarns 39 and 42 , and then passes over bottom weft yarn 44 , then passes under bottom weft yarns 47 and 49 . The bottom warp yarn 5 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 12 , 19 , 37 and 44 . The pattern formed by bottom warp yarn 5 is the same as that of bottom warp yarn 3 except that it is shifted sideways by four bottom weft yarns.
[0047] Also seen in FIG. 2 a , binding warp yarn 6 weaves with the top weft yarns 1 , 3 , 5 and 6 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 8 and 10 , then passes over bottom weft yarn 12 , then passes under bottom weft yarns 14 and 17 , then passes over bottom weft yarn 19 , then passes from the bottom layer to the top layer by passing under top weft yarns 20 , 21 and 23 , then weaves with the top weft yarns 25 , 26 , 28 , 30 and 31 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 33 and 35 , then passes over bottom weft yarn 37 , then passes under bottom weft yarns 39 and 42 , then passes over bottom weft yarn 44 , then passes from the bottom layer to the top layer by passing under top weft yarns 45 , 46 and 48 , then passes over top weft yarn 50 . The binding warp yarn 6 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 5 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 12 , 19 , 37 and 44 . The pattern formed by binding warp yarn 6 is the same as that of binding warp yarn 4 except that it is shifted sideways by six top weft yarns.
[0048] FIG. 2 a further shows bottom warp yarn 7 passing under bottom weft yarn 2 , then passes over bottom weft yarn 4 , then passes under bottom weft yarns 7 , 9 , 12 , 14 , 17 and 19 , then passes over bottom weft yarn 22 , then passes under bottom weft yarns 24 and 27 , then passes over bottom weft yarn 29 , then passes under bottom weft yarns 32 , 34 , 37 , 39 , 42 and 44 , and then passes over bottom weft yarn 44 , then passes under bottom weft yarn 49 . The bottom warp yarn 7 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 4 , 22 , 29 and 47 . The pattern formed by bottom warp yarn 7 is the same as that of bottom warp yarn 5 except that it is shifted sideways by four bottom weft yarns.
[0049] Also seen in FIG. 2 a , binding warp yarn 8 passes under bottom weft yarn 2 , then passes over bottom weft yarn 4 , then passes from the bottom layer to the top layer by passing under top weft yarns 5 , 6 and 8 , then weaves with the top weft yarns 10 , 11 , 13 , 15 and 16 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 18 and 20 , then passes over bottom weft yarn 22 , then passes under bottom weft yarns 24 and 27 , then passes over bottom weft yarn 29 , then passes from the bottom layer to the top layer by passing under top weft yarns 30 , 31 and 33 , then weaves with the top weft yarns 35 , 36 , 38 , 40 and 41 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 43 and 45 , then passes over bottom weft yarn 47 , then passes under bottom weft yarn 49 . The binding warp yarn 8 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 7 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 4 , 22 , 29 and 47 . The pattern formed by binding warp yarn 8 is the same as that of binding warp yarn 6 except that it is shifted sideways by six top weft yarns.
[0050] Additionally, FIG. 2 a shows bottom warp yarn 9 passing under bottom weft yarns 2 and 4 , then passes over bottom weft yarn 7 , then passes under bottom weft yarns 9 and 12 , then passes over bottom weft yarn 14 , then passes under bottom weft yarns 17 , 19 , 22 , 24 , 27 and 29 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 34 and 37 , and then passes over bottom weft yarn 39 , then passes under bottom weft yarns 42 , 44 , 47 and 49 . The bottom warp yarn 9 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 7 , 14 , 32 and 39 . The pattern formed by bottom warp yarn 9 is the same as that of bottom warp yarn 7 except that it is shifted sideways by four bottom weft yarns.
[0051] Finally, FIG. 2 a shows binding warp yarn 10 passing over the top weft yarn 1 , then passes from the top layer to the bottom layer by passing under top weft yarns 3 and 5 , then passes over bottom weft yarn 7 , then passes under bottom weft yarns 9 and 12 , then passes over bottom weft yarn 14 , then passes from the bottom layer to the top layer by passing under top weft yarns 15 , 16 and 18 , then weaves with the top weft yarns 20 , 21 , 23 , 25 and 26 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 28 and 30 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 34 and 37 , then passes over bottom weft yarn 39 , then passes from the bottom layer to the top layer by passing under top weft yarns 40 , 41 and 43 , then weaves with binding warp yarns 45 , 46 , 48 and 50 to form a plain weave. The binding warp yarn 10 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 9 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 7 , 14 , 32 and 39 . The pattern formed by binding warp yarn 10 is the same as that of binding warp yarn 8 except that it is shifted sideways by six top weft yarns.
[0052] With reference to FIG. 2 b , bottom warp yarn 11 passes under bottom weft yarns 2 , 4 , 7 , 9 , 12 and 14 , then passes over bottom weft yarn 17 , then passes under bottom weft yarns 19 and 22 , then passes over bottom weft yarn 24 , then passes under bottom weft yarns 27 , 29 , 32 , 34 , 37 and 39 , then passes over bottom weft yarn 42 , then passes under bottom weft yarns 44 and 47 , and then passes over bottom weft yarn 49 . The bottom warp yarn 11 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 17 , 24 , 42 and 49 .
[0053] Also seen in FIG. 2 b , binding warp yarn 12 passes from the bottom layer to the top layer by passing under top weft yarns 1 and 3 , then weaves with the top layer weft yarns 5 , 6 , 8 , 10 and 11 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 13 and 15 , then passes over bottom weft yarn 17 , then passes under bottom weft yarns 19 and 22 , then passes over bottom weft yarn 24 , then passes from the bottom layer to the top layer after passing under top weft yarns 25 , 26 , and 28 , then weaves with the top weft yarns 30 , 31 , 33 , 35 and 36 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 38 and 40 , then passes over bottom weft yarn 42 , then passes under bottom weft yarns 44 and 47 , then passes over bottom weft yarn 49 , and then begins to pass back to the top layer. The binding warp yarn 12 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 11 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 17 , 24 , 42 and 49 .
[0054] FIG. 2 b also illustrates bottom warp yarn 13 passing over bottom weft yarn 2 , then passes under bottom weft yarns 4 and 7 , then passes over bottom weft yarn 9 , then passes under bottom weft yarns 12 , 14 , 17 , 19 , 22 and 24 , then passes over bottom weft yarn 27 , then passes under bottom weft yarns 29 and 32 , then passes over bottom weft yarn 34 , and then passes under bottom weft yarns 37 , 39 , 42 , 44 , 47 and 49 . The bottom warp yarn 13 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 2 , 9 , 27 and 34 . The pattern formed by bottom warp yarn 13 is the same as that of bottom warp yarn 11 except that it is shifted sideways by six bottom weft yarns.
[0055] Also seen in FIG. 2 b , binding warp yarn 14 passes over bottom weft yarn 2 , then passes under bottom weft yarns 4 and 7 , then passes over bottom weft yarn 9 , then passes from the bottom layer to the top layer by passing under top weft yarns 10 , 11 and 13 , then weaves with the top layer weft yarns 15 , 16 , 18 , 20 and 21 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 23 and 25 , then passes over bottom weft yarn 27 , then passes under bottom weft yarns 29 and 32 , then passes over bottom weft yarn 34 , then passes from the bottom layer to the top layer by passing under top weft yarns 35 , 36 , and 38 , then weaves with the top weft yarns 40 , 41 , 43 , 45 and 46 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 48 and 50 . The binding warp yarn 14 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 13 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 2 , 9 , 27 and 34 . The pattern formed by binding warp yarn 14 is the same as that of binding warp yarn 12 except that it is shifted sideways by six top weft yarns.
[0056] FIG. 2 b also illustrates bottom warp yarn 15 passing under bottom weft yarns 2 , 4 , 7 and 9 , then passes over bottom weft yarn 12 , then passes under bottom weft yarns 14 and 17 , then passes over bottom weft yarn 19 , then passes under bottom weft yarns 22 , 24 , 27 , 29 , 32 and 34 , then passes over bottom weft yarn 37 , then passes under bottom weft yarns 39 and 42 , and then passes over bottom weft yarn 44 , then passes under bottom weft yarns 47 and 49 . The bottom warp yarn 15 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 12 , 19 , 37 and 44 . The pattern formed by bottom warp yarn 15 is the same as that of bottom warp yarn 13 except that it is shifted sideways by four bottom weft yarns.
[0057] Also seen in FIG. 2 b , binding warp yarn 16 weaves with the top weft yarns 1 , 3 , 5 and 6 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 8 and 10 , then passes over bottom weft yarn 12 , then passes under bottom weft yarns 14 and 17 , then passes over bottom weft yarn 19 , then passes from the bottom layer to the top layer by passing under top weft yarns 20 , 21 and 23 , then weaves with the top weft yarns 25 , 26 , 28 , 30 and 31 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 33 and 35 , then passes over bottom weft yarn 37 , then passes under bottom weft yarns 39 and 42 , then passes over bottom weft yarn 44 , then passes from the bottom layer to the top layer by passing under top weft yarns 45 , 46 and 48 , then passes over top weft yarn 50 . The binding warp yarn 16 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 15 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 12 , 19 , 37 and 44 . The pattern formed by binding warp yarn 16 is the same as that of binding warp yarn 14 except that it is shifted sideways by six top weft yarns.
[0058] FIG. 2 b further illustrates bottom warp yarn 17 passing under bottom weft yarn 2 , then passes over bottom weft yarn 4 , then passes under bottom weft yarns 7 , 9 , 12 , 14 , 17 and 19 , then passes over bottom weft yarn 22 , then passes under bottom weft yarns 24 and 27 , then passes over bottom weft yarn 29 , then passes under bottom weft yarns 32 , 34 , 37 , 39 , 42 and 44 , and then passes over bottom weft yarn 44 , then passes under bottom weft yarn 49 . The bottom warp yarn 17 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 4 , 22 , 29 and 47 . The pattern formed by bottom warp yarn 17 is the same as that of bottom warp yarn 15 except that it is shifted sideways by four bottom weft yarns.
[0059] FIG. 2 b further shows binding warp yarn 18 passing under bottom weft yarn 2 , then passes over bottom weft yarn 4 , then passes from the bottom layer to the top layer by passing under top weft yarns 5 , 6 and 8 , then weaves with the top weft yarns 10 , 11 , 13 , 15 and 16 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 18 and 20 , then passes over bottom weft yarn 22 , then passes under bottom weft yarns 24 and 27 , then passes over bottom weft yarn 29 , then passes from the bottom layer to the top layer by passing under top weft yarns 30 , 31 and 33 , then weaves with the top weft yarns 35 , 36 , 38 , 40 and 41 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 43 and 45 , then passes over bottom weft yarn 47 , then passes under bottom weft yarn 49 . The binding warp yarn 18 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 17 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 4 , 22 , 29 and 47 . The pattern formed by binding warp yarn 18 is the same as that of binding warp yarn 16 except that it is shifted sideways by six top weft yarns.
[0060] FIG. 2 b also shows bottom warp yarn 19 passing under bottom weft yarns 2 and 4 , then passes over bottom weft yarn 7 , then passes under bottom weft yarns 9 and 12 , then passes over bottom weft yarn 14 , then passes under bottom weft yarns 17 , 19 , 22 , 24 , 27 and 29 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 34 and 37 , and then passes over bottom weft yarn 39 , then passes under bottom weft yarns 42 , 44 , 47 and 49 . The bottom warp yarn 19 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., four non-adjacent bottom weft yarns 7 , 14 , 32 and 39 . The pattern formed by bottom warp yarn 19 is the same as that of bottom warp yarn 17 except that it is shifted sideways by four bottom weft yarns.
[0061] Finally, as seen in FIG. 2 b , binding warp yarn 20 passes over the top weft yarn 1 , then passes from the top layer to the bottom layer by passing under top weft yarns 3 and 5 , then passes over bottom weft yarn 7 , then passes under bottom weft yarns 9 and 12 , then passes over bottom weft yarn 14 , then passes from the bottom layer to the top layer by passing under top weft yarns 15 , 16 and 18 , then weaves with the top weft yarns 20 , 21 , 23 , 25 and 26 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 28 and 30 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 34 and 37 , then passes over bottom weft yarn 39 , then passes from the bottom layer to the top layer by passing under top weft yarns 40 , 41 and 43 , then weaves with binding warp yarns 45 , 46 , 48 and 50 to form a plain weave. The binding warp yarn 20 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 19 was woven with, e.g., by passing over the four non-adjacent bottom weft yarns 7 , 14 , 32 and 39 . The pattern formed by binding warp yarn 20 is the same as that of binding warp yarn 18 except that it is shifted sideways by six top weft yarns.
[0062] As is apparent from a comparison of FIG. 2 a and 2 b , the paths taken by the warp yarns 1 - 10 through the weft yarns 1 - 50 are respectively the same as paths taken by the warp yarns 11 - 20 through the weft yarns 1 - 50 , i.e., warp yarn 1 has the same path through the weft yarns 1 - 50 as warp yarn 11 , warp yarn 2 has the same path through the weft yarns 1 - 50 as warp yarn 12 , etc,.
[0063] FIG. 3 shows a photograph of a top side or paper facing side of an actual forming fabric utilizing the weave pattern shown in FIG. 1 and FIG. 4 shows a photograph of a bottom side or machine side of the forming fabric shown in FIG. 3 .
[0064] By way of non-limiting example, the binding warp yarns 2 , 4 , 6 , 8 , 10 , 12 , 14 , 16 , 18 and 20 of the embodiment shown in FIGS. 1-2 b can have the following characteristics: acceptable size range of between approximately 0.10 mm and approximately 0.50 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.80 mm, and most preferred size range of between approximately 0.12 mm and approximately 0.20 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament.
[0065] By way of non-limiting example, the bottom warp yarns 1 , 3 , 5 , 7 , 9 , 11 , 13 , 15 , 17 and 19 of the embodiment shown in FIGS. 1-2 b can have the following characteristics: acceptable size range of between approximately 0.15 mm and approximately 0.60 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.40 mm, and most preferred size range of between approximately 0.25 mm and approximately 0.35 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament. The bottom warp yarns can preferably be constructed using relatively large diameter yarns that are well suited to sustain the wear caused by the friction between the machine side surface of the fabric and the papermaking machine during use of the fabric.
[0066] By way of non-limiting example, the top weft yarns 1 , 3 , 5 , 6 , 8 , 10 , 11 , 13 , 15 , 16 , 18 , 20 , 21 , 23 , 25 , 26 , 28 , 30 , 31 , 33 , 35 , 36 , 38 , 40 , 41 , 43 , 45 , 46 , 48 and 50 of the embodiment shown in FIGS. 1-2 b can have the following characteristics: acceptable size range of between approximately 0.10 mm and approximately 0.50 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.80 mm, and most preferred size range of between approximately 0.12 mm and approximately 0.80 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament.
[0067] By way of non-limiting example, the bottom weft yarns 2 , 4 , 7 , 9 , 12 , 14 , 17 , 19 , 22 , 24 , 27 , 29 , 32 , 34 , 37 , 39 , 42 , 44 , 47 and 49 of the embodiment shown in FIGS. 1-2 b can have the following characteristics: acceptable size range of between approximately 0.15 mm and approximately 0.60 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.40 mm, and most preferred size range of between approximately 0.25 mm and approximately 0.35 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament. These bottom weft yarns may also be constructed using larger diameter yarns than the upper warp yarns.
[0068] In the embodiment shown in FIGS. 1-2 b all of the binding warp yarns form a plain weave in the top layer by weaving with five top weft yarns and bind to the bottom layer by weaving with four bottom weft yarns with a non-plain weave in two spaced apart locations, i.e., spaced apart by ten top weft yarns and/or sic bottom weft yarns in each repeat of the fabric. Furthermore, all of the bottom warp yarns weave only in the bottom layer. Additionally, when a binding warp yarn passes from the bottom layer to the top layer, it passes under three adjacent top weft yarns before weaving with a plain weave in the top layer. When a binding warp yarn passes from the top layer to the bottom layer, it passes under two adjacent top weft yarns before weaving with a non-plain weave in the bottom layer. Thus, the area of the plain weave (between a binding warp yarn and top weft yarns) is off-center with respect to an area or spacing between the two areas where the same binding warp yarn weaves to the bottom layer. Also, in the area or spacing between two the plain weave areas (between a binding warp yarn and top weft yarns), the area where the binding warp weaves with the bottom layer is off-center. These features are also desirable in numerous papermaking applications.
[0069] FIG. 5 shows a second non-limiting embodiment of the invention and depicts a top pattern view of the top fabric layer of the multilayer fabric (i.e., a view of the papermaking surface). The numbers 1 - 20 shown on the bottom of the pattern identify the upper and lower warp yarns while the right side numbers 1 - 45 show the upper and lower weft yarns. The upper warp yarns shown on the bottom of the pattern are 1 , 3 , 5 , 7 , 9 , 11 , 13 , 15 , 17 and 19 . The lower warp yarns shown on the bottom of the pattern are 2 , 4 , 6 , 8 , 10 , 12 , 14 , 16 , 18 and 20 . The top weft yarns shown on the right side of the pattern are 1 , 3 , 4 , 6 , 7 , 9 , 10 , 12 , 13 , 15 , 16 , 18 , 19 , 21 , 22 , 24 , 25 , 27 , 28 , 30 , 31 , 33 , 34 , 36 , 37 , 39 , 40 , 42 , 43 and 45 . The bottom weft yarns shown on the right side of the pattern are 2 , 5 , 8 , 11 , 14 , 17 , 20 , 23 , 26 , 29 , 32 , 35 , 38 , 41 and 44 .
[0070] Also in FIG. 5 , a blank cell is shown in locations where a binding warp yarn passes under a top weft yarn while a bottom warp yarn passes under a bottom weft yarn. Symbol X is shown in locations where a binding warp yarn passes over a top weft yarn while a bottom warp yarn passes under a bottom weft yarn. A shaded cell is shown in locations where a binding warp yarn passes over a bottom weft yarn while a bottom warp yarn passes over the same bottom weft yarn. As used herein, the term “over” in reference to a weave pattern of a warp yarn in the top layer means that the yarn passes vertically above a paper-side surface of the fabric and then over a top weft yarn. The term “over” in reference to a weave pattern of a warp yarn in the bottom layer means that the yarn passes vertically below a machine-side surface and then over a top weft yarn as opposed to passing between the top and bottom weft yarns.
[0071] FIGS. 6 a and 6 b depict the paths of the upper and lower warp yarns 1 - 20 as they weave through the upper and lower weft yarns 1 - 45 . The fabric of FIG. 5 thus shows a single repeat of the fabric that encompasses 45 weft yarns (yarns 1 - 45 represented horizontally in the figures) and 20 warp yarns (yarns 1 - 20 represented vertically in the figures). While FIGS. 5-6 b only show a single repeat unit of the fabric, those of skill in the art will appreciate that in commercial applications, the repeat unit shown in FIGS. 5-6 b would be repeated many times, in both the warp and weft directions, to form a large fabric suitable for use on a papermaking machine.
[0072] As seen in FIG. 6 a , binding warp yarn 1 passes from the bottom layer to the top layer by passing under top weft yarns 1 and 3 , then weaves with the top layer weft yarns 4 , 6 , 7 , 9 and 10 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 12 , 13 and 15 , then passes over bottom weft yarn 17 , then passes under bottom weft yarn 20 , then passes over bottom weft yarn 23 , then passes from the bottom layer to the top layer by passing under top weft yarns 24 and 25 , then weaves with the top weft yarns 27 , 28 , 30 , 31 and 33 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 34 and 36 , then passes over bottom weft yarn 38 , then passes back to the top layer by passing under top weft yarns 39 , 40 , 42 , 43 and 45 . The binding warp yarn 1 binds to the bottom layer by weaving with the same adjacent bottom weft yarns that the bottom warp yarn 2 was woven with, e.g., by passing over the three non-adjacent bottom weft yarns 17 , 23 and 38 .
[0073] Also seen in FIG. 6 a , bottom warp yarn 2 passes under bottom weft yarns 2 , 5 , 8 , 11 and 14 , then passes over bottom weft yarn 17 , then passes under bottom weft yarn 20 , then passes over bottom weft yarn 23 , then passes under bottom weft yarns 26 , 29 , 32 and 35 , then passes over bottom weft yarn 38 , then passes under bottom weft yarns 41 and 44 . The bottom warp yarn 2 weaves only in the bottom layer, weaves first with three adjacent bottom weft yarns, e.g., bottom weft yarns 17 , 20 and 23 , and then binds with only one bottom weft yarn, e.g., bottom weft yarn 38 .
[0074] FIG. 6 a also illustrates binding warp yarn 3 passing over bottom weft yarn 2 , then passes under bottom weft yarns 3 , 4 , 6 , 7 , 9 , 10 and 12 , then weaves with the top layer weft yarns 13 , 15 , 16 , 18 and 19 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 21 , 22 and 24 , then passes over bottom weft yarn 26 , then passes under bottom weft yarn 29 , then passes over bottom weft yarn 32 , then passes from the bottom layer to the top layer by passing under top weft yarns 33 and 34 , then weaves with the top weft yarns 36 , 37 , 39 , 40 and 42 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 43 and 45 . The binding warp yarn 3 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 4 was woven with, e.g., by passing over the three non-adjacent bottom weft yarns 2 , 26 and 32 . The pattern formed by binding warp yarn 3 is different from that of binding warp yarn 1 in both position and weaving path.
[0075] Also seen in FIG. 6 a , bottom warp yarn 4 passes over bottom weft yarn 2 , then passes under bottom weft yarns 5 , 8 , 11 , 14 , 17 , 20 and 23 , then passes over bottom weft yarn 26 , then passes under bottom weft yarn 29 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 35 , 38 , 41 and 44 . The bottom warp yarn 4 weaves only in the bottom layer, weaves first with one bottom weft yarn, e.g., bottom weft yarn 2 , and then weaves with three bottom weft yarns, e.g., bottom, weft yarns 26 , 29 and 32 . The pattern formed by bottom warp yarn 4 is the same as that of bottom warp yarn 2 except that it is shifted sideways by three bottom weft yarns.
[0076] FIG. 6 a also shows binding warp yarn 5 weaving with the top weft yarns 1 , 3 , 4 and 6 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 7 and 9 , then passes over bottom weft yarn 11 , then passes from the bottom layer to the top layer by passing under top weft yarns 12 , 13 , 15 , 16 , 18 , 19 and 21 , then weaves with the top weft yarns 22 , 24 , 25 , 27 and 28 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 30 , 31 and 33 , then passes over bottom weft yarn 35 , then passes under bottom weft yarn 38 , then passes over bottom weft yarn 41 , then passes from the bottom layer to the top layer by passing under top weft yarns 42 and 43 , then passes over top weft yarn 45 . The binding warp yarn 5 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 6 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 11 , 35 and 41 . The pattern formed by binding warp yarn 5 is the same as that of binding warp yarn 3 except that it is shifted sideways by nine top weft yarns.
[0077] As seen in FIG. 6 a , bottom warp yarn 6 passes under bottom weft yarns 2 , 5 and 8 , then passes over bottom weft yarn 11 , then passes under bottom weft yarns 14 , 17 , 20 , 23 , 26 , 29 and 32 , then passes over bottom weft yarn 35 , then passes under bottom weft yarn 38 , then passes over bottom weft yarn 41 , then passes under bottom weft yarn 44 . The bottom warp yarn 6 weaves only in the bottom layer, weaves first with one bottom weft yarn, e.g., bottom weft yarn 11 , and then weaves with three bottom weft yarns, e.g., bottom weft yarns 35 , 38 and 41 . The pattern formed by bottom warp yarn 6 is the same as that of bottom warp yarn 4 except that it is shifted sideways by three bottom weft yarns.
[0078] Additionally, FIG. 6 a shows binding warp yarn 7 passing from the top layer to the bottom layer by passing under top weft yarns 1 and 3 , then under bottom weft yarn 5 , then passes from the bottom layer to the top layer by passing under top weft yarns 6 and 7 , then weaves with the top weft yarns 9 , 10 , 12 , 13 and 15 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 16 and 18 , then passes over bottom weft yarn 20 , then passes from the bottom layer to the top layer by passing under top weft yarns 21 , 22 , 24 , 25 , 27 , 28 and 30 , then weaves with the top weft yarns 31 , 33 , 34 , 36 and 37 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 39 , 40 and 42 , then passes over bottom weft yarn 44 , then begins to pass back to the top layer from the bottom layer by passing under top weft yarn 45 . The binding warp yarn 7 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 8 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 5 , 20 and 44 . The pattern formed by binding warp yarn 7 is different from that of the binding warp yarns 1 , 3 , 5 and 9 .
[0079] As seen in FIG. 6 a , bottom warp yarn 8 passes under bottom weft yarn 2 , then passes over bottom weft yarn 5 , then passes under bottom weft yarns 8 , 11 , 14 and 17 , then passes over bottom weft yarn 20 , then passes under bottom weft yarns 23 , 26 , 29 , 32 , 35 , 38 and 41 , then passes over bottom weft yarn 44 . The bottom warp yarn 8 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., three non-adjacent bottom weft yarns 5 , 20 and 44 . The pattern formed by bottom warp yarn 8 is different from that of the bottom warp yarns 2 , 4 , 6 and 10 .
[0080] Furthermore, FIG. 6 a shows binding warp yarn 9 passing over the top weft yarn 1 , then passes from the top layer to the bottom layer by passing under top weft yarns 3 , 4 and 6 , then passes over bottom weft yarn 8 , then passes under bottom weft yarn 11 , then passes over bottom weft yarn 14 , then passes from the bottom layer to the top layer by passing under top weft yarns 15 and 16 , then weaves with the top weft yarns 18 , 19 , 21 , 22 and 24 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 25 and 27 , then passes over bottom weft yarn 29 , then passes from the bottom layer to the top layer by passing under top weft yarns 30 , 31 , 33 , 34 , 36 , 37 and 39 , then weaves with top weft yarns 40 , 42 , 43 and 45 to form a plain weave. The binding warp yarn 9 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 10 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 8 , 14 and 29 . The pattern formed by binding warp yarn 9 is the same as that of binding warp yarn 1 except that it is shifted sideways by six top weft yarns.
[0081] Finally, as seen in FIG. 6 a , bottom warp yarn 10 passes under bottom weft yarns 2 and 5 , then passes over bottom weft yarn 8 , then passes under bottom weft yarn 11 , then passes over bottom weft yarn 14 , then passes under bottom weft yarns 17 , 20 , 23 and 26 , then passes over bottom weft yarn 29 , then passes under bottom weft yarns 32 , 35 , 38 , 41 and 44 . The bottom warp yarn 10 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., three bottom weft yarns 8 , 14 and 29 . The pattern formed by bottom warp yarn 10 is the same as that of bottom warp yarn 2 except that it is shifted sideways by three bottom weft yarns.
[0082] With reference to FIG. 6 b , binding warp yarn 11 passes from the bottom layer to the top layer by passing under top weft yarns 1 and 3 , then weaves with the top layer weft yarns 4 , 6 , 7 , 9 and 10 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 12 , 13 and 15 , then passes over bottom weft yarn 17 , then passes under bottom weft yarn 20 , then passes over bottom weft yarn 23 , then passes from the bottom layer to the top layer by passing under top weft yarns 24 and 25 , then weaves with the top weft yarns 27 , 28 , 30 , 31 and 33 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 34 and 36 , then passes over bottom weft yarn 38 , then passes back to the top layer by passing under top weft yarns 39 , 40 , 42 , 43 and 45 . The binding warp yarn 11 binds to the bottom layer by weaving with the same adjacent bottom weft yarns that the bottom warp yarn 12 was woven with, e.g., by passing over the three non-adjacent bottom weft yarns 17 , 23 and 38 .
[0083] Also seen in FIG. 6 b , bottom warp yarn 12 passes under bottom weft yarns 2 , 5 , 8 , 11 and 14 , then passes over bottom weft yarn 17 , then passes under bottom weft yarn 20 , then passes over bottom weft yarn 23 , then passes under bottom weft yarns 26 , 29 , 32 and 35 , then passes over bottom weft yarn 38 , then passes under bottom weft yarns 41 and 44 . The bottom warp yarn 12 weaves only in the bottom layer, weaves first with three adjacent bottom weft yarns, e.g., bottom weft yarns 17 , 20 and 23 , and then binds with only one bottom weft yarn, e.g., bottom weft yarn 38 .
[0084] FIG. 6 b also illustrates binding warp yarn 13 passing over bottom weft yarn 2 , then passes under bottom weft yarns 3 , 4 , 6 , 7 , 9 , 10 and 12 , then weaves with the top layer weft yarns 13 , 15 , 16 , 18 and 19 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 21 , 22 and 24 , then passes over bottom weft yarn 26 , then passes under bottom weft yarn 29 , then passes over bottom weft yarn 32 , then passes from the bottom layer to the top layer by passing under top weft yarns 33 and 34 , then weaves with the top weft yarns 36 , 37 , 39 , 40 and 42 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 43 and 45 . The binding warp yarn 13 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 14 was woven with, e.g., by passing over the three non-adjacent bottom weft yarns 2 , 26 and 32 . The pattern formed by binding warp yarn 13 is different from that of binding warp yarn 11 in both position and weaving path.
[0085] Also seen in FIG. 6 b , bottom warp yarn 14 passes over bottom weft yarn 2 , then passes under bottom weft yarns 5 , 8 , 11 , 14 , 17 , 20 and 23 , then passes over bottom weft yarn 26 , then passes under bottom weft yarn 29 , then passes over bottom weft yarn 32 , then passes under bottom weft yarns 35 , 38 , 41 and 44 . The bottom warp yarn 14 weaves only in the bottom layer, weaves first with one bottom weft yarn, e.g., bottom weft yarn 2 , and then weaves with three bottom weft yarns, e.g., bottom weft yarns 26 , 29 and 32 . The pattern formed by bottom warp yarn 14 is the same as that of bottom warp yarn 12 except that it is shifted sideways by three bottom weft yarns.
[0086] FIG. 6 b also illustrates binding warp yarn 15 weaving with the top weft yarns 1 , 3 , 4 and 6 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 7 and 9 , then passes over bottom weft yarn 11 , then passes from the bottom layer to the top layer by passing under top weft yarns 12 , 13 , 15 , 16 , 18 , 19 and 21 , then weaves with the top weft yarns 22 , 24 , 25 , 27 and 28 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 30 , 31 and 33 , then passes over bottom weft yarn 35 , then passes under bottom weft yarn 38 , then passes over bottom weft yarn 41 , then passes from the bottom layer to the top layer by passing under top weft yarns 42 and 43 , then passes over top weft yarn 45 . The binding warp yarn 15 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 16 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 11 , 35 and 41 . The pattern formed by binding warp yarn 15 is the same as that of binding warp yarn 13 except that it is shifted sideways by nine top weft yarns.
[0087] Additionally, FIG. 6 b shows bottom warp yarn 16 passing under bottom weft yarns 2 , 5 and 8 , then passes over bottom weft yarn 11 , then passes under bottom weft yarns 14 , 17 , 20 , 23 , 26 , 29 and 32 , then passes over bottom weft yarn 35 , then passes under bottom weft yarn 38 , then passes over bottom weft yarn 41 , then passes under bottom weft yarn 44 . The bottom warp yarn 16 weaves only in the bottom layer, weaves first with one bottom weft yarn, e.g., bottom weft yarn 11 , and then weaves with three bottom weft yarns, e.g., bottom weft yarns 35 , 38 and 41 . The pattern formed by bottom warp yarn 16 is the same as that of bottom warp yarn 14 except that it is shifted sideways by three bottom weft yarns.
[0088] Also seen in FIG. 6 b , binding warp yarn 17 passes from the top layer to the bottom layer by passing under top weft yarns 1 and 3 , then under bottom weft yarn 5 , then passes from the bottom layer to the top layer by passing under top weft yarns 6 and 7 , then weaves with the top weft yarns 9 , 10 , 12 , 13 and 15 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 16 and 18 , then passes over bottom weft yarn 20 , then passes from the bottom layer to the top layer by passing under top weft yarns 21 , 22 , 24 , 25 , 27 , 28 and 30 , then weaves with the top weft yarns 31 , 33 , 34 , 36 and 37 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 39 , 40 and 42 , then passes over bottom weft yarn 44 , then begins to pass back to the top layer from the bottom layer by passing under top weft yarn 45 . The binding warp yarn 17 binds to the bottom layer by weaving with the same non-adjacent bottom weft yarns that the bottom warp yarn 18 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 5 , 20 and 44 . The pattern formed by binding warp yarn 17 is different from that of the binding warp yarns 11 , 13 , 15 and 19 .
[0089] FIG. 6 b also illustrates bottom warp yarn 18 passing under bottom weft yarn 2 , then passes over bottom weft yarn 5 , then passes under bottom weft yarns 8 , 11 , 14 and 17 , then passes over bottom weft yarn 20 , then passes under bottom weft yarns 23 , 26 , 29 , 32 , 35 , 38 and 41 , then passes over bottom weft yarn 44 . The bottom warp yarn 18 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., three non-adjacent bottom weft yarns 5 , 20 and 44 . The pattern formed by bottom warp yarn 18 is different from that of the bottom warp yarns 12 , 14 , 16 and 20 .
[0090] Also shown in FIG. 6 b , binding warp yarn 19 passes over the top weft yarn 1 , then passes from the top layer to the bottom layer by passing under top weft yarns 3 , 4 and 6 , then passes over bottom weft yarn 8 , then passes under bottom weft yarn 11 , then passes over bottom weft yarn 14 , then passes from the bottom layer to the top layer by passing under top weft yarns 15 and 16 , then weaves with the top weft yarns 18 , 19 , 21 , 22 and 24 to form a plain weave, then passes from the top layer to the bottom layer by passing under top weft yarns 25 and 27 , then passes over bottom weft yarn 29 , then passes from the bottom layer to the top layer by passing under top weft yarns 30 , 31 , 33 , 34 , 36 , 37 and 39 , then weaves with top weft yarns 40 , 42 , 43 and 45 to form a plain weave. The binding warp yarn 19 binds to the bottom layer by weaving with the same bottom weft yarns that the bottom warp yarn 20 weaves with, e.g., by passing over the three non-adjacent bottom weft yarns 8 , 14 and 29 . The pattern formed by binding warp yarn 19 is the same as that of binding warp yarn 11 except that it is shifted sideways by six top weft yarns.
[0091] Finally, as seen in FIG. 6 b , bottom warp yarn 20 passes under bottom weft yarns 2 and 5 , then passes over bottom weft yarn 8 , then passes under bottom weft yarn 11 , then passes over bottom weft yarn 14 , then passes under bottom weft yarns 17 , 20 , 23 and 26 , then passes over bottom weft yarn 29 , then passes under bottom weft yarns 32 , 35 , 38 , 41 and 44 . The bottom warp yarn 20 weaves only in the bottom layer and only with non-adjacent bottom weft yarns, e.g., three bottom weft yarns 8 , 14 and 29 . The pattern formed by bottom warp yarn 20 is the same as that of bottom warp yarn 12 except that it is shifted sideways by three bottom weft yarns.
[0092] As is apparent from a comparison of FIG. 6 a and 6 b , the paths taken by the warp yarns 1 - 10 through the weft yarns 1 - 45 are respectively the same as paths taken by the warp yarns 11 - 20 through the weft yarns 1 - 45 , i.e., warp yarn 1 has the same path through the weft yarns 1 - 45 as warp yarn 11 , warp yarn 2 has the same path through the weft yarns 1 - 45 as warp yarn 12 , etc,.
[0093] FIG. 7 shows a photograph of a top side or paper facing side of an actual forming fabric utilizing the weave pattern shown in FIG. 5 and FIG. 8 shows a photograph of a bottom side or machine side of the forming fabric shown in FIG. 7 .
[0094] By way of non-limiting example, the binding warp yarns 1 , 3 , 5 , 7 , 9 , 11 , 13 , 15 , 17 and 19 of the embodiment shown in FIGS. 5-6 b can have the following characteristics: acceptable size range of between approximately 0.10 mm and approximately 0.50 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.80 mm, and most preferred size range of between approximately 0.12 mm and approximately 0.20 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament.
[0095] By way of non-limiting example, the bottom warp yarns 2 , 4 , 6 , 8 , 10 , 12 , 14 , 16 , 18 and 20 of the embodiment shown in FIGS. 5-6 b can have the following characteristics:,acceptable size range of between approximately 0.15 mm and approximately 0.60 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.40 mm, and most preferred size range of between approximately 0.25 mm and approximately 0.35 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament. The bottom warp yarns can preferably be constructed using relatively large diameter yarns that are well suited to sustain the wear caused by the friction between the machine side surface of the fabric and the papermaking machine during use of the fabric.
[0096] By way of non-limiting example, the top weft yarns 1 , 3 , 4 , 6 , 7 , 9 , 10 , 12 , 13 , 15 , 16 , 18 , 19 , 21 , 22 , 24 , 25 , 27 , 28 , 30 , 31 , 33 , 34 , 36 , 37 , 39 , 40 , 42 , 43 and 45 of the embodiment shown in FIGS. 5-6 b can have the following characteristics: acceptable size range of between approximately 0.10 mm and approximately 0.50 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.80 mm, and most preferred size range of between approximately 0.12 mm and approximately 0.80 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament.
[0097] By way of non-limiting example, the bottom weft yarns 2 , 5 , 8 , 11 , 14 , 17 , 20 , 23 , 26 , 29 , 32 , 35 , 38 , 41 and 44 of the embodiment shown in FIGS. 5-6 b can have the following characteristics: acceptable size range of between approximately 0.15 mm and approximately 0.60 mm, preferable size ranges of between approximately 0.20 mm and approximately 0.40 mm, and most preferred size range of between approximately 0.25 mm and approximately 0.35 mm. The material for these yarns can be any natural or synthetic material, preferably a synthetic monofilament, and most preferably a polyester monofilament. These bottom weft yarns may also be constructed using larger diameter yarns than the upper warp yarns.
[0098] In the embodiment shown in FIGS. 5-6 b all of the binding warp yarns form a plain weave in the top layer by weaving with five top weft yarns and bind to the bottom layer by weaving With at least one bottom weft yarns in two or more spaced apart locations. Furthermore, all of the bottom warp yarns weave only in the bottom layer. Additionally, when a binding warp yarn passes from the bottom layer to the top layer, it passes under at least two adjacent top weft yarns before weaving with a plain weave in the top layer. When a binding warp yarn passes from the top layer to the bottom layer, it passes under at least two adjacent top weft yarns before weaving with the bottom layer. The area of the plain weave (between a binding warp yarn and top weft yarns) is off-center with respect to an area or spacing between the two areas where the same binding warp yarn weaves to the bottom layer. Also, in the area or spacing between two the plain weave areas (between a binding warp yarn and top weft yarns), the area where the binding warp weaves with the bottom layer is off-center. These features are also desirable in numerous papermaking applications.
[0099] The invention encompasses a variety of different types of fabrics. For instance, the invention noted herein encompasses fabrics woven with different repeat than that pictured and described above. The fabric can have various top to bottom warp yarn ratios. The invention further contemplates other multilayer fabrics and not just the multilayer fabrics depicted in the figures.
[0100] The fabrics pictured and otherwise described and claimed herein may be employed in a variety, of applications, including board and packaging grades.
[0101] The configurations of the individual yarns utilized in the fabrics of the present invention can vary, depending upon the desired properties of the final papermakers' fabric. For example, the yarns may be multifilament yarns, monofilament yarns, twisted multifilament or monofilament yarns, spun yarns, or any combination thereof. Also, the materials comprising yarns employed in the fabric of the present invention may be those commonly used in papermakers' fabric. For example, the yarns may be formed of polypropylene, polyester, nylon, or the like. The skilled artisan should select a yarn material according to the particular application of the final fabric. Those of skill in the art will appreciate that yarns having diameters outside the herein disclosed ranges may be used in certain applications. In one embodiment of the present invention, one or more of the weft and warp yarns can have a diameter of about 0.13 mm, or about 0.17 mm, or about 0.33, or about 0.36 mm. Fabrics employing these yarn sizes may be implemented with polyester yarns or with a combination of polyester and nylon yarns.
[0102] The fabrics of the present invention have been described herein are flat woven fabrics and hence the warp yarns for these fabrics run in the machine direction (a direction aligned with the direction of travel of the papermakers' fabric on the papermaking machine) when the fabric is used on a papermaking machine and the weft yarns for these fabrics run in the cross machine direction (a direction parallel to the fabric surface and traverse to the direction of travel) when the fabric is used on a papermaking machine. However, those of skill in the art will appreciate that the fabrics of the present invention could also be woven using an endless weaving process. If such endless weaving were used, the warp yarns would run in the cross machine direction and the weft yarns would run in the machine direction when the fabric was used on a papermaking machine.
[0103] Pursuant to another aspect of the present invention, methods of making the papermaker's fabrics are provided. Pursuant to these methods, the fabrics can be woven using separate warp and weft beams.
[0104] Pursuant to another aspect of the present invention, methods of making paper are provided. Pursuant to these methods, one of the exemplary papermaker's forming fabrics described herein is provided, and paper is then made by applying paper stock to the forming fabric and by then removing moisture from the paper stock. As the details of how the paper stock is applied to the forming fabric and how moisture is removed from the paperstock is well understood by those of skill in the art, additional details regarding this aspect of the present invention will not be provided herein.
[0105] To the extent that the pattern repeat symbols shown in FIGS. 1 and 5 are inconsistent with the respective weave patterns shown in FIGS. 2 a - 2 b and 6 a - 6 b , the paths shown in FIGS. 2 a - 2 b and 6 a - 6 b shall serve as a basis for correcting the symbols shown in FIGS. 1 and 5 . Applicant also reserves the right to submit any additional drawings showing weave patterns of the type shown in FIGS. 2 a - 2 b and 6 a - 6 b for any pattern repeat shown in FIGS. 1 and 5 which are not deemed to be consistent with the weave patterns shown in FIGS. 2 a - 2 b and 6 a - 6 b.
[0106] It is noted that the: foregoing examples have been provided merely for the purpose of explanation and are in no way to be construed as limiting of the present invention. While,the present invention has been described with reference to exemplary embodiments, it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Changes may be made, within the purview of the appended claims, as presently stated and as amended, without departing from the scope and spirit of the present invention in its aspects. Although the present invention has been described herein with reference to particular means, materials and embodiments, the present invention is not intended to be limited to the particulars disclosed herein; rather, the present invention extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims. | Forming fabric that includes a top layer including top weft yarns and a bottom layer including bottom weft yarns. Binding warp yarns weave with the top weft yarns and bind to the bottom layer. This Abstract is not intended to define the invention disclosed in the specification, nor intended to limit the scope of the invention in any way. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. application Ser. No. 13/274,763, filed Oct. 17, 2011, now pending, which in turn, is a continuation-in-part of U.S. application Ser. No. 13/006,316 filed Jan. 13, 2011, now pending. Each of the aforementioned applications is incorporated herein by reference in its entirety.
BACKGROUND
[0002] The present disclosure relates to improved systems and methods for hanging or standing shelving units for a number of applications including without limitation support units for building heating, ventilation, and air conditioning (“HVAC”) systems and components, as well as suspended shelving units for holding, for example, children's games and toys, closet organizers with hangers and shelves, adjustable pipe hangers with preset means to ensure proper drainage pitch, for storage space in a garage or workshop, storage shelves over a garage door, and as a hanging unit for audio/visual equipment.
DESCRIPTION OF RELATED ART
[0003] Interior spaces of homes and other buildings are typically provided with areas for storage and storage solutions which are not adequate for the storage needed in the home or building. Hangers for mounting HVAC units, hanging pipes, and storing other items in a building are known in the prior art. More specifically, by way of example, U.S. PreGrant Publication No. 2007/0145222 to Rausch discloses a method and device for a hanging apparatus that is used to support ductwork, pipes, wiring, conduit and the like from support beams such as I-Joists.
[0004] U.S. Pat. No. 7,596,962 to Karamanos discloses, prior to installation into a HVAC system a fully-functional zone-control unit which also includes a pair of caps which seal the ends of the piping assemblies, and a pressure gauge for sensing pressurization of the piping assemblies and coil which the caps seal. A pressure gauge permits testing to insure that the piping assemblies and coil are leak free.
[0005] U.S. Pat. No. 7,261,256 to Pattie, et al. discloses a variable-duct support assembly for mounting a duct. The variable-duct support assembly includes rails having a groove which has a pair of support brackets for supporting ducts. The support brackets are coupled to one or more flexible bands for clamping the duct between the support brackets and the flexible bands.
[0006] U.S. Pat. No. 7,083,151 to Rapp discloses a laterally-reinforced duct saddle for hanging a length of horizontal flexible duct from a supporting structure. The duct saddle includes a generally flat, elongated blank adapted for bending around and receiving a portion of the flexible duct.
[0007] U.S. Pat. No. 6,866,579 to Pilger discloses a boot hanger mounting bracket assembly formed of a sturdy yet bendable material so that it can be configured and adjusted on-site. Once configured, the boot hanger mounting bracket assembly is secured to the building structure by securing a pair of boot hanger arms to the ceiling joists, wall studs or other support structure to provide a positive inexpensive way to mount the duct components.
[0008] U.S. Pat. No. 6,719,247 to Botting discloses a hanger for seating a flexible duct. The hanger has one end that can be attached to a support structure, such as a beam or joist, and a second end with a cradle for receiving a duct that can be freely seated in the cradle.
[0009] U.S. Pat. No. 5,741,030 to Moore, et al. discloses an air duct starting collar having integral clips used for installation in a planar surface of an air duct. A flange of the device permits variance in hole size, and roughness of the hole's edge.
SUMMARY
[0010] In one aspect, an apparatus is provided for a hanging shelving unit having at least one arm adapted to be attached at its top end to a steel beam, wood rafter, wood joist, wood beam, or ceiling, a bar adapted to be slidably coupled to the arm having a first horizontally extending arm located at the bottom of the bar to form a J bar, clearance openings located in the arm and in the J bar for receiving fasteners for attaching the arm to the J bar to raise or lower the first horizontally extending arm to provide for storage at different heights, a first extension member removably coupled to the first vertically displaced horizontally extending arm, and wherein the first extension member has a length that provides for storage space of different widths and is adapted to be removably attached to a first vertically displaced horizontally extending arm on an opposing J bar.
[0011] In another aspect, an apparatus is provided for a standing shelving unit having at least one leg adapted to be attached at its bottom end to a steel beam, wood rafter, wood joist, or wood beam, a bar adapted to be slidably coupled to the leg having a first horizontally extending arm located at the top of the bar to form a L bar, clearance openings located in the leg and in the L bar for receiving fasteners for attaching the leg to the L bar to raise or lower the first horizontally extending arm to provide for storage at different heights, a first extension member removably coupled to the first vertically displaced horizontally extending arm, and wherein the first extension member has a length that provides for storage space of different widths and is adapted to be removably attached to a first vertically displaced horizontally extending arm on an opposing L bar.
[0012] In yet another aspect, a method for hanging the adjustable shelving unit is provided.
[0013] In a further aspect, a method for securing the standing adjustable shelving unit is provided.
[0014] One advantage of the present development resides in the versatility of the shelving unit which provides for a variety of widths and heights to provide a hanging or standing shelving unit that can be used for a number of applications including building heating, ventilation, and air conditioning (“HVAC”) systems, a shelving unit for holding children's games and toys, as a closet organizer with hangers and shelves, for storage space in a garage or workshop, storage shelves over a garage door, and as an audio/visual equipment hanging unit.
[0015] Another advantage of the present development is the ability to easily adjust the height of the hanging or standing unit.
[0016] Still another advantage of the present development is the ability to easily add additional shelves to the unit and to adjust the height to accommodate what needs to be stored.
[0017] Other benefits and advantages of the present disclosure will become apparent to those skilled in the art upon a reading and understanding of the preferred embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The invention may take form in various components and arrangements of components, and in various steps and arrangements of steps. The drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting the invention.
[0019] FIG. 1 is a side view of the rear left and rear right hanging arms of the support unit, the front left and front right hanging arms not being shown, where the hanging arms consist of upper paddle arms attached at their upper ends to separate support members and at their lower ends to a J shaped bar having an upper horizontal extension for receiving a telescoping connecting member for supporting an HVAC unit and a telescoping lower horizontal extension for receiving a telescoping extension for supporting an emergency drain pan; and
[0020] FIG. 2 is a side view of the rear left and rear right hanging arms of the support unit, the front left and front right hanging arms not being shown, where the hanging arms consist of upper paddle arms which are turned ninety degrees and are attached at their upper ends to a common support member, and at their lower ends to “J” shaped bars having an upper horizontal extension for receiving an AC unit and a lower horizontal extension for receiving an emergency drain pan.
[0021] FIG. 3 is a front perspective view of a second embodiment support unit, having front and rear, left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member or the ceiling, and at their lower ends to “J” shaped bars having a horizontal extension for holding various items, including HVAC units, clothes, toys, games, television and audio visual equipment, and the like.
[0022] FIG. 4A is a fully retracted side view of the embodiment appearing in FIG. 3 , having rear left and rear right hanging arms of the support unit, the front left and front right hanging arms not being shown, where the hanging arms consist of an attachment section and are attached at their upper ends to a common support member, and at their lower ends to “J” shaped bars having a horizontal extension for receiving an AC unit and a drain pan support member for receiving an emergency drain pan.
[0023] FIG. 4B is a fully expanded side view of the embodiment of FIG. 4A , having rear left and rear right hanging arms of the support unit, the front left and front right hanging arms not being shown, where the hanging arms consist of an attachment section and are attached at their upper ends to a common support member, and at their lower ends to “J” shaped bars having a horizontal extension for receiving an AC unit and a drain pan support member for receiving an emergency drain pan.
[0024] FIG. 4C is a fully retracted side view of the support member appearing in FIGS. 4A and 4B .
[0025] FIG. 4D is a fully expanded side view of the support member appearing in FIGS. 4A-4C .
[0026] FIG. 5 is an exploded side view of the support unit embodiment appearing in FIGS. 3 , 4 A and 4 B.
[0027] FIG. 6 is a side view of a third embodiment support unit, having front and rear, left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member or the ceiling, and at their lower ends to “J” shaped bars having a horizontal extension for holding various items, and a plurality of the shelves and hanging bars for holding various items, including HVAC units, clothes, toys, games, and the like.
[0028] FIG. 7 is a side view of a forth embodiment support unit, having front and rear, left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member or the ceiling, at their lower ends to “J” shaped bars having a horizontal extension for holding various items such as DVD players, blue ray players, cable boxes, and the like, and an upper shelf having a horizontal extension for holding a television unit.
[0029] FIG. 8 is a side view of a fifth embodiment support unit, having front and rear, left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member, ceiling, or closet system, at their lower ends to “J” shaped bars having a horizontal extension and adjustable shelves for holding various items such as clothes, toys, games, and the like.
[0030] FIG. 9 is a front perspective view of a sixth embodiment support unit for hanging over a garage door, having front and rear, left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member or ceiling, at their lower ends to “J” shaped bars having a horizontal extension and a plurality of supports for holding various items such as tools, yard equipment, and the like.
[0031] FIG. 10A is a fully expanded front view of the support unit, having front right and front left standing legs, the rear right and rear left standing legs not being shown, where the standing legs consist of an attachment section and are attached at their lower ends to a common support member, and at their upper ends to bars at right angles having a horizontal extension.
[0032] FIG. 10B is a fully retracted front view of the support unit embodiment appearing in FIG. 10A .
[0033] FIG. 10C is a partially expanded side view of the support unit embodiment of FIGS. 10A and 10B , having front right and rear right standing legs and a right center support member, the front left and rear left standing legs and the left center support member not being shown, where the standing legs consist of an attachment section and are attached at their lower ends to a common support member, at their upper ends to bars at right angles having a horizontal extension, and center support members attached to and connecting the bars of the front right and rear right standing legs and the bars of the front left and rear left standing legs.
[0034] FIG. 10D is a fully retracted side view of the support unit embodiment appearing in FIG. 10C .
[0035] FIG. 11A is an exploded front view of the support unit embodiment appearing in FIGS. 10A-10D .
[0036] FIG. 11B is an exploded side view of the support member appearing in FIGS. 10A-10D .
[0037] FIG. 12 is an isometric view of a support unit similar to the embodiment appearing in FIGS. 10A-10D and 11 A- 11 B except the corner joint is a tee joint in this embodiment.
[0038] FIG. 13 is an enlarged exploded view of one of the lower legs in FIG. 12 with a first alternative embodiment base plate.
[0039] FIG. 14 is an enlarged exploded view of one of the lower legs in FIG. 12 with a second alternative embodiment base plate.
[0040] FIG. 15 is an isometric view of a further alternative embodiment of a support unit similar to the embodiment appearing in FIG. 12 wherein the base plates are omitted.
[0041] FIG. 16 is a front perspective view of an alternative embodiment support unit, having left and right hanging arms, where the hanging arms consist of a means of attachment at their upper ends to a support member or the ceiling, and at their lower ends to “U” shaped bar having an attachment mechanism for holding various items, including HVAC units, television and audio visual equipment, hanging storage units, pot racks, and the like.
[0042] FIG. 17 is a top plan view of yet a further stand embodiment.
[0043] FIG. 18 is side elevational view of the embodiment appearing in FIG. 17 .
[0044] FIG. 19 is an end view of the embodiment appearing in FIG. 17 .
[0045] FIG. 20 is an enlarged, fragmentary, side cross-sectional view taken along the lines 20 - 20 in FIG. 18 .
[0046] FIGS. 21A-21E illustrate the manner in which a modular system consisting of two segment lengths can be adapted for myriad HVAC configurations.
[0047] FIG. 22 is side view of an exemplary system carrying a first multi-module HVAC system.
[0048] FIG. 23 is side view of an exemplary system carrying a second multi-module HVAC system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0049] Referring to FIGS. 1 and 2 the support unit embodiment disclosed is composed of four upper arms adapted to be connected to four “J” shaped bars where each J shaped bar has an upper horizontal extension for receiving an HVAC unit and a lower horizontal extension for receiving an emergency drain pan. The upper arms and the J bars are composed of square metal tubing precut to size and fabricated to shape. The upper arms and the J bars have drilled or punched openings located on centers which are between one and two inches for adjustability. The upper arms are sized to telescope into and out of the J bars to provide for different height adjustments.
[0050] Each J bar has two horizontal arms where the upper horizontal arm is used to provide support for an HVAC unit and the lower horizontal arm is used to provide support for an emergency drain pan. Each horizontal arm is sized to telescope into a connecting sleeve and the horizontal arms and connection sleeves have openings for receiving ringed clevis pins or nuts and bolts to lock the two together. Extension members of various lengths are available which telescope into the coupling sleeves for adjusting the width between the left and right J bars to the width of the HVAC unit which is to be supported by the air handler support unit. The extension members and the coupling sleeves each have openings which are spaced apart by between one and two inches, more or less for receiving ringed clevis pins or nuts and bolts to lock the two together for different dimension applications.
[0051] The paddle arms each have at their upper ends a flat plate which is adapted to be located next to a wood support member and has openings which are provided to receive bolts or screws which are used to attach the paddle arm to a wood support member such as a wood rafter, joist or beam.
[0052] In another embodiment the flat plate at the upper ends of the paddle arms is adapted to receive at least one C clamp which is used to attach the paddle arms to steel beams.
[0053] The air handler support unit disclosed telescopes both horizontally and vertically to accommodate units having various heights and widths. The spacing between the front and rear paddle arms is varied to accommodate the length of the HVAC unit. The support unit bottom shelf may be outfitted with two “H” hangers to receive the telescoping emergency drain pan horizontal arm, which can be relocated to the upper shelf to help in removing internal parts of each unit. The entire support unit disclosed is adjustable to receive HVAC units of different heights, widths and lengths.
[0054] Referring to FIG. 1 , there is disclosed a side view of the rear left hanging arm 10 and rear right hanging arm 12 of the air handler support unit, the front left and front right hanging arms not shown, where each hanging arm consists of an upper paddle arm 14 and a “J” bar 16 at its lower end. In this embodiment each of the hanging arms, the left and right rear hanging arms and the left and right front hanging arms are similar in all aspects and, therefore, the detailed description of the rear left hanging arm which follows applies to each of the other hanging arms.
[0055] Upper paddle arm 14 is a square tube composed of steel and having a length of about twenty four inches, more or less. The top of the paddle arm 14 is welded to a flat plate 18 having a length of about eight inches, a width of about three inches and a thickness of about one-eighth of an inch, more or less. The flat plate 18 has two columns of openings 20 , (see FIG. 2 ), which are sized for receiving screws or bolts for attaching the paddle arm 14 to a wood support member such as a wood rafter, joist or beam. In the embodiment of FIG. 1 the upper paddle arms are attached to separate wood rafters, joists or rafters.
[0056] The paddle arm 14 has a first plurality of openings 24 located at spaced apart intervals (e.g., on two inch centers) which are parallel to the width of the flat plate, and a second plurality of openings 26 , (see FIG. 2 ), located at spaced apart intervals (e.g., on two inch centers) which are transverse to the width of the flat plate and are located between the first plurality of openings 24 . The paddle arm 14 which is a square tube composed of steel with an outside dimension of between one-half of an inch and one inch, more or less, telescopes into the J bar 16 . The J bar 16 is a square tube composed of steel with an inside dimension which makes a sliding fit with the outside dimension of paddle arm 14 and has a length of about twenty two and one-half inches, more or less. Located at the bottom of the J bar 16 are two horizontally extending arms 28 , 30 which are welded to the J bar 16 and are vertically displaced from each other by a distance of about five inches, more or less. Each arm 28 , 30 is a square tube with a width that is similar to the width of the tube 14 , is made of steel, has a length of about two inches, more or less, and telescopes into connecting sleeves 32 , 34 . The J bar 16 and horizontal arms 28 , 30 have clearance openings for receiving ringed Clevis pins or nuts and bolts for attaching the J bar 16 to the paddle arm 14 and the arms 28 , 30 to connecting sleeves 32 , 34 . Connecting sleeves 32 , 34 each have a length of about fourteen inches, more or less.
[0057] Referring to FIG. 2 , there is disclosed a side view of the rear left and rear right hanging arms of the support unit, the front left and front right hanging arms not shown, where the support unit of FIG. 2 differs from FIG. 1 only in that the upper paddle arms of the hanging arms are turned ninety degrees and are attached at their upper ends to a common support member rather than to separate support members such as a wood rafter, joist or beam 36 with bolts or screws.
[0058] Each J bar telescopes over and is adjustably attached to a paddle arm which allows for different height adjustments from twenty six inches to forty inches in two inch increments. Connecting sleeves 32 , 34 on opposing horizontally extending arms 32 , 34 of the J bars telescope around horizontal extension members 38 for different width adjustments of between twenty eight inches and forty inches in two inch increments.
[0059] Referring now to FIGS. 3 , 4 A- 4 B, and 5 there appears a second embodiment of the support unit 100 having four hanging arms 102 and where each hanging arm 102 consists of an upper arm 104 and a “J” bar 106 at its lower end. The upper arms 104 are a square tube composed of steel or another metal/metal alloy and the top of the upper arms 104 having a first plurality of openings 108 on the front and rear of upper arms 104 , three openings in the preferred embodiment, which are sized for receiving screws, bolts, or the like for attaching the upper arms 104 to hang the support unit 100 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like. If the first plurality of openings 108 does not align with the desired support member the upper arms 104 may be rotated ninety degrees to align with the desired support member for attachment using a screw, bolt, or the like. Alternatively, the arms 104 may have a plurality of openings 109 on the left and right of the upper arms 104 , three openings in the preferred embodiment, offset from the first plurality of openings 108 which are sized for receiving screws, bolts, or the like for attaching the upper arms 104 to hang the support unit 100 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like.
[0060] In the present embodiment, a second plurality of openings 130 of the upper arms 104 are located at spaced apart intervals (e.g., on two inch centers) on the front and rear of the square tube, and a third plurality of openings 136 , are located at spaced apart intervals (e.g., on two inch centers) on the left and right side of the square tube offset from the second plurality of openings 130 . The second and third plurality of openings 130 and 136 , respectively, are located at a desired interval for the intended use of the support unit 100 . The upper arms 104 telescope into the J bars 106 . The J bars 106 may be square tubes composed, for example, of steel or other metal or metal alloy with an inside dimension which makes a sliding fit with the outside dimension of the upper arms 104 . Located at the bottom of each J bar 106 is a horizontally extending arm 110 which may be integral with the vertical portion of the J bar bent to form the horizontally extending portion 110 of the J bar 106 . Alternatively, the horizontal arms 110 may be separately formed and attached, e.g., by welding the horizontally extending arms 110 to the bottom of the upper portion of the J bars 106 . The arms 110 may be square tubes with the same width as the width of the vertically extending portion of the J bars 106 .
[0061] The extension members 112 are telescopically received within the arms 110 . The J bars 106 and horizontal arms 110 have one or more clearance openings 114 for receiving fasteners 116 for securing the J bars and the telescopically received arms 104 and extension members 112 in fixed position. The fasteners 116 may be, for example, pins, Clevis pins, thumb screws, nuts and bolts, or the like for attaching the J bars 106 to the arms 104 and the horizontally extending arms 110 to the extension members 112 . Depending on the means used to secure the extension members 112 inside of the horizontally extending arms 110 , the extension members 112 may include a plurality of openings 132 evenly spaced apart along the member 112 . In the preferred exemplary embodiment the extension members 112 enable the support unit 100 to expand from approximately 32 inches wide to approximately 48 inches wide although other dimensions are contemplated. The extension members 112 are secured inside of the horizontally extending arms 110 via fasteners 116 which pass through the clearance openings 114 and into one of the plurality of openings 132 to secure the unit 100 at the desired width.
[0062] One or more support members 118 may optionally be attached to the horizontal arms 110 . The support members 118 are attached to the arms 110 using coupling sleeves or hooks 120 . The coupling hook 120 at a first end of the support member 118 attaches to one horizontally extending arm 110 and the coupling hook 120 at a second end of the support member 118 attaches to a parallel horizontal arm 110 . The support members 118 provide additional support for items that are being stored on the support unit 100 . The support members 118 may be square tubes composed, for example, of steel or other metal or metal alloy with a dimension to hold the weight of the item selected for supporting. The coupling hooks 120 may be welded to the ends of the support members 118 and may be made of a sheet of steel or other metal or metal alloy which is bent to create three sides which slip over the square tubes of the horizontal arms 110 . The inside dimension of the coupling hooks 120 makes a sliding fit with the outside dimension of the horizontal arms 110 .
[0063] In an alternative embodiment, the support members 118 may include two arms (not shown) where the first arms (not shown) telescope into the second arms (not shown) to increase and decrease the width between the horizontal arms 110 of the support unit 100 . The first and second arms (not shown) each having a coupling hook 120 attached at the outside end for securing to the horizontal arms 110 . The first and second arms may be square tubes composed of a metal or metal alloy (e.g., steel) with the inside dimension of the first arm making a sliding fit with the outside dimension of the second arm at their inside ends.
[0064] As best seen in FIGS. 3 , 4 A- 4 D and 5 an optional pan support 122 having a lower pan 124 and “J” bars 126 . The “J” bars 126 have hooks 128 on the upper end for securing the pan support 122 to the arms 110 of the support unit 100 and are secured at the lower end to the pan 124 . In the exemplary embodiment, the pan 124 may be used to catch water from an HVAC unit that is not working properly.
[0065] Referring now to FIG. 6 , there appears a further embodiment support unit 200 which may be used as a suspended shelving unit. The unit 200 may advantageously be used for holding children's games and toys, however, myriad of other uses are contemplated. The support unit 200 may be hung, for example, from the ceiling of a child's bedroom or playroom to provide additional storage for toys, games, stuffed animals, and the like. The support unit 200 includes four hanging arms 202 , where each hanging arm 202 consists of an upper arm 204 and a “J” bar 206 telescopically receiving the upper arm 204 at its lower end. The upper arms 204 may be a square tube and may be composed of steel or another metal or metal alloy. The top of the upper arm 204 having a first plurality of openings 208 , which are sized for receiving screws, bolts, or the like for attaching the upper arms 204 to hang the support unit 200 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like.
[0066] In the present embodiment, the first plurality of openings 208 of the upper arms 204 are located at spaced apart intervals (e.g., on two inch centers) on the front and rear of the square tube, and a second plurality of openings 209 , are located at spaced apart intervals (e.g., on two inch centers) on the left and right side of the square tube offset from the first plurality of openings 208 . The first and second plurality of openings 208 and 209 , respectively, are located at a desired interval for the intended use of the support unit 200 . The upper arms 204 telescope into the J bar 206 to raise and lower the height of the support unit 200 . The J bar 206 may be a square tube composed of a metal or metal alloy (e.g., steel) with an inside dimension which makes a sliding fit with the outside dimension of the upper arms 204 .
[0067] Located at the bottom of the J bar 206 is one horizontally extending arm 210 which may be integral with the vertical portion of the J bar and bent to form the horizontally extending portion 210 of the J bar 206 . Alternatively, the horizontal arms 210 may be separately formed and attached, e.g., by welding the horizontally extending arms 210 to the bottom of the upper portion of the J bars 206 . The arms 210 may be square tubes with the same width as the width of the vertically extending portion of the J bars 206 . One or more additional horizontally extending arms 220 are located on the vertical portion of the J bar 206 above the horizontally extending arm 210 and are welded to the J bar 206 . Each arm 220 is a square tube with a width the same as the width of the horizontally extending arm 210 . The arms 220 may alternately be attached to the J bar 206 using coupling sleeves, the coupling sleeve may slide over the vertical portion of the J bar 206 and may be secured to the J bar 206 via a fastener. The extension member 212 telescopes into the arm 210 and each of the extension members 222 telescope into the corresponding and aligned arms 220 . The J bar 206 and horizontal arms 210 and 220 have clearance openings 214 for receiving fasteners 216 for securing the J bars 206 to the arms 204 and the telescopically received extension members 212 and 222 to the arms 210 and 220 , respectively, in a fixed position. The fasteners 216 may be, for example, pins, Clevis pins, thumb screws, nuts and bolts, or the like for attaching the J bars 206 to the arms 204 and the extension members 212 and 222 to the arms 210 and 220 .
[0068] Referring now to FIG. 7 , there appears yet another embodiment support unit 300 which may advantageously be used as a hanging support unit for audio and/or video equipment, such as televisions and related audio and visual equipment. The support unit 300 includes four hanging arms 302 , where each hanging arm 302 consists of an upper arm 304 and a “J” bar 306 at its lower end. The upper arms 304 are square tubes composed of metal or metal alloy (e.g., steel). The top of the upper arm 304 has a first plurality of openings 308 , which are sized for receiving screws, bolts, or the like for attaching the upper arms 304 to hang the support unit to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like. For attachment to a finished ceiling, an attachment plate 324 may be secured to the top of each upper arm 304 . The attachment plate 324 has a plurality of openings 326 , four openings in the preferred exemplary embodiment, which are sized for receiving screws, bolts, or the like for attaching the upper arms 304 to a joist in the ceiling or anchoring the upper arms 304 into the drywall.
[0069] The upper arms 304 and horizontally extending arms 310 are of the type described above with reference to FIGS. 3-6 . The upper arms 304 are telescopically received into the J bars 306 . The J bars 306 are of the type described above with reference to FIGS. 3-6 . Located at the bottom of the J bar 306 are two horizontally extending arms 310 and 320 . The arms 310 may be integral with the vertical portion of the J bar and bent to form the horizontally extending portions 310 of the J bar 306 , while the horizontal arms 320 may be separately formed and attached, e.g., by welding the horizontally extending arms 320 to the vertical portion of the J bars 306 at a desired separation above the horizontally extending arms 310 . Alternatively, the horizontal arms 310 may be separately formed and attached, e.g., by welding the horizontally extending arms 310 to the bottom of the vertical portion of the J bars 306 . The extension members 312 and 322 are telescopically received within the arms 310 and 320 , respectively, to obtain the desired separation between opposing J bars 306 . The extension members 312 and 322 are of the type described above with reference to FIGS. 3-6 .
[0070] The shelf created by arms 310 and extension members 312 may be used to hold audio and visual equipment, such as cable boxes, DVD players, game consoles, and the like. The shelf created by arms 320 and extension members 322 may be used to suspend a television from the ceiling at a desired height rather than mounting it onto a wall or supported on a stand. Although the illustrated embodiment shows two horizontal shelves, it will be recognized that additional supports may be inserted to provide additional support for the television and audio and visual components.
[0071] Referring now to FIG. 8 , there appears another embodiment support unit 400 which may advantageously be used as a closet organizer with hangers and shelves. The support unit 400 includes four hanging arms 402 where each hanging arm 402 consists of an upper arm 404 and a “J” bar 406 at its lower end. The upper arms 404 are a square tube composed of a metal or metal alloy, such as steel. The top of the upper arm 404 having a first plurality of openings 408 , which are sized for receiving screws, bolts, or the like for attaching the upper arms 404 to hang the support unit 400 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like. For attachment to a finished ceiling, an attachment plate not shown may be secured to the top of each upper arm 404 . The attachment plates may have a plurality of openings not shown, which are sized for receiving screws, bolts, or the like for attaching the upper arms 404 to a joist in the ceiling or anchoring the upper arms 404 into the ceiling drywall.
[0072] The upper arms 404 and horizontally extending arms 410 are of the type described above with reference to FIGS. 3-7 . The upper arms 404 telescope into the J bar 406 . The J bar 406 is of the type described above with reference to FIGS. 3-7 . Located at the bottom of the J bar 406 are a plurality of horizontally extending arms, there are three horizontally extending arms in the preferred embodiment 410 , 418 , and 422 . Although the illustrated embodiment shows three horizontal arms, it will be recognized that arms may be removed or additional arms may be added to provide more or less shelves for the shelving unit 400 . The horizontally extending arm 410 may be integral with the vertical portion of the J bar and bent to form the horizontally extending portion 410 of the J bar 406 , while the arms 418 and 422 may be secured onto the J bar 406 at a desired separation above the arm 410 using coupling sleeves 420 . The coupling sleeves 420 may be secured to the J bar 406 using fasteners 416 , e.g., pins, Clevis pins, nuts and bolts, or the like. Alternatively, the arms 410 , 418 and 422 may be separately formed and attached, e.g. via welding, at fixed positions on the J bars 406 .
[0073] The extension member 412 telescopes into arm 410 and is slidably adjustable to obtain the desired separation between opposing J bars 406 . The extension member 412 is of the type described above with reference to FIGS. 3-7 . The arms 418 and 422 may come in a variety of sizes to correspond to the sizes of the arms 410 and extension member 412 . In one alternative embodiment, the arms 418 and 422 may be segmented, including an extension member in the center of the segmented arms 418 and 422 which telescopes into the arms 418 and 422 to allow for adjustment of the arms 418 and 422 in the same manner as arm 410 . In another alternative embodiment, the arms 418 and 422 may be comprised of two telescopic segments.
[0074] The shelves created by arm 410 and extension member 412 , and arms 418 , and 422 may advantageously be used as closet shelves for clothes, shoes, sheets, towels, and any other items stored in a closet and may include transversely-extending rods for clothing and other items on clothes hangers. Additional arms may be added to provide additional shelves and rods for alternative closet storages shelving arrangements.
[0075] Referring now to FIG. 9 , there appears yet another embodiment of the support unit 500 which may be used to provide storage shelves in the empty space found over a garage door. The support unit 500 may be sized to fit between the rails 524 for a garage door 526 and above the garage door 526 when it is in the open position to provide additional storage in the space above the garage door. The support unit 500 includes four hanging arms 502 and where each hanging arm 502 consists of an upper arm 504 and a “J” bar 506 at its lower end. The upper arms 504 may be a square tube composed of steel or another metal or metal alloy. The top of the upper arm 504 includes a first plurality of openings 508 , which are sized for receiving screws, bolts, or the like for attaching the upper arms 504 to hang the support unit 500 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like. For attachment to a finished ceiling, an attachment plate not shown may be secured to the top of each upper arm 504 . The attachment plate may have a plurality of openings not shown, which are sized for receiving screws, bolts, or the like for attaching the upper arms 504 to a joist in the ceiling or anchoring the upper arms 504 into the drywall.
[0076] The upper arms 504 and horizontally extending arms 510 are of the type described above with reference to FIGS. 3-8 . The upper arms 504 telescope into the J bar 506 and are secured using fasteners 516 , e.g., pins, Clevis pins, nuts and bolts, or the like. The J bar 506 is of the type described above with reference to FIGS. 3-8 . The arms 510 may be integral with the vertical portion of the J bar and bent to form the horizontally extending arms 510 of the J bar 506 . Alternatively, the horizontal arms 510 may be separately formed and attached, e.g., by welding the horizontally extending arms 510 to the bottom of the vertical portion of the J bars 506 . The extension member 512 is telescopically received within the arm 510 to obtain the desired separation between opposing J bars 506 . The extension member 512 is of the type described above with reference to FIGS. 3-8 .
[0077] Additional support for items to be stored above the garage door 526 is provided by a plurality of support members 518 , in the preferred embodiment there are four additional support members. Although the illustrated embodiment shows four support members, it will be recognized that support members may be removed or added to provide the desired amount of support for items stored on the unit 500 . The support members 518 are secured onto the arms 510 at a desired separation using coupling hooks 520 . The coupling hooks 520 at the first end of the support member 518 are secured to the arms 510 at a desired point and the coupling hooks 520 at the second end of the support member 518 are secured to a parallel arm 510 the same distance from the curve of the J bar 506 . In alternative embodiments fasteners, such as pins, Clevis pins, nuts and bolts, or the like may be used to secure the support members 518 to the arms 510 . In another alternative embodiment, the support members 518 may be comprised of two telescopic segments. The support members 518 and coupling hooks 520 may be of the type described above with reference to FIGS. 3 , 4 A- 4 B, and 5 .
[0078] The shelves created by arm 510 and extension member 512 , and support members 518 are used to create additional storage in the space above an open garage door.
[0079] Referring now to FIGS. 10A-10D , 11 A- 11 B, and 12 , there appears yet another embodiment support unit 600 having four legs 602 and where each leg 602 consists of a lower leg 604 and an “L” bar 606 at its upper end. The lower legs 604 may be square tubes composed of a metal or metal alloy, such as steel. An attachment plate 608 may be secured to the bottom of each lower leg 604 , e.g., via welding. The attachment plates 608 have a plurality of openings 610 , four openings in the preferred exemplary embodiment, which are sized for receiving screws, bolts, or the like for attaching the lower legs 604 to the top of a steel or wood beam, floor joist, floor or the like 612 .
[0080] In the present embodiment, the lower legs 604 may have a plurality of openings 614 located at spaced apart intervals (e.g., on two inch centers) on the front and rear of the square tube, and a second plurality of openings 640 , are located in the preferred exemplary embodiment at spaced apart intervals (e.g., on two inch centers) on the left and right side of the square tube between the plurality of openings 614 . The plurality of openings 614 and second plurality of openings 640 may be located at any desired interval based on the intended use of the support unit 600 .
[0081] The lower legs 604 telescope into the L bars 606 . The L bars 606 are square tubes composed of metal or metal alloy with an inside dimension which makes a sliding fit with the outside dimension of the lower legs 604 . The L bars 606 have clearance openings 620 for receiving fasteners 622 , such as pins, Clevis pins, thumb screws, nuts and bolts, or the like which align with the plurality of openings 614 and 640 in the lower legs 604 for attaching the L bars 606 to the lower legs 604 . Located at the top of each L bar 606 is a horizontally extending arm 616 which is attached to the upright portion to form the L bars 606 . The L bars 606 may be formed by welding the horizontally extending arms 616 to the top of the upper portion of the L bars 606 or alternatively may be formed by bending a single length of tubing as described above. The arms 616 are square tubes with the same width as the width of the top of the L bars 606 and may be made of steel or another metal or metal alloy. The arms 616 of the front right and front left L bars 606 and the arms 616 of the rear right and rear left L bars 606 are connected using extension members 618 . The extension members 618 telescope into the horizontally extending arms 616 . The arms 616 have clearance openings 624 for receiving fasteners, such as pins, Clevis pins, thumb screws, nuts and bolts, or the like for attaching the horizontally extending arms 616 to the extension members 618 . Depending on the means used to secure the extension members 618 inside of the horizontally extending arms 616 , the extension members 618 may include a plurality of openings 638 evenly spaced apart along the extension members 618 . In the preferred exemplary embodiment the extension members 618 enable the support unit 600 to expand from approximately two feet two inches to approximately three feet two inches although other dimensions are contemplated.
[0082] One or more support members 626 may optionally be attached to the horizontal arms 616 . The support members 626 are attached using coupling hooks 630 . The coupling hooks 630 are attached at a first end of the support member 626 to a front horizontally extending arm 616 and at a second end of the support member 626 to the corresponding rear horizontally extending arm 616 . The support members 626 and coupling hooks 630 may be of the type described above with reference to FIGS. 3 , 4 A- 4 B, and 5 . The support members 626 provide additional support for the items to be stored on the support unit 600 .
[0083] The support members 626 can be a set length or extendable. If the support members 626 are to be extendable they may include a first arm 632 and a second arm 634 . The first and second arms 632 and 634 , respectively, are square tubes made of metal or metal alloy, such as steel. The first arms 632 are preferably the same width as the width of the L bars 606 . The second arms 634 are telescopically received within the first arms 632 . The first and second arms 632 and 634 may have clearance openings 636 for receiving a fastener for securing the arms 632 and 634 at a defined width, such as a pin e.g., a Clevis pin, thumb screw, nut and bolt, or the like for attaching the first arms 632 to the second arms 634 . Depending on the means used to secure the second arm 634 inside of the first arm 632 , the second arms 634 may include a plurality of openings (not shown) evenly spaced apart along the second arms 634 to provide a plurality of sizing options. In the preferred exemplary embodiment the support members 626 may expand from two feet eight inches to four feet, although other dimensions are contemplated.
[0084] When the support unit 600 is used for an HVAC system an optional pan (not shown) may be placed under the horizontally extending arms 616 and the support members 626 and/or on the top of base support structure 612 to catch any water that may be expelled if the HVAC system is not working properly.
[0085] As best seen in FIG. 13 , an alternative attachment mechanism 700 is shown. The embodiment 700 can be used as an alternative support member with any of the stand embodiments described above, including the embodiment 600 appearing in FIG. 12 , as well as the stands appearing in FIGS. 10A-D and 11 A-B, wherein the base plate is replaced with a generally oval or circular attachment foot 702 that is attached to the bottom of each lower leg 604 . The attachment feet 702 may be made of steel or other metal and include a cross member 704 secured inside a frame 706 . The frame 706 and cross member 704 may be secured, e.g. via welding. The cross member may have an attachment post 708 having at least one set of corresponding holes 710 for securing the lower leg 604 to the foot 702 via a fastener 712 , e.g., a pin, a Clevis pin, thumb screw, nut and bolt, or the like. The frame 706 may be formed of the same tubular stock material used for the L bars 606 . The cross member 704 and post 708 may be formed of a similar tubular stock material used for the L bars 606 in a smaller size to allow the lower leg 604 to fit over the post 708 thereby securing the support unit to the attachment mechanisms 700 . The embodiment of FIG. 13 is especially advantageous for use in supporting an HVAC condensing unit on a flat roof, e.g., having rubber or other flat roofing material while eliminating sharp corners, thus minimizing the likelihood that the base member will puncture or damage the roof membrane.
[0086] Another alternative embodiment 800 , also advantageous for use on a flat roof, appears in FIG. 14 . The embodiment 800 is as described above by way of reference to the embodiment 700 appearing in FIG. 13 , but wherein alternative attachment feet 802 to be secured to the bottom of each lower leg 604 are generally rectangular or square. The attachment feet 802 may be formed of a steel or other metal and have a cross member 804 secured inside a frame 806 . The frame 806 and cross member 804 may be secured, e.g. via welding. The cross member may have an attachment post 808 having at least one set of corresponding holes 810 for securing the lower leg 604 to the foot 802 via a fastener 812 , e.g., a pin, a Clevis pin, thumb screw, nut and bolt, or the like. The frame 806 may be formed of the same tubular stock material used for the L bars 606 . The cross member 804 and post 808 may be formed of a similar tubular stock material used for the L bars 606 in a smaller size to allow the lower leg 604 to fit over the post 808 thereby securing the support unit to the attachment mechanisms 800 .
[0087] As best seen in FIG. 15 , another alternative embodiment 900 of the support unit is shown. The support unit embodiment 900 is similar to the embodiment 600 appearing in FIG. 12 , but is adapted for the attachment of the lower legs 604 directly to the desired attachment surface, for example using a fastener (not shown) such as a pin, a Clevis pin, thumb screw, nut and bolt, or the like. The fastener may be received within one or more of the plurality of openings 614 and the second plurality of openings 640 and secured to the attachment surface. Alternatively, the fasteners may be omitted and the unit 900 may rest directly on the support surface.
[0088] Referring now to FIG. 16 , there appears a further embodiment support unit 950 having upper hanging arms 952 and 954 which each mate with an end of a “U” bar 956 . The hanging arm 952 mates with a first end 958 of the U-bar 956 and hanging arm 954 mates with a second end 960 of the U-bar 956 . The hanging arms 952 and 954 are square tubes composed of steel or another metal/metal alloy and having a first plurality of openings 962 on the front and rear of the hanging arms 952 and 954 , which are sized for receiving screws, bolts, or the like for attaching the hanging arms 952 , 954 to hang the support unit 950 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like at a first end and to secure the hanging arms 952 and 954 to the U-bar 956 at a second end. If the first plurality of openings 962 does not align with the desired support member the hanging arms 952 and 954 may be rotated ninety degrees to align with the desired support member for attachment using a screw, bolt, or the like. Alternatively, the arms 952 and 954 may have a second plurality of openings 964 , as shown in FIG. 16 , offset from the first plurality of openings 962 which are sized for receiving screws, bolts, or the like for attaching the hanging arms 952 and 954 to hang the support unit 950 to a steel beam, wood rafter, wood joist, wood beam, ceiling, or the like and to secure the hanging arms 952 and 954 to the U-bar 956 at a second end. The hanging arms 952 are secured to the U-bar 956 via fasteners 970 , for example, pins, Clevis pins, thumb screws, nuts and bolts, or the like.
[0089] In the present embodiment, the first plurality of openings 962 are located at spaced apart intervals (e.g., on two inch centers) on the front and rear of the square tube, and the second plurality of openings 964 , are located at spaced apart intervals (e.g., on two inch centers on the left and right side of the square tube offset from the first plurality of openings 962 . The first and second plurality of openings 962 and 964 , respectively, are located at a desired interval for the intended use of the support unit 950 . The hanging arms 952 and 954 telescope into the U-bar 956 . The U-bar 956 may be a square tube bent into a U shape and composed, for example, of steel or other metal or metal alloy with an inside dimension which makes a sliding fit with the outside dimension of the hanging arms 952 and 954 .
[0090] Located at the bottom of the U-bar 956 is an attachment opening 966 for attaching a rotating support member 968 , such as a fastener, bracket, or the like, for securing a HVAC unit, television and audio visual equipment, hanging storage units, pot racks, and the like to the support unit 950 . The rotating support member 968 is secured to the U-bar 956 via a fastener 972 , for example, pins, Clevis pins, thumb screws, nuts and bolts, or the like, which enables the support member 968 to rotate 360 degrees about the fastener 972 .
[0091] Referring now to FIGS. 17-19 , a further exemplary stand embodiment 1000 herein is illustrated. The stand appearing in FIGS. 17-19 is adapted for HVAC systems that need to be elevated above the ground or roof, and particularly modular HVAC system such as the CITY MULTI® HVAC systems available from Mitsubishi Electric, although it will be recognized that the present system could be adapted for other HVAC systems that are similar in terms of physical size, design, and function, including other variable refrigerant flow (VRF) units from other manufacturers including Carrier, Trane, Toshiba, Daikin, Fujitsu, LG, Panasonic, and others. Likewise, it will be recognized that all dimensions appearing in the drawings are exemplary and explanatory only and are not intended to be limitative of the present invention.
[0092] The stand includes a plurality of leg members 1002 axially spaced apart. Each leg member 1002 is generally an inverted U-shape and includes first and second generally vertical legs 1004 and a generally horizontal cross beam 1006 extending transversely therebetween.
[0093] The horizontal beam 1006 includes a first set of transversely spaced apart pegs 1008 (two in the embodiment shown) secured to the beam 1006 . The pegs 1008 may be welded to the horizontal beam 1006 . The first set of pegs 1008 extend in one axial direction. A second set of pegs 1008 aligned with the first set of pegs 1008 extend on the opposite axial direction. The second set of pegs 1008 may be omitted for leg members forming the terminus of the stand.
[0094] The leg members 1002 may be formed of tubular steel, e.g., 1.5 inch×1.5 inch 11 gauge steel bar. Each vertical leg 1004 includes an associated foot 1010 comprising a plate 1012 and a horizontal post 1014 . The plates 1012 may have a relatively large surface area to distribute the weight of an HVAC system supported on the stand. For example, the plates 1012 may be 12 inch×12 inch steel plates, although other sizes are contemplated. The plates 1012 have openings 1014 adapted to receive fasteners to secure the foot 1010 to a surface 1016 . The surface 1016 may be a concrete pad. Other surfaces are also contemplated, such as building roofs and others. The fasteners may be, for example, ½ inch bolts embedded in the surface and extending through the openings 1014 in the plate to allow the plate 1012 to be bolted to the surface.
[0095] The upstanding post 1014 is telescopically received in the bottom of the vertical leg 1004 . The post 1014 is secured with one or more threaded fasteners 1018 passing through aligned openings in the post 1014 and the vertical leg portion 1004 to secure the post 1014 and the leg 1004 in fixed position. In alternative embodiments (not shown), the plates 1012 are secured to the lower end of the vertical legs 1004 via welding. In still further alternative embodiments, the post 1014 and the vertical leg 1004 may be telescopically secured at a plurality of positions to provide a height adjustable stand in the manner described above.
[0096] Two transversely spaced apart cross rails 1020 b , 1020 a , and 1020 a 1 , and designated herein generally as 1020 , extend between each adjacent pair of leg members 1002 . Each cross rail rests on a corresponding pair of transversely aligned pegs 1008 . The cross rails 1020 may have an inverted U-shaped cross-section, and more preferably are formed of a hat channel having a generally hat shaped cross-sectional shape comprising an inverted U shaped portion 1022 defining a channel for receiving the pegs and outward extending axial flanges or fins 1024 . The cross rails 1020 may be of a roll-formed steel construction. Fasteners 1026 extend through openings 1028 in the cross rails 1020 and openings 1030 in the pegs 1008 to secure the cross rails 1020 to the horizontal beam portions 1006 of the leg members 1002 . Each cross rail 1020 may have one or more openings 1032 in the upper surface to receive mounting bolts or other fastening hardware to secure the HVAC system to the stand.
[0097] As noted above, the stand herein can be advantageously used with modular HVAC systems, e.g., HVAC systems of the type having HVAC modules of different heating or cooling capacities that can be used individually, or, can be used in combination to create an HVAC system with increased capacity. The present system is especially advantageous for use with the Mitsubishi CITY MULTI® HVAC systems which comprise modular HVAC units which can be readily combined in the field to create larger capacity systems. By way of example only, the CITY MULTI® product line includes the following 11 heat pump models shown in Table 1, including 4 modular units that can be used individually as well as at least 7 systems which combine the modular components to create larger capacity systems:
[0000] TABLE 1 Cooling Capacity Model (BTU/hour) Component Models PURY-P72YKMU-A (-BS) 69,000 — — PURY-P96YKMU-A (-BS) 92,000 — — PURY-P120YKMU-A (-BS) 114,000 — — PURY-P144YKMU-A (-BS) 137,000 — — PURY-P144YSKMU-A (-BS) 137,000 PURY-P72YKMU-A(-BS) PURY-P72YKMU-A(-BS) PURY-P168YSKMU-A (-BS) 161,000 PURY-P96YKMU-A(-BS) PURY-P72YKMU-A(-BS) PURY-P192YSKMU-A (-BS) 183,000 PURY-P96YKMU-A(-BS) PURY-P96YKMU-A(-BS) PURY-P216YSKMU-A (-BS) 206,000 PURY-P120YKMU-A(-BS) PURY-P96YKMU-A(-BS) PURY-P240YSKMU-A (-BS) 228,000 PURY-P120YKMU-A(-BS) PURY-P120YKMU-A(-BS) PURY-P264YSKMU-A (-BS) 251,000 PURY-P144YKMU-A(-BS) PURY-P120YKMU-A(-BS) PURY-P288YSKMU-A (-BS) 274,000 PURY-P144YKMU-A(-BS) PURY-P144YKMU-A(-BS)
In especially preferred embodiments, a modular system can be provided, wherein stand segments having cross rails with a first length “B” and stand segments having a second length “A” can be combined in various combinations to produce stands adapted to accommodate HVAC systems of various capacities. A third cross rail length “A 1 ” (see FIGS. 17 and 18 ) may also be provided to provide still further expanded capacity. By providing two or more standard cross rail lengths which can be combined in multiple combinations, the system can be tailored to a wide variety of HVAC systems while reducing manufacturing costs as compared to custom or dedicated stands.
[0098] For example, in the illustrated preferred embodiment adapted for the CITI MULTI® HVAC systems, the cross rail length B may be selected to produce a stand segment having an axial length of about 71⅝ inches on center and the cross rail length A may be selected to produce a stand segment having an axial length of about 50¾ inches on center. The third cross rail length A 1 may be selected to product a stand segment having an axial length of about 38 15/16 inches on center.
[0099] As shown in FIGS. 21A-21E , using only cross rail lengths A and B, the 5 combinations shown in FIGS. 21A-21E can be produced which can accommodate all 11 models shown in Table 1, while also providing an appropriate spacing between adjacent modules. For example, the stand 1000 a comprising one segment having cross rails 1020 a of length A appearing in FIG. 21A will accommodate the models PURY-P72YKMU-A (-BS) and PURY-P96YKMU-A (-BS). The stand 1000 b comprising one segment having cross rails 1020 b of length B appearing in FIG. 21B will accommodate the models PURY-P120YKMU-A (-BS) and PURY-P144YKMU-A (-BS). The stand 1000 c comprising two stand segments, each having cross rails 1020 a of length A appearing in FIG. 21C will accommodate the models PURY-P144YSKMU-A (-BS), PURY-P168YSKMU-A (-BS) and PURY-P192Y SKMU-A (-BS). The stand 1000 d comprising one stand segment having cross rails 1020 a of length A and one segment having cross rails 1020 b of length B appearing in FIG. 21D will accommodate the model PURY-P216YSKMU-A (-BS). The stand 1000 e comprising two segments having cross rails 1020 b of length B appearing in FIG. 21E will accommodate the models PURY-P240YSKMU-A (-BS), PURY-P264YSKMU-A (-BS), and PURY-P288YSKMU-A (-BS). Still further configurations are possible with systems employing three or more cross rail lengths.
[0100] The cross rail lengths are also selected to provide an adequate spacing between adjacent modules in multi-unit systems. For example, as shown in FIG. 22 , there appears the stand 1000 c of FIG. 21C , comprising two segments having cross rails 1020 a of length A. The stand 1000 c is shown with an HVAC system 1040 , which is a CITY MULTI® model PURY-P192YSKMU-A comprising two PURY-P96YKMU-A modules 1042 twinned together. A space 1044 is provided between the adjacent modules 1042 .
[0101] As shown in FIG. 23 , the stand 1000 e of FIG. 21E , comprising two segments having cross rails 1020 b of length B. The stand 1000 e is shown with an HVAC system 1050 , which is a CITI MULTI® model PURY-P288YSKMU-A comprising two PURY-P144YKMU-A modules 1052 twinned together. A space 1054 is provided between the adjacent modules 1052 . It will be recognized that the present development could be adapted for use with other CITY MULTI® models, as well as other modular HVAC systems from other manufacturers.
[0102] The invention has been described with reference to the preferred embodiments. Modifications and alterations will occur to others upon a reading and understanding of the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. | The present disclosure relates to shelving systems and methods that are adaptable to a number of applications, including building heating, ventilation, and air conditioning (“HVAC”) systems, shelving units for holding children's games and toys, closet organizers with hangers and shelves, storage systems in a garage or workshop, storage shelves over a garage door, and as a shelving unit for audio and visual equipment. The shelving unit includes a means for attachment to an overhead member, such as a steel beam, wood rafter, wood joist, wood beam, or ceiling, a generally J or L shaped bar, the ability to raise or lower the J or L shaped bar to provide for storage at different heights, an extension member removably coupled to the J or L bar, and wherein the extension member has a length that provides for storage space of different widths. In another aspect, an inverted shelving stand is provided. In still a further aspect, a U shaped swiveling hanging unit is provided. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a division of application Ser. No. 09/055,089, filed Apr. 3, 1998, now U.S. Pat. No. 5,957,312, which is a continuation-in-part of application, Ser. No. 08/808,682, filed Feb. 28, 1997, now U.S. Pat. No. 5,810,184, which is a continuation of application Ser. No. 08/380,832, filed Jan. 30, 1995, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a new and improved fitment having a removable membrane which closes off the interior of the fitment spout. More particularly, the invention relates to a fitment which fits around a hole in a panel of a carton or other container, used for packaging liquids and powders.
2. Description of Related Art
Fitments having membranes are shown in such patents as U.S. Pat. No. 5,303,838, issued Apr. 19, 1994, and particularly FIGS. 14-16 thereof. Other patents showing membranes are U.S. Pat. No. 3,458,080, issued Jul. 29, 1969, U.S. Pat. No. 4,380,303, issued Apr. 19, 1983, and others. The present invention is an improvement on the prior art in that in some modifications of the invention the membrane is located approximately midway of the height of the spout.
Other fitments are moved from a chute or other source to the interior of a carton by a spud which is attached to the fitment by vacuum. The present invention eliminates the use of vacuum and the mechanical problems inherent therein.
SUMMARY OF THE INVENTION
The fitment of the present invention comprises a spout portion having a peripheral flange which may be welded or otherwise attached to a panel of a paperboard carton or to a flexible plastic container. A spout projects upward from the flange and, in the preferred embodiments, is externally threaded adjacent its upper end. In some modifications of the invention, positioned within the spout is an internal membrane which may be concave and is joined to an inward projection of the spout along a line of weakness. A pull tab, such as a ring, is connected to the membrane in such fashion that by pulling the pull tab the membrane is detached from the inward projection of the spout. The concave membrane facilitates the consumer gripping the ring and has certain advantages in molding the part.
The cap of the present invention has a skirt which is internally threaded to engage the threads of the spout. A lower portion of the cap may have a tear band having a bead which snaps under a shoulder on the lower portion of the spout. The tear band may be connected to the upper portion of the skirt by frangible means so that the cap may not be removed without giving external evidence of tampering.
One of the features of the invention is the fact that the cap may be attached to the spout by pressing the cap downward relative to the spout, the mating threads on the spout and cap skirt slipping past each other and then interengaging. The tamper-evident band has a bead which engages a shoulder on the spout so that the cap cannot be unscrewed without severing the bridges which connect the band to the skirt and giving evidence of tampering.
The tear band not only provides tamper-evidencing in addition to the membrane being intact, it also is an anti-back-off feature to keep the cap from unscrewing during initial distribution.
A particular object and advantage of the present invention is that the fitment is so constructed that, by means of a spud of a mandrel, it may be moved from a chute of other storage location to the carton. In preferred embodiments the mandrel is moved to place the fitment inside the carton and maneuvered so that the spout fits through and extends outside a hole in a wall of the carton. In the prior art, the fitment has been held on the spud by vacuum. This method is undesirable in that a source of vacuum must be provided and, further, drawing the vacuum to a sufficient extent to hold the fitment on the stud is time consuming, as is release of the vacuum.
One means for attachment to the spud is to locate the membrane which seals the spout above the lower end of the spout a sufficient distance for the spud to enter the lower end of the fitment. One means for holding the fitment on the spud is to provide an internal bead near the bottom of the spout which frictionally engages the spud. In a modification of the present invention, such a bead is intermittent rather than continuous. In another version of the invention, vertical internal ribs are formed on the lower end of the spout to grip the spud.
In another modification of the invention, the membrane, if desired, may be positioned at or adjacent the lower end of the spout. A ring depending from fitment engages the exterior of the spud. Optionally, instead of a continuous ring, fingers may project below the flange engaging the exterior of the spud. Such fingers may be rectangular in cross section or hooked. In a further modification, the ring or fingers may engage a groove formed in the spud.
Another optional feature of the invention is to form the connector or post between the pull tab and the membrane of a resilient material and make it longer than the distance between the membrane and the upper end of the spout. With a cap applied to the spout, the pull tab bears against the underside of the top of the cap. When the cap is removed, the post straightens so that the pull tab pops above the upper edge of the spout, where it may be conveniently gripped by the consumer.
In a still further modification of the invention, a curvilinear tear line is formed on the membrane either on the top or bottom surface thereof which intersects the line of weakness between the membrane and the interior of the spout. The post connecting the membrane to the pull tab is preferably located at the intersection of the curvilinear line and the line of weakness. By pulling the pull tab, the membrane tears at the curvilinear line and also tears at the line of weakness, faciliating removal of the membrane.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention:
FIG. 1 is a vertical sectional view through the cap and one form of spout in assembled condition.
FIG. 2 is a side elevational view of the spout of FIG. 1.
FIG. 3 is a top plan view of the spout of FIG. 1.
FIG. 4 is a vertical sectional view tat substantially along the line 4--4 of FIG. 3.
FIG. 5 is a schematic view showing how the fitment may be temporarily attached to the spud of an anvil of a machine for inserting the fitment into a panel of a carton.
FIG. 6 is a view similar to FIG. 4 showing a modification.
FIG. 6A is an enlarged fragmentary perspective view of a portion of FIG. 6.
FIG. 7 is a bottom plan view of the structure of FIG. 6.
FIG. 8 is a view similar to FIG. 4 of a further modification.
FIG. 9 is a bottom plan view of the structure of FIG. 8.
FIG. 10 is a view similar to FIG. 1 of a further modification.
FIG. 11 illustrates the structure of FIG. 10 with the cap removed.
FIG. 12 is a bottom plan view of the structure of FIG. 10.
FIG. 13 is a view similar to FIG. 1 of another modification.
FIG. 14 is a bottom plan view of the modification of FIG. 13.
FIG. 15 is a fragmentary view showing a further modification of FIG. 13.
FIG. 16 is a fragmentary sectional view of a spud used with the modifications of, for example, FIGS. 13 and 17.
FIG. 17 is a view similar to FIG. 13 of a modification.
FIG. 18 is a bottom plan view of the modification of FIG. 17.
FIG. 19 is a view similar to FIG. 13 of a still further modification.
FIG. 19A is a sectional view of a modified structure taken substantially along the line 19A--19A of FIG. 19.
FIG. 19B is a section view of the structure of FIG. 19A taken substantially along line 19B--19B of FIG. 19A.
FIG. 19C is a bottom plan view of a further modification of a portion of the structure of FIG. 8.
FIG. 20 is a view similar to FIG. 5 of another modification.
FIG. 21 is a view similar FIG. 5 of still another modification.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. While the invention will be described in conjunction with the preferred embodiments, it will be understood that they are not intended to limit the invention to those embodiments. On the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims.
One environment in which the present invention may be employed is by attachment to a carton panel 11 having a hole 12 therein. Fitment 16 is provided with a flange 17 which is welded or otherwise attached to the underside of panel 11 surrounding hole 12. Projecting up from the inner edge of flange 17 there may be a step 18 having an outside dimension to fit within the hole 12 and having a height approximately equal to the thickness of panel 11. Above step 18, the fitment has an inward extending portion 19. Extending upward from the inner edge of portion 19 is lower spout stretch 21 and thereabove is an upward-inward extending slanted stretch 22 which merges into a vertically extending upper stretch 23 terminating in a top edge 24. The inner and outer surfaces of the spout may be termed the "inner wall surface" and "outer wall surface", respectively.
Formed on the inside of the lower portion of lower spout stretch 21 is an inward-downward slanted bead 26 having a purpose which hereinafter appears.
An external shoulder 27 is formed at the juncture of lower spout stretch 21 and slanted stretch 22 for the purpose of attachment to the tamper-evidencing band of the cap as hereinafter explained. On the interior of the spout at approximately the juncture of the slanted stretch 22 and the upper stretch 23 is an inward projection 29 having an upper inner corner 31. The underside of p-ion 29 and its juncture with lower spout stretch 21 is a curved surface 30 which faciltates dispersing the contents of the container. Projection 29 is positioned upward from the bottom of the spout. On the exterior of upper spout stretch 23 are external threads 28, here shown as eight in number, of an arcuate length of approximately 270°.
Above and inward of corner 31 is membrane 32 molded integrally with the fitment 16. The central portion of membrane 32 may be concave as shown by reference numeral 33. The lower outer edge 34 of membrane 32 joins the upper inner corner 31 of projection 29 and the connection therebetween is thin and constitutes a line of weakness or tear line 36. At one portion of member 32 is an upward connection or post 37 reinforced by thin vertical gusset 38 and connected to horizontal pull ring 39 which is located below the level of top edge 24. When the user grips ring 39 and pulls upward, the tear line 36 breaks and the membrane 32 may be removed.
Cap 46 used with fitment 16 has a top 47 from which depends an upper skirt 48 joined to top 47 by a downwardly rounded corner 49. On the exterior of upper skirt 48 are vertical ribs 51 which assist the user in unscrewing the cap from the fitment. Upper skirt 48 is provided with internal threads 52 mating with the external threads 28 of fitment 16. The shape of the threads is such that when the cap 46 is pressed vertically downwardly on fitment 16, the threads 52 slip over threads 28 and interengage.
In the form of the invention shown in FIG. 1, a hollow plug 53 is formed on the underside of top 57, the lower outer corner thereof having a curved edge 54 which engages the inside of upper fitment 23 in a liquid tight seal.
Optionally, a tamper-evident band 56 is integrally attached to the bottom of upper skirt 48 by means of 8 angularly-spaced frangible bridge connections 61, it being understood that the number and placement of such connections is subject to variation. Band 56 is provided with an internal bead 57 which snaps under shoulder 27 when the cap is applied to the fitment. To facilitate engagement of shoulder 27, an internal groove 58 is formed in band 56 immediately above internal bead 57.
Directing attention to FIG. 5, automatic equipment for welding the fitment flange 17 to the underside of peel 11 is known in the art. In one form of such equipment an anvil or mandrel 71 has a flange 72 to which is attached a spud 73 which picks the fitment off of a chute (not shown) by fitting inside the lower spout stretch 21. The lowest portion of the concave area 33 of membrane 32 is above the upper edge of spud 73. In the form of the invention shown in FIG. 5, spud 73 has an external diameter such that when it is inserted through the lower end of the fitment 16 the inner bead 26 frictionally engages the exterior of spud 73. The spud is formed with a concavity 74 so as not to conflict with the concavity 33 of membrane 32. Holes 76 in spud 73 relieve any vacuum which might tend to impede release of fitment 16 from spud 73 when the fitment has been positioned in the carton panel 11, as shown in FIG. 1.
As shown in FIGS. 6 and 7, inner bead 26 need not be continuous. Bead 26a is interrupted, there being gaps 81 between segments 82. The number and placement of gaps 81 is subject to variation. The structure shown makes the bead 26a more flexible when engaging spud 76. Further the gaps 81 make it possible to pour out the contents of the carton more completely. As shown in FIG. 6A the upper surfaces of segments 82 slope downward-inward to facilitate engagement with spud 73.
FIGS. 8 and 9 illustrate a construction wherein the bead 26 is eliminated. Vertical internal ribs 84 are formed extending upward from adjacent the bottom edge of lower spout stretch 21b. Such ribs 84 engage the exterior of spud 73 to detachably secure the fitment 16b on the anvil 71. The number, width, thickness, and length of ribs 84 is subject to variation. Preferably the lower ends of ribs 84 are formed with downward-outward beveled surfaces 85 to facilitate the ribs 84 slipping over the spud.
FIGS. 10 and 11 illustrate a still further modification. The connector or post 37c is elongated and resilient. Pull tab 39c bears against the underside of top 47c of cap 46c. As shown in FIG. 11, when the cap 46c is removed, post 37c straightens and tab 39c assumes a position above the top edge 24c of the upper stretch 23c of the spout. Accordingly, tab 39c is more easily gripped by the consumer.
The modification of FIG. 12 is shown applied to the modification of FIGS. 10 and 11. However, it could be incorporated in any of the other modification. FIG. 12 shows a modified membrane 32c having a curvilinear groove 86 formed on the upper surface or the underneath surface thereof. The post or connector 37c connects tab 39c to the membrane 32c adjacent the intersection of groove 86 with the tearline or line of weakness 36c. The groove 86 is similar to the groove denominated "51" in U.S. Pat. No. 5,303,834, FIGS. 9-17.
Directing attention to FIG. 13, it will be seen that the membrane 32e may be located at the bottom edge of lower spout stretch 21e or at any desired location above said bottom edge. Attachment to spud 73 of anvil 71 shown in FIG. 16 is accomplished by means of downward extending fingers 91 on the lower surface or of inward extending portion 19e. The fingers 91 fit into groove 92 in spud 73e to detachably secure the fitment 16e thereon. Step 96 of spud 73e accommodates flange 17e being lower than portion 19e. The number of fingers 91, spacing between and length thereof is subject to variation. It will be understood that fingers 91 might be formed on flange 17e. It is desirable that fingers 91 be used, rather than a continuous ring in order to facilitate dispensing all the contents of the container.
FIG. 15 illustrates that in cross section the fingers 91f may be hooked.
FIG. 17-18 illustrate a modification of FIGS. 13-14 where the fingers 91 are replaced by a ring 93 which fits into the groove 92 of spud 73e of FIG. 16. Although shown as continuous, ring 93 may be formed with an opening (not shown) to facilitate complete dispensing of the contents of the container.
FIG. 19 is a view similar to FIG. 17 in which ring 93h depends from membrane 32h. It will be understood that the groove (not shown) in the spud (not shown) which engages ring 93h is suitably positioned and dimensioned for such purpose. It will further understood that the position of membrane 32h relative to the height of spout stretch 21h is also subject to variation.
The ring 93h shown in FIG. 19 may be modified, as shown in FIGS. 19A and 19B by forming hooks 111 on its lower end, thereby resembling the hooked ring shown in FIG. 6A. Further, the ring 93m shown in FIG. 19C may also be interrupted by forming segments 112 therein separated by gaps 113.
FIG. 20 shows a stud 97 depending from membrane 32j. Stud 97 is received in bore 98 formed in boss 99 in the upper surface of spud 73j or of a mandrel. Stud 97 frictionally engages bore 98 as the fitment is transported from a chute or other source to the carton.
FIG. 21 illustrates a reinforcing ring 101 on or near the periphery of flange 17k which depends below flange 17k. Preferably openings 102 are formed at one or more locations around ring 101 to facilitate dispensing all the contents of the container. Spud 73k may be modified to engage ring 101. Thus an outer ring 106 of greater inside diameter than the outside diameter of ring 101 and preferably formed with an internal upward-outward taper 107 projects above spud 73k and engages the outside of ring 106. Inner ring 104 having an outside diameter less than that of the inside diameter of ring 101 also projects above spud or mandrel 73k. Groove 96 between rings 103 and 104 frictionally engages ring 101.
In other respects, the modifications of FIGS. 6-7, 8-9, 10-12, 13-14, 15, 17-18, 19, 19A-19B, 19C, 20, & 21 resemble those of the preceding modifications and the same reference numerals followed by the subscripts a, b, c, e, f, g, h, k, m, j, and k respectively indicate corresponding parts.
For purpose of convenience, as used in the accompanying claims, "upper", "lower", "upward", "downward", "above", and "below" refer to the position of the fitment shown in the accompanying drawings. It will be understood that during manufacture, attachment and use, the parts may be positioned in other orientations.
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents. | A fitment for use as a pour spout for a paper carton or flexible bag for liquids and powders has a flange which may be welded around a hole in the carton or bag. A spout projecting outward from the flange is provided with a removable membrane integral with the interior of the spout. Preferably the membrane is concave. A horizontally disposed pull ring is attached to the membrane by a connector so that pulling the ring removes the membrane by fracturing the tear line at the juncture of the outer edge of the membrane and the projection. A cap snaps over the spout and may be removed by unscrewing the complementary threads on cap and spout. Optionally, a tamper-evidencing band frangibly connected to the lower edge of the cap skirt engages the exterior of the spout so that the cap cannot be removed without breaking the frangible connection. Various means for detachably securing the fitment to a spud during delivery of the fitment from a chute to the interior of a carton are disclosed. | 1 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to supercharger bypass valves and in particular to an external spring used to alter closing of the supercharger bypass valve.
[0002] Power production of an internal combustion engine is ultimately limited by the amount of air introduced into each engine cylinder. Fuel systems can at best provide an optimal amount of fuel to burn with the air contained in the cylinder, and adding more fuel than required for a stoichiometric air-fuel ratio does not result in more energy being produced. The power production of non-supercharged engines is thus limited by the engine's ability to draw air into each cylinder, referred to the Volumetric Efficiency (VE) of the engine, where 100 percent VE is equivalent to complete filling of the cylinder at bottom dead center at one atmosphere of pressure. While some engines achieve greater than 100 percent VE using tuned intake manifolds, the effects are generally limited to a small RPM range which the intake is tuned to.
[0003] Power production may also be realized by raising the RPM that an engine is operated at, thereby pumping more air through the engine. Unfortunately, high RPM operation requires cam lobe designs which are inefficient at low RPM, and is also stressful on engine parts.
[0004] An alternative method for increasing power production is to pump (or force) air into the engine. This approach is commonly called supercharging because more air is forced into each cylinder than 100 percent VE produces. For many years, supercharging was limited to special applications because of the power required to operate the supercharger (i.e., the parasitic draw of the supercharger) resulting in reduced fuel economy under all operating conditions.
[0005] One known supercharger is a screw compressor type supercharger employed to pump air into the engine at greater than atmospheric pressure to increasing horsepower. Screw compressor superchargers employ a pair of rotating screw elements within a confined cylindrical housing. The rotating screw elements draw air from a throttle body at an aft end of the housing and push the air progressing toward a forward end of the housing thereby compressing the air. The compressed air is then delivered into an intake manifold of the internal combustion engine. Providing the compressed air (commonly referred to as boost) dramatically increases engine horsepower production and allows immediate and tremendous acceleration.
[0006] However, maximum performance is not always required or desired from an engine and is only infrequently required from the engine in a street driven vehicle. The pressure boost generated by constantly running a supercharger elevates intake air temperature that causes ill effects on the engine, performance, fuel economy, and emissions. Therefore, for normal driving, it is ideal to effectively disconnect the compressor, but unfortunately, known means for selectively engaging and disengaging a supercharger are not cost effective.
[0007] As a solution to the ill effects of a constantly running supercharger, both original equipment and aftermarket supercharger systems have been developed which selectively bypass the compressed heated air flow back to the supercharger inlet during non-performance driving. Such bypassing eliminates the negative effects of the supercharger at low speeds while still providing a highly efficient method for producing significant horse power gains. Such bypassing further maintains reasonable and often provides improved fuel economy. The control of such bypassed air flow is commonly performed by a bypass valve. Unfortunately, known bypass valves work well at low boost pressures common in production cars, for example, below 6 PSI boost (or MAP of 20.7 PSIA), but not always satisfactory for high boost pressures, for example, from 6 to 20 PSI (or MAP from 20.7 PSIA to 34.7 PSIA) of modern high performance superchargers.
[0008] Further, modern vehicle engines provide significant improvements in speed, economy, and emissions through the use of computer controlled Electronic Fuel Injection (EFI) systems. The EFI systems measure engine parameters and determine how much fuel to provide to the engine for efficient operation. Known EFI systems fall into three categories Alpha N systems; Speed Density systems; and Mass Air Flow systems.
[0009] Alpha N systems tend to be simple and compute fuel requirements based on RPM and throttle position. The RPM and throttle position are provided to simple lookup tables and the fuel requirement results. Alpha N systems often work well in racing engines operated at wide open throttle, but are difficult to tune to a wide operating range.
[0010] Speed Density systems receive engine RPM, throttle position, intake manifold vacuum, and intake air temperature, and compute airflow requirements using a much larger lookup table than an Alpha N system. Some Speed Density systems also include an oxygen (O 2 ) sensor in the exhaust system to provide closed loop operation. In closed loop operation the system uses the air/fuel ratio from the O2 sensor to adapt to current conditions and adjust for engine wear. Some General Motors and most Dodge fuel injection systems use Speed Density systems.
[0011] Mass Air Flow (MAF) systems include an MAF sensor mounted in front of the throttle body which directly measures the amount (mass) of air inducted into the engine. A known MAF sensor is a hot wire sensor. Air flows over a heated wire and draws away some of the heat. The amount of current required to maintain the temperature of the wire is measured and used to determine the mass of air flowing across the wire. The mass of air flow, plus additional sensor data, is input to a map, and fuel requirements determined. The MAF systems offer good performance by directly measuring the air flow, but the required air flow sensor creates a restriction in some systems and reduces performance.
[0012] Chrysler Speed Density systems include Drive-By-Wire throttle position control and are designed to operate in a Manifold Air Pressure (MAP) range of approximately zero to 15 Pounds per Square Inch Absolute (PSIA) (where one atmosphere equals approximately 14.7 PSIA.) As a result, the software running the Chrysler Speed Density system does not lend itself to supercharged applications where MAP can exceed 15 PSIA.
[0013] More specifically, the Chrysler throttle position is controlled by software via a MAP sensor output which is translated to an airflow estimate by the Speed Density system and the airflow value is translated into a torque estimate. Under normal driving conditions, throttle position is controlled based on demand from the driver in the form of pedal position, but is also limited by a lookup table based on instantaneous torque estimates. When the driver advances the pedal position, the software limits the actual throttle position based on the lookup table. The system assumes that if the MAP sensor output reaches 14 PSIA to 15 PSIA, the airflow into the engine is at a maximum independent of throttle position, and the software no longer limits the throttle position. Under normally aspirated conditions (no boost), there is no reaction to this, because once the intake manifold absolute pressure is near or equal to one atmosphere, greater throttle position has no affect on air flow into the engine. The software thus allows throttle position to match the pedal position once one atmosphere is attained (approx 14.7 PSIA).
[0014] Unfortunately, such throttle position control produces undesirable results for supercharged (or boosted, pressures above one atmosphere) applications. Because the Chrysler software immediately allows the throttle position to match pedal position once the MAP sensor outputs reach one atmosphere, the unexpected increase in throttle position compounds the effect of boost when boost is created. In other words, there is an rapid transition from limited throttle position to unlimited throttle position (throttle position is now commanded to pedal position) as soon as the MAP sensor output increases to above one atmosphere because the Chrysler software incorrectly assumes that no boost is present.
[0015] Additionally, the bypass valve present on known superchargers rapidly closes over the same MAP range as where the throttle position is allowed to open rapidly, causing boost to increase even more rapidly. An example comparing throttle voltage (proportional to throttle position) and MAP with a standard “pre-loaded” bypass valve (STD bypass) to an throttle voltage and MAP with an improved bypass valve according to the present invention and discussed below is shown in FIG. 10 . The MAP (boost) increases rapidly as the STD bypass valve closes at just below one atmosphere MAP (i.e., just before the engine transitions from vacuum to boost) just as throttle position limits are removed. This compounded application of increased throttle position and increased boost produces an undesirable “ON/OFF” feel to the driver.
[0016] Unfortunately, the Chrysler software does not have a provision to allow for a smooth transition of throttle position control above 14.7 PSIA, so it is necessary to find another way to attenuate the instantaneous increase in power being experienced with supercharged engines. Many solutions have been tried over a period of five years, including switches on the pedal, and other, but no simple, robust, solution has been found, and Chrysler engineers have failed to provide a solution to this problem.
[0017] Further, both Ford and GM Mass Air Flow (MAF) systems using STD bypass valves in conjunction with race or high lift, high overlap cams, may cause overheating of the supercharger because the STD bypass valve closes prematurely. The STD bypass valve is almost fully closed at 10 inches Hg (i.e., Map of 9.8 PSIA). Most race or high lift, high overlap cams reduce vacuum to a maximum of 10 inches Hg or less (i.e., a MAP of 9.8 PSIA or more) during cruising even where throttle positions are very low. This vacuum level forces the STD bypass valve to remain closed during most operation, often overheating the supercharger and causing premature failure.
BRIEF SUMMARY OF THE INVENTION
[0018] The present invention addresses the above and other needs by providing a solution requiring only limited altering of the Speed Density system's throttle position control. Previous unsuccessful efforts were directed to controlling throttle position. By limiting alteration of the Speed Density system's control of the throttle position, the basic off-boost operation of the vehicle is not affected by the present invention thus allowing certification for on-road use. Unlike the previous attempts, the present invention address the problem by incorporating an improved bypass valve to shift and smooth the transition from open to closed, the goals being: 1) extend valve closing period to “soften” the transition into boost; 2) shift bypass valve closing to higher MAP to lower charge temperatures; 3) smooth the ON/OFF application of power to provide fuel savings; and 4) hold the bypass valve open at cruising speeds when a high lift/duration cam is used to prevent damage to the supercharger.
[0019] The goals of the present invention are achieved by modifying the opening of the supercharger bypass valve. While an expensive computer controlled servo mechanism might be used, a simple and robust solution was found only requiring a modification involving biasing the bypass valve to close at higher boost. One method according to the present invention is to remove the internal diaphragm spring and install a compression spring inside the diaphragm housing to bias the diaphragm membrane towards an open bypass valve position. Another method according to the present invention is to remove the internal diaphragm spring and install a torsion spring on the bypass valve arm to bias the bypass valve towards the open position. A third method according to the present invention is to remove the internal diaphragm spring and install an external tension spring biasing the bypass valve to the open position. All three methods hold the bypass valve open until boost pressure (MAP greater than one atmosphere) begins to close the bypass valve and thereby smooth the application of power. Such modifications attenuate the rapid increase in power at the onset of boost due to the Chrysler software control of the throttle position, thereby providing a more acceptable driving experience.
[0020] In accordance with one aspect of the invention, there is provided a screw compressor type supercharger including an improved supercharger bypass valve including a spring biasing the bypass valve towards an open position. The spring may be a compression spring integrated into a bypass valve diaphragm, an extension spring extending parallel to a diaphragm arm, or a torsion spring on a bypass valve butterfly shaft. The spring is selected and installed to hold the bypass valve fully open at all vacuum levels and at up to one PSI of boost (i.e., MAP of 15.7 PSIA), and then to allow the bypass to transition from the open position to the closed position over the interval from one PSI boost (i.e., MAP of 15.7 PSIA) to six PSI boost (i.e., MAP of 20.7 PSIA), and to be fully closed at above six PSI boost (i.e., above MAP of 20.7 PSIA). The resulting control of the bypass valve prevents damage to the supercharger.
[0021] In accordance with another aspect of the invention, there is provided a supercharged engine. The supercharged engine includes an intake manifold and a screw compressor type supercharger connected to the intake manifold. The screw compressor type supercharger includes a supercharger housing, a forward end of the supercharger housing, a rearward end of the supercharger housing, and a compressed air passage between the forward end and the rearward end and in fluid communication with the intake manifold. A first screw rotatably resides in the supercharger housing and a second screw rotatably resides in the supercharger housing and cooperates with the first screw to draw air into the housing through the rearward end and to pump compressed air out of the housing and into the intake manifold through the compressed air passage. A bypass passage connects the compressed air passage to the rearward end and a bypass valve controls the passage of the compressed air through the bypass passage from the compressed air passage to the rearward end. A bypass valve diaphragm has an engine vacuum port in fluid communication with intake manifold vacuum and boost (i.e., MAP), and is connected to the bypass valve for opening and closing the bypass valve. The diaphragm moves the bypass valve towards an open position for increased vacuum and towards a closed position for increased boost. A bypass valve spring biases the bypass valve towards the open position, wherein the combination of the diaphragm and the spring combine to position the bypass valve in the open position for engine MAP less than approximately 15.7 PSI and in the closed position for engine MAP greater than approximately 20.7 PSI.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0022] The above and other aspects, features and advantages of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
[0023] FIG. 1A is side view of a supercharged engine according to the present invention.
[0024] FIG. 1B is top view of the supercharged engine according to the present invention.
[0025] FIG. 2A is a side view of a screw compressor type supercharger according to the present invention.
[0026] FIG. 2B is a top view of the screw compressor type supercharger according to the present invention.
[0027] FIG. 3 is a cross-sectional view of the screw compressor type supercharger according to the present invention taken along line 3 - 3 of FIG. 2B .
[0028] FIG. 4 is a cross-sectional view of the screw compressor type supercharger according to the present invention taken along line 4 - 4 of FIG. 2B .
[0029] FIG. 5A is a prior art supercharger bypass valve in an open position.
[0030] FIG. 5B is the prior art supercharger bypass valve in a closed position.
[0031] FIG. 6A is a first supercharger bypass valve according to the present invention in an open position.
[0032] FIG. 6B is the first supercharger bypass valve according to the present invention in a closed position.
[0033] FIG. 7A is a second supercharger bypass valve according to the present invention in an open position.
[0034] FIG. 7B is the second supercharger bypass valve according to the present invention in a closed position.
[0035] FIG. 8A is a third supercharger bypass valve according to the present invention in an open position.
[0036] FIG. 8B is the third supercharger bypass valve according to the present invention in a closed position.
[0037] FIG. 9 is a plot of the position of the supercharger bypass valve according to the present invention as a function of vacuum and boost.
[0038] FIG. 10 shows throttle voltage and Manifold Absolute Pressure (MAP) for both a standard (STD) supercharger bypass valve and an improved supercharger bypass valve according to the present invention versus pedal voltage and a Chrysler Speed Density system controlled engine modified by adding a supercharger.
[0039] Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0040] 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 one or more preferred embodiments of the invention. The scope of the invention should be determined with reference to the claims.
[0041] In the following description, pressure is referred to as vacuum, boost, and PSI Absolute (PSIA) depending on the context. Where Manifold Absolute Pressure (MAP) is referenced, the value in units of pounds per square inch is, PSIA. Where vacuum in referenced, the value in inches of Hg is 2.04*(14.7 PSI minus PSIA). There boost is referenced, the value in units of pounds per square inch is (PSIA minus 14.7).
[0042] A side view of a supercharged engine 10 according to the present invention is shown in FIG. 1A and a top view of the supercharged engine 10 is shown in FIG. 1B . The supercharged engine 10 includes a screw compressor type supercharger 12 attached to an intake manifold 11 . The screw compressor type supercharger 12 compressed air received through a throttle body 16 and provides the compressed air to the supercharged engine 10 through the intake manifold 11 . The screw compressor type supercharger 12 is driven by a belt 14 connecting a crankshaft pulley to a supercharger pulley.
[0043] A side view of the screw compressor type supercharger 12 according to the present invention is shown in FIG. 2A and a top view of the screw compressor type supercharger 12 is shown in FIG. 2B . A supercharger pulley 18 is attached to the screw compressor type supercharger 12 at a forward end 12 a of the supercharger and the throttle body 16 is attached at a rearward end 12 b.
[0044] A cross-sectional view of the screw compressor type supercharger 12 taken along line 3 - 3 of FIG. 2B is shown in FIG. 3 and a cross-sectional view of the screw compressor type supercharger 12 taken along line 4 - 4 of FIG. 2B is shown in FIG. 4 . A first screw 20 and a second screw 22 are rotatably housed in a housing 13 of the screw compressor type supercharger 12 . The screws 20 and 22 are turned by the pulley 18 and draw ambient air 24 through the throttle body 16 and through the rearward end 12 b and into the screw compressor type supercharger 12 . The ambient air is compressed inside the screw compressor type supercharger 12 by the screws 20 and 22 . The compressed air 26 is pumped through compressed air passage 30 and into the intake manifold 11 . A bypass passage 29 connects the compressed air passage 30 with the rearward end 12 b of the screw compressor type supercharger 12 . During off boost operation, a bypass valve 31 is open, allowing a portion 28 of the compressed air 26 to flow back through the bypass passage 29 to the rearward end 12 b for re-circulation through the screw compressor type supercharger 12 . The bypass valve 31 opens and closes to control the re-circulation of compressed air 26 .
[0045] A prior art supercharger bypass valve is shown in an open position in FIG. 5A and in a closed position in FIG. 5B . A butterfly valve 62 is attached to a butterfly shaft 63 which is turned by a butterfly arm 60 . A diaphragm 50 a is connected to the butterfly arm 60 by a diaphragm arm 58 . A compression spring 52 resides inside the diaphragm 50 a and against a membrane 56 biasing the membrane 56 down and the butterfly 62 towards a closed position. A vacuum line 54 provides an intake manifold vacuum signal to the diaphragm 50 a and moves the butterfly 62 towards an open position for increases vacuum and towards a closed position for increased boost.
[0046] A first supercharger bypass valve according to the present invention is shown in an open position in FIG. 6A and in a closed position in FIG. 6B . A first improved diaphragm 51 a includes a compression spring 66 a inside the diaphragm housing under the diaphragm membrane 56 and biasing the butterfly valve towards an open position. The combination of intake manifold vacuum and force from the spring 66 a preferably provides a transition from open to closed bypass between a MAP of 15.7 PSIA and 20.7 PSIA. By holding the bypass valve open longer, the problems experienced with the known bypass valve described in FIGS. 5A and 5B is addressed.
[0047] A second supercharger bypass valve including a second diaphragm 51 b according to the present invention is shown in an open position in FIG. 7A and in a closed position in FIG. 7B . A tension spring 66 b is connected to the butterfly arm 60 and biases the butterfly valve 62 towards the open position. The tension spring 66 b resides approximately parallel to the diaphragm arm 58 and is sufficiently parallel to the diaphragm arm 58 to be coupled to the action of the diaphragm arm 58 on the butterfly arm 60 to act in unison with the diaphragm arm 58 to control the position of the butterfly valve 62 . The combination of intake manifold vacuum and force from the spring 66 b provides a transition from open to closed bypass between a MAP of 15.7 PSIA and 20.7 PSIA. By holding the bypass valve open longer, the problems experienced with the known bypass valve described in FIGS. 5A and 5B are addressed. A typical membrane 56 is approximately 2 inches in diameter and a suitable tension spring 66 b is a number 443 spring manufactured by Century Spring in Los Angeles, Calif. Other applications will generally require selecting different springs with appropriate mechanical characteristics.
[0048] A third supercharger bypass valve according to the present invention is shown in an open position in FIG. 8A and in a closed position in FIG. 8B . A torsion spring 66 c is connected to the butterfly arm 60 and biases the butterfly valve 62 towards the open position. The combination of intake manifold vacuum and force from the spring 66 c provides a transition from open to closed bypass a MAP of between 15.7 PSIA and 20.7 PSIA. By holding the bypass valve open longer, the problems experienced with the known bypass valve described in FIGS. 5A and 5B is addressed.
[0049] While the present invention is described above as controlling a butterfly type valve, other valves are known in the art, and controlling any type valve as described herein is intended to come within the scope of the present invention.
[0050] A plot of a preferred positioning of the supercharger bypass valve according to the present invention as a function of vacuum and boost (and alternatively of MAP) is shown in FIG. 9 . The bypass valve starts closing at P 1 and completes closing at P 2 . For typical applications, P 1 is preferably between approximately 14.7 PSIA and approximately 16.7 PSIA and P 2 is preferably between approximately 19.7 PSIA and approximately 21.7 PSIA, and more preferably P 1 is approximately 15.7 PSIA and P 2 is approximately 20.7 PSIA. The bypass valve remains closed at boost greater than P 2 . In other applications with higher boost, the bypass valve closing may be adjusted to close at higher PSIA. For example, P 2 may preferably be relative to maximum boost and is adjusted to be between one PSI and two PSI below the peak boost of the supercharger, and more preferably P 2 may be adjusted to be approximately one PSI below the peak boost of the supercharger. Adjusting the closing of the bypass valve is generally performed by using a different spring 66 a , 66 b , or 66 c or by preloading the spring 66 a , 66 b , or 66 c.
[0051] The throttle voltage and Manifold Absolute Pressure (MAP) for both a standard (STD) supercharger bypass valve and an improved supercharger bypass valve according to the present invention versus pedal voltage and a Chrysler Speed Density system controlled engine modified by adding a supercharger are shown by four plots in FIG. 10 . The throttle position and MAP resulting from a STD bypass valve show a sharp increase between pedal voltage between 2.1 and 2.5 volts, resulting in an undesirable OFF/ON driving experience. The throttle position and MAP resulting from the improved bypass valve show a smooth and more gradual increase between pedal voltage between 3.1 and 4 volts, resulting in a more acceptable driving experience.
[0052] 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 screw compressor type supercharger includes an improved supercharger bypass valve including a spring biasing the bypass valve towards an open position. The spring may be a compression spring integrated into a bypass valve diaphragm, an extension spring extending parallel to a diaphragm arm, or a torsion spring on a bypass valve butterfly shaft. The spring is selected and installed to hold the bypass valve open at all vacuum levels and at up to one PSI of boost, and then to allow the bypass to close between one PSI and six PSI boost, and to be closed at above six PSI boost. The resulting control of the bypass valve prevents damage to the supercharger. | 5 |
FIELD OF THE INVENTION
The present invention pertains to a process and a device.
BACKGROUND OF THE INVENTION
It has been known in practice that the cover films, which are stretched above and below between the pressed bale and the pressure rams, are wrapped by pins and placed on the lateral surfaces of the pressed bale after the press box has been pulled off. If desired, a belly band is placed around the bale, and the package is finally fixed by straps. The relatively inaccurate wrapping with the cover film has proved to be disadvantageous in practice, because the usually rectangular cover film, which projects beyond the base of the bale on all sides, is crumpled in the corners in an undefined manner, and it may become detached, despite strapping, when the pressed bale expands after releasing the pressure exerted by the pressure rams or later, during storage. As a result, the bale package may open, as a consequence of which the pressed bale will be exposed to environmental effects, such as soiling, rain water, etc., in an undesired manner.
SUMMARY AND OBJECTS OF THE INVENTION
It is therefore the task of the present invention to provide a process and a device for reliably and durably wrapping a cover film around a pressed bale.
According to the present invention, a defined fold is formed in the corner zones of the cover film when the cover film is placed on the lateral surfaces of the pressed bale, and this fold is subsequently folded over with a likewise defined movement, and is placed on the pressed bale or the lateral film web already placed around the bale. The entire cover film is thus wrapped around the head area of the pressed bale as a flat envelope in contact with the bale. Due to the defined shaping and end position of the fold in the corner zone, the fold cannot become loose later. The package remains tight, and the pressed bale is protected. In addition, one strapping device is sufficient. Crosswise strapping is not necessary.
The fold can be formed and folded over in the same manner with the upper as well as the lower cover film. The fold is preferably folded over toward the broad side of the pressed bale, because it is fixed directly there by the strapping, which is usually placed around the broad sides. Due to the strapping and the accurate fold formation, the upper edge of the bale, which sometimes tends to bulge out after removal of the pressure ram, is held down better as well. The fold is stretched down by a counteracting force, which is directed downward and inward, counteracts bulging out, and fixes the edge of the bale.
To secure the fold position until strapping, the fold is temporarily held by a folding finger. If the straps or other bale fixing means are placed in another manner rather than over the broad sides of the bale in the case of different packing techniques, the fold is shaped and folded over in a correspondingly different manner, so that it will ultimately be held by the final bale fixing means in the same manner.
The folds are formed by a movable folding frame, which may have different shapes and be moved in different manners. In one of the two preferred embodiments, the folding frame is designed as a rigid stripping frame with stripping openings made in one piece with it for the folds. This embodiment is particularly suitable for the lower cover film, because the stripping frame can be connected to the press box and can be pulled off. As a result, the cover film is also folded and wrapped around along with the pulling off of the box. This makes it possible to eliminate the need for a separate drive for the folding frame. However, the stripping frame can also be used to wrap around the upper cover film. In this case, it is a multiple-part that is movable in itself in order to provide place for the box pulled off and to subsequently close it again around the pressed bale for the folding function.
The second variant provides for a multipart folding frame, which consists of a plurality of rakes, which are movable around a plurality of axes and are able to perform a horizontal movement and a vertical movement in the preferred embodiment. This design is preferable for wrapping over the upper cover film, but it is also suitable for the lower cover film. The folds are formed here by the vertical lowering movement and the horizontal feeding movement of the rakes. The folding fingers for folding over the folds are parts of the rakes here and are also able to support fold formation during feeding by an additional transverse movement.
The above-mentioned distinctions between a lower cover film and an upper cover film are based on the assumption of an overhead baling press, in which the lower pressure ram is stationary, while the upper one is held and driven movably. The press box is also pulled off in the upward direction. The associations and the preferred fields of application of the folding device change correspondingly in baling presses of different design.
Both embodiments of the folding frame are suitable for different bale sizes and bale materials. The machine operators sometimes deliberately produce different bale sizes. In addition, different bale materials expand to different extents on release. The differences may reach up to 150 mm or more. In prior-art packing devices, this often leads to problems in terms of adjustment. This is not true in the case of the embodiments according to the present invention. In addition, adjustment takes place automatically. It is also advantageous that, despite the different bale sizes, the cover films will not be impaled on the rake, the pins, or the folding fingers, which would be undesirable. As a result, damage to the films or parts of the device, as well as malfunctions are avoided.
The process according to the present invention and the corresponding device are particularly suitable for use on carrousel baling presses, in which packing is performed within the baling press. As an alternative, the process and the device may also be used in other designs, e.g., with external packing stations, in which the pressed bales are moved from the press into the packing station with the pressure rams placed against them.
The process according to the present invention and the corresponding device have a low manufacturing cost and are particularly economical. It is also possible to retrofit existing baling presses or packing stations with the device according to the present invention, or existing wrapping devices can be replaced with it.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is represented as an example in the drawings and is schematically described in two exemplary embodiments. Specifically,
FIG. 1 shows a perspective view of a carrousel baling press with device for wrapping over the cover films,
FIGS. 2-4 show a perspective view of an embodiment with a rigid folding frame in three positions,
FIG. 5 shows a top view of the folding frame corresponding to the arrow V in FIG. 3,
FIGS. 6 and 7 show the second embodiment with a movable folding frame in two movement positions and in a perspective view,
FIG. 8 shows a simplified top view of the lifting drives for the folding frame according to FIGS. 6 and 7, and
FIGS. 9 and 10 show the arrangement of the lifting drives according to FIG. 8 in an enlarged and cutaway detail top view and in two positions.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a baling press (1) in the form of a carrousel baling press with two stations. In one of them, the lowered press box (5) is filled with fibrous material, tow or other flowable and pressable materials, pre-pressed if desired, and then turned into the next station. The final pressing and packing of the pressed bale (4) take place here. In the baling press shown, the lower pressure rams (3) are arranged on a yoke beam and are able to rotate in it only in the horizontal plane, but they are unable to perform lifting and lowering movements. For pressing the bale, the said upper pressure ram (2) is moved up and down by the piston rod (23) of a hydraulic drive (not shown).
After final pressing, the bale (4), which is still under pressing pressure, is packed. To do so, the said press box (5) is pulled off in the upward direction via a suitable lifting device. Before a said press box (5) is filled, a cover sheet (7) each is placed over the said lower pressure ram (3), and secured. The lower cover film will hereinafter be called the bottom film (7). The upper cover film (6), hereinafter called the head film, is placed onto the material pressed in the said press box (5) prior to the final pressing, and is carried by the said lowered upper pressure ram (2).
The said head film (6) and the said bottom film (7) are wrapped around the said pressed bale (4) in the manner described below, and they lie tightly on the said bale like a cap. A belly band or middle film, which overlaps the said cover films (6, 7) wrapped around, is subsequently placed around the said pressed bale (4). Finally, the films are fixed by a hoop-casing device (17); a single strap over the broad side (19) of the said pressed bale (4) is sufficient.
Folding devices (8), one of which is associated with the said upper pressure ram (2) and another with the said lower pressure ram (3), are used to wrap the said cover films (6, 7) around the head area and the foot area of the said pressed bale (4), respectively. Two embodiments of the said folding device (8) are represented; of these, FIGS. 2 through 5 show the variant for the said bottom film (7), and FIGS. 6 and 7 show the variant for the said head film (6). The two embodiments can be interchanged in the case of a corresponding change in design. As an alternative, it is also possible to use two identical units of only one variant.
As is illustrated in FIGS. 2 through 5, one said folding device (8) is formed of a vertically movable stripping frame (14), which is connected, in the embodiment shown, to the bottom side of the said press box (5) via suitable supports, and is raised and lowered with the press box 5. To ensure this, it the stripping frame 14 is preferably located at a closely spaced location below the lower edge of the box. As a result, the said pressed bale (4) can stretch only insignificantly at most when the box is being pulled off and the said stripping frame is moved over it. Thus, the said stripping frame fits different bale sizes and bale materials. Four folding fingers (13) also belong to the said folding device (8).
FIG. 5 illustrates a top view of the said stripping frame (14). The said stripping frame (14) has the shape of an I and surrounds the said pressed bale (4) on the side. There is a certain distance between it the said stripping frame 14 and the lateral surfaces of the said pressed bale (4) in order to provide space for the said bottom film (7). The free I-shaped inner surface of the said stripping frame (14) consists of an essentially rectangular base corresponding to the shape of the bale and of four stripping openings (15) arranged in the corner areas. These stripping openings 15 extend laterally and in the extension of the narrow sides (18) of the said pressed bale (4) in the outward direction. They have the task of forming a laterally projecting, defined fold (9) in the corners of the said bottom film (7).
During the final pressing of the said bale (4), the said stripping frame (14) is located at the level of or below the said lower pressure ram (3). FIG. 2 shows a position after completion of the pressing process, in which the said press box (5) with the said stripping frame (14) has already been raised somewhat in the direction of movement (20). The said stripping frame (14) now grips under the said bottom film (7) hanging down from the said pressure ram (3) and raises it. The said bottom film (7) now lies flatly, as shown in FIG. 2, on the lateral projections and shoulders (24) of the said frame. With the lifting movement of the said stripping frame (14), the said bottom film (7) is placed over the lateral surfaces of the said pressed bale (4), and a fold (9) each is formed in the said stripping openings (15) at the same time. FIG. 3 shows the stripping position, in which the said bottom film (7) has left the said stripping frame (14) and lies, with projecting folds (9), in contact with the said pressed bale (4).
To secure the said bottom film (7) placed over the bale 4, a plurality of height-adjustable pins (16) are arranged distributed around the said pressure ram (3). On the said two broad sides (19), the said pins (16) are positioned staggered with the strapping grooves (22) in the said pressure ram (3), which said grooves open there. The said pins (16) are also raised with the said proceeding stripping frame (14), and they press the said cover film (7), which has already been stripped out and placed over, against the said pressed bale (4).
At least on the said two broad sides (19), the said pins (16) are arranged together on a lifting bar (21), which carries, at its ends, an obliquely outwardly directed folding finger (13) each. The said pins (16) may still be missing on the narrow sides (18) of the said pressed bale (4).
As soon as the said bottom film (7) has been stripped out and placed over according to. FIG. 3, the said folding fingers (13) come into action. They are located approximately at the level of the said broad sides (19) of the said bale (4), but they are outside the said folds (9) due to their oblique position. From the position shown in FIG. 3, they pivot inward along an axis extending along the said narrow sides (18), and fold the said fold (9) associated with them onto the said broad side (19) of the said pressed bale (4). The said actually adjacent pins (16) can now act as a holder. The said fold (9), folded over, comes to lie on the said pins (16) or the film web already placed on. It is held in this position by its swung-in folding finger (13). The said bottom film (7) is placed tautly around the said pressed bale (4), and it fits tightly due to the said defined folds (9).
The said second folding device (8) according to FIGS. 6 through 9 is used to wrap around the said head film (6). The said folding frame (10) is a multisectional frame here, and is movable in itself. It consists of four rakes (11) with downwardly projecting tines (12), which are staggered, like the said pins (16), in relation to the said strapping grooves (22). The said four rakes (11) are arranged distributed over the four sides of the pressure ram, and are moved via pushing and lowering drives. For clarity's sake, FIGS. 8 through 10 show only the said pushing drives (26), which impart a horizontal movement to the said rakes (11). The movements of the rakes are symbolized by arrows.
The said pushing drives (26) with the said rakes (12) are seated in a frame (25) on the said upper pressure ram (2). The said pushing drives (26) consist of cylinders (30) and guides for the horizontal movement of the said individual rakes (12). A common drive, e.g., with a two-sided cylinder, may also be provided for said rakes (26) which are located opposite each other. In the resting position, the said rakes (11) are retracted behind the edge of the said pressure ram (2). If desired, the said pressure ram (2) may also have lateral grooves for receiving the said rakes (11). FIG. 8 shows the resting position by solid lines, and the extended position on the right-hand side by broken lines.
The said frame (25) can be moved up and down together with the said rakes (12) in relation to the said pressure ram (2) via a lowering drive, not shown. The said piston rod (23) has corresponding, longitudinally and transversely extending recesses for accommodating the said, essentially cross-shaped frame (25).
The said rakes (11) arranged on the said two narrow sides (18) additionally have, at their two ends, longitudinally movable and pivotable tines, which act as said folding fingers (13). Corresponding pushing and pivoting drives (28, 29) are arranged for this purpose on the connection yoke (27) of the said rakes (11). The said drives (28, 29) preferably consist of hydraulic or pneumatic cylinders (30, 34).
FIGS. 9 and 10 illustrate the design of the said drives (28, 29), FIG. 9 showing the retracted position, and FIG. 10 showing the extended position.
The said folding fingers (13) are arranged at one end of bent straps (32), which are mounted rotatably around the vertical axis at the other end via a pivot bearing (34) on a carriage (31). The said rod-shaped carriages (31) in turn are arranged movably next to each other via suitable guides along the said narrow side (18) of the said pressure ram (2) in the said connection yoke (27). The said cylinder (30) of the said two pushing drives (28) for the said folding fingers (13) is arranged in the said connection yoke (27) and is mounted with its housing on one of the said carriages (31) (cf. FIG. 10). The end of its piston rod is connected via a bracket to the said other carriage (31). The said cylinder (30) pushes the said carriage (31) with the said straps (33) and the said folding fingers (13) in the outward direction, and again retracts them.
The said cylinders (34) of the said pivoting drive (29) for the said folding fingers (13) are guided within the said connection yoke (27) and are arranged on the associated carriage (31). They are extended and retracted with the said carriage (31). The piston rods of the said cylinders (34)are connected to the said bent straps (33) approximately in their middle. The said cylinders (34) are able to pivot the said folding fingers (13) by 90° from their starting position on the said narrow side (18) to the said broad side (19) of the said pressed bale (4) and back.
As is illustrated in FIG. 8, one horizontal carrier (35) each, which extends along the said broad side (19) of the said pressed bale (4), is arranged at the ends of the said carriages (31). The carrier 35 is guided movably on the said connection yoke (27) along the said narrow side (18). For clarity's sake, the said carrier (35) is represented only at one of the said extended carriages (31). The said carrier (35) is so long that it is located in the path of movement of the said adjacent rake (11). In addition, the said rakes (11) extend farther out than the said folding fingers (13). During the extension movement, the said two carriages (31) with the said carriers (35) strike a stop of the said adjacent rakes (11) on both sides. During the subsequent retracting movement of the said rakes (11), the said carriers (35) and the said folding fingers (13) are carried to the said broad side (19) of the said pressed bale (4). To achieve this, the pressure of the said cylinder (30) of the said pushing drive (28) can be released, and it does not offer any resistance to the retracting movement of the said carriages (31).
After the said press box (5) has been pulled off, the said upper folding device (8) starts to function. The said press box (5) has carried the said head film (6) in the upward direction and brought it into the position according to FIG. 6. The said four rakes (11) and the said folding fingers (13) with their said carriages (31) are now extended horizontally in the outward direction, until they slightly project over the edges of the said pressure ram (2) and the said pressed bale (4), respectively. The said head film (6) is now carried, and it spontaneously folds partially downward. The said rakes (11) and the said folding fingers (13) are subsequently lowered from the extended position along the lateral surfaces of the bale, and they fold down the said head film (6).
As soon as the said rakes (11) assume the lowered position shown in FIG. 7, they are again retracted horizontally toward the said pressed bale (4), while they wrap over the said head film (6). The retracting movement of the said four rakes (11) may take place simultaneously or consecutively. A fold (9) each is formed in the corners during the vertical and horizontal movements of the said rakes (11). The fold formation is preferably supported by the extending movement of the said folding fingers (13) along the said narrow side (18) of the said pressed bale (4). Thus, the said folding fingers (13) assume a stripping function and allow the said folds (9) to project along the said narrow sides 18.
The said folding fingers (13) and their said carriages (31) are carried during the horizontal pressing movement of the said rakes (11) toward the said broad side (19) of the said pressed bale. Due to the horizontal movement and the carrying, the said complete folding device (8) is automatically adjusted to the existing bale size and to the possible expansion of the bale. The said folding fingers (13) are subsequently pivoted by 90° to the said broad side (19). They now bend over the said projecting folds (9) and fold them over onto the said broad side (19). As in the exemplary embodiment described first, the said folds (9) now lie flat on the film web already placed on, and are temporarily held by the said folding fingers (13).
As was mentioned in the introduction, after the said cover films (6, 7) have been wrapped around, the belly band or middle film is placed with an overlap over the said cover films (6, 7) and over the said pins (16), the said tines (12), and the said folding finger (13). Strapping through the said strapping grooves (22), which have been left open, is subsequently performed. When packing of the said pressed bale (4) is now completed, the said rakes (11) together with the said folding fingers (13) are raised and pulled out of the said film package. The said pins (16) with the said folding fingers (13) at the bottom are lowered correspondingly as well. The said folds (9) are now secured in their positions by at least one strap band and are no longer able to leave their contact position in an uncontrolled manner on swelling of the said pressed bale (4).
The said rakes (11) are now moved back into their retracted starting position on the said pressure ram (2), and the said folding fingers (13) are also pivoted back and retracted. They are now ready for the next folding process. The said carriers (35) find place in the edge-side recesses of the said piston rod (23).
After ejection of the said completely packed pressed bale (4), the said press box (5) is also again lowered, and the said stripping frame (14) is thus again brought into the starting position at the said lower pressure ram (3). During the subsequent pivoting movement of the said yoke beam to the filling station, the said stripping frame (14) follows the movement of the said press box (5). A new bottom film (7) can optionally be placed in the final pressing station onto the said empty pressure ram (3), and the said stripping frame (14), which is subsequently lowered, will strip the said bottom film (7) downward at the edges around the said pressure ram (3). As an alternative, the said bottom film (7) can also be introduced, with the said stripping frame (14) lowered, into the gap between the said press box (5) and the said stripping frame (14), and be placed onto the said pressure ram (3). This can be carried out optionally in the final pressing station or in the filling station. As soon as the said stripping frame (14) is located under the said bottom film (7), this said folding device (8) is also ready again for the next wrapping process.
List of Reference Numerals
1. Baling press
2. Pressure ram, upper
3. Pressure ram, lower
4. Pressed bale, bale
5. Press box
6. Cover film, top, head film
7. Cover film, bottom, bottom film
8. Folding device
9. Fold
10. Folding frame
11. Rake
12. Tine
13. Folding finger
14. Stripping frame
15. Stripping opening
16. Pins
17. Strapping device
18. Narrow side
19. Broad side
20. Direction of movement
21. Bar, lifting bar
22. Strapping groove
23. Piston rod
24. Shoulder
25. Frame
26. Pushing drive, rake
27. Connection yoke
28. Pushing drive, folding finger
29. Pivoting drive, folding finger
30. Cylinder, pushing drive
31. Carriage
32. Pivot bearing
33. Strap
34. Cylinder, pivoting drive
35. Carrier | The present invention pertains to a process and a device for wrapping a cover film (6, 7) around a pressed bale (4) on a baling press (1), wherein the cover film (5, 6) stretched between the pressure ram (2, 3) and the pressed bale (4) is placed on the lateral surfaces of the pressed bale (4). A laterally projecting fold is formed in the cover film (6, 7) in the corner areas via a folding frame (10), and this fold is subsequently folded over and placed on the pressed bale (4). The vertically movable folding frame (10) may be designed as a stripping frame (14), or it may consist of a plurality of multiaxially movable rakes (11). Figure selected: FIG. 3. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the general art of doors, and to the particular field of covers for door handles.
2. Discussion of the Related Art
Many people are reluctant to use public restrooms due to actual or perceived sanitary conditions of those restrooms. However, in some instances, such use is unavoidable.
These people try to avoid touching any surface after they have washed their hands. However, touching a surface of the restroom is nearly unavoidable because the person must touch the handle of the door to exit the restroom.
Some people carry gloves, wipes or the like to use in such public restrooms. Some people take an extra paper towel to use to cover the door handle. All of these techniques work, but are not efficient. Therefore, there is a need for a means and a method for efficiently and effectively covering a handle of a door so a person opening that door can avoid direct contact with the handle.
Covering a door handle is quite effective in preventing a person from contacting the door handle during operation of the door. However, there are times when it is also desirable to clean the door handle and disinfect the door handle. This generally requires a person to carry a liquid spray into a room, spray that liquid onto the door handle and then wipe the handle clean. This procedure requires a person to carry items with him or her for the cleaning procedure. This can be cumbersome and inefficient.
Therefore, there is a need for a means and a method for efficiently cleaning a handle of a door.
Still further, some people wonder when the last time a door handle was cleaned, and even if there is some form of protection for this person, they are uncomfortable touching the door handle. These people are not satisfied by the mere existence of some means for avoiding contact with the door handle.
Therefore, there is a need for a means and a method for efficiently cleaning a handle of a door which can be operated at any time by any user.
PRINCIPAL OBJECTS OF THE INVENTION
It is a main object of the present invention to provide a means and a method for efficiently and effectively covering a handle of a door so a person opening that door can avoid direct contact with the handle.
It is another object of the present invention to provide a means and a method for efficiently cleaning a handle of a door.
It is another object of the present invention to provide a means and a method for efficiently cleaning a handle of a door which can be operated at any time by any user.
SUMMARY OF THE INVENTION
These, and other, objects are achieved by a means and a method in which long tissues are stored in a dispenser housing superadjacent to a handle of a door. The tissues are dispensed in a known manner but are different from known tissues in that they are long enough to remain attached to the dispenser housing but to also cover a handle of a door. A spray system includes a spray nozzle on the housing and which is oriented to spray fluid from the housing onto the handle of the door.
The door handle protector of the present invention thus places tissues in position for anyone to use a tissue to grasp a door handle and thus avoid contact with the door handle. The protector also includes a spray system that the user can activate to spray cleaning fluid or disinfecting fluid onto the door handle at any time. The tissue can be used to wipe the handle dry. This will be convenient if the protector has run out of tissues. The handle can be cleaned before touching it and a degree of comfort can be obtained.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
FIG. 1 is a perspective view showing the door handle protector dispensing unit embodying the present invention.
FIG. 2 is a bottom perspective view of a portion of the housing of the device embodying the present invention.
FIG. 3 is a partially perspective view showing the device embodying the present invention including a door and a door handle which is to be protected.
FIG. 4 is a side elevational view of the device embodying the present invention with a dispensed tissue being indicated.
FIG. 5 is a front elevational view of the device embodying the present invention with a spray and a dispensed tissue being indicated.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Other objects, features and advantages of the invention will become apparent from a consideration of the following detailed description and the accompanying drawings.
Referring to the figures, it can be understood that the present invention is embodied in a door handle protector 10 . Door handle protector 10 comprises a door 12 having a handle 14 which is used to open and close the door 12 . Handle 14 has a top end 15 , a bottom end 16 , and a length dimension 17 which extends between the top end 15 of the handle 14 and the bottom end 16 of the handle 14 .
A housing 19 is mounted on the door 12 superadjacent to handle 14 of the door 12 . Housing 19 includes a front wall 20 , a rear wall 21 , a top wall 22 , a bottom wall 24 , a first side wall 26 , and a second side wall 28 . An axial dimension 30 extends between the top wall 22 and the bottom wall 24 , a width dimension 32 extends between the first side wall 26 and the second side wall 28 , and a thickness dimension 34 extends between the front wall 20 and the rear wall 21 .
An interior wall 40 extends between the top wall 22 and the bottom wall 24 in the direction of the axial dimension 30 of the housing 19 . A liquid-containing compartment 42 is defined between first side wall 26 and interior wall 40 and between top wall 22 and bottom wall 24 . A tissue-containing compartment 44 is defined between the interior wall 40 and the second side wall 28 and between the top wall 22 and the bottom wall 24 . The rear wall 20 of the housing 19 is mounted on the door 12 . A length dimension 18 is defined between the bottom wall 24 of the housing 19 and the bottom end 16 of the handle 14 .
The housing 19 is mounted on the door 12 so that a dimension 45 is defined between the bottom of the housing 19 and the bottom of the handle 14 .
A tissue-compartment cover 50 is removably mounted on the top wall 22 of the housing 19 between the interior wall 40 of the housing 19 and the second side wall 28 of the housing 19 .
A liquid-compartment cover 52 is removably mounted on the top wall 22 of the housing 19 between the interior wall 40 of the housing 19 and the first side wall 26 of the housing 19 .
As will be understood from the teaching of this disclosure, the covers 50 and 52 are removed to replenish either tissues or liquid contained in the housing 19 .
A tissue-dispensing slot 60 is defined in the bottom wall 24 of the housing 19 between the interior wall 40 of the housing 19 and the second side wall 28 of the housing 19 . Tissue-dispensing slot 60 is located superadjacent to the handle 14 of the door 12 . Tissues 62 are dispensed through slot 60 .
Tissue 62 includes a top 63 located inside compartment 44 and a bottom 64 located outside the tissue compartment 44 when the tissue 62 is in use. Tissue 62 has a length dimension 66 measured between the top 63 of the tissue 62 and the bottom 64 of the tissue 62 . Length dimension 66 is greater than length dimension 67 defined between the bottom wall 24 of the housing 19 and the bottom end 16 of the handle 14 . This length dimension 66 can be, for example more than one foot. Thus, when the tissue 62 is located outside of the housing 19 as shown in FIG. 1 with the top 63 of the tissue 62 still inside the housing 19 , the length of the tissue 62 is sufficient to cover the handle 14 from the top 15 end of the handle 14 to the bottom end 16 of the handle 14 while the tissue 62 is still attached to the housing 19 .
The length dimension 66 of the tissues 62 allows each tissue 62 to be dispensed in a known manner, but the tissue 62 will be long enough to cover the handle 14 of the door 12 . This will permit a user to operate the door 12 using the handle 14 of the door 12 by grasping the handle 14 via the tissue 62 covering the handle 14 . After opening the door 12 , the user then simply pulls the tissue 62 out of the housing 19 and discards the tissue 62 . As the tissue 62 exits the housing 19 , it pulls the next tissue 62 down out of the dispensing slot 60 far enough so that this next tissue 62 covers, or at least partially covers, the handle 14 of the door 12 and is ready for the next user. If a tissue 62 does not fully cover the handle 14 , a user can pull the tissue 62 out of the housing 19 far enough to cover the handle 14 of the door 12 while he or she is using the handle 14 to open the door 12 .
A liquid dispenser nozzle 70 is located on the bottom wall 24 of the housing 19 between the interior wall 40 of the housing 19 and the first side wall 26 of the housing 19 . The liquid dispenser nozzle 70 is a known type of nozzle and is fluidically connected to the liquid compartment 44 of the housing 19 to receive fluid therefrom. The liquid dispenser nozzle 70 is oriented to spray liquid in direction 72 . Direction 72 is in the direction of the axial dimension 30 of the housing 19 away from the bottom wall 24 of the housing 19 and in a direction away from the first wall 26 of the housing 19 toward the second wall 28 of the housing 19 and is toward the handle 14 of the door 12 when the liquid dispenser nozzle 70 is activated. This spray will impinge on the handle 14 of the door 12 .
The liquid sprayed on the handle 14 can be a cleaning liquid or a disinfecting liquid or the like. The liquid is sprayed on the handle 14 prior to a user grasping a tissue 62 and using that tissue 62 to grasp the handle 14 of the door 12 . In this manner, the handle 14 can be cleaned and/or disinfected prior to a user grasping the handle 14 . A tissue 62 will then dry the handle 14 as the user grasps the handle 14 via the tissue 62 .
A spray-actuator button 76 is mounted on the front wall 20 of the housing 19 and suitable means, which includes elements such as movable wall 78 of a liquid-containing package 80 located in the housing 19 with the package 80 fluidically connected to the nozzle 70 , connects the spray-actuator button 76 to the liquid dispenser nozzle 70 and to the liquid compartment 42 of the housing 19 to spray liquid contained in the liquid compartment 42 of the housing 19 from the liquid dispenser nozzle 70 when the spray-actuator button 76 is operated.
The present invention is also embodied in a method of protecting a door handle. As can be understood from the foregoing disclosure, the method comprises mounting a dispenser unit on a door superadjacent to a door handle used to open and close the door; spraying door handle cleaning liquid from the dispenser onto the door handle; dispensing a door handle covering tissue from the dispenser unit; covering the door handle with the tissue while the tissue is connected to the dispenser unit and forming a covered door handle; grasping the covered door handle via the tissue covering the door handle; opening the door using the covered door handle; after the door is opened, removing the tissue covering the door handle from the dispenser unit to form a removed tissue; as the removed tissue is removed from the dispenser unit, pulling another tissue out of the dispenser unit to replace the removed tissue; and discarding the removed tissue.
It is understood that while certain forms of the present invention have been illustrated and described herein, it is not to be limited to the specific forms or arrangements of parts described and shown. | A handle of a door is covered by a disposable tissue when that handle is used to open the door. The tissue is dispensed from a housing mounted on the door superadjacent to the handle. Tissues from the housing are sized so the tissue will remain attached to the housing but will cover the handle. Disinfectant can be sprayed onto a handle before the handle is grasped via the tissue. Once the door is opened, a user simply pulls the tissue out of the housing and discards it. As one tissue is pulled out of the housing, that tissue pulls the next tissue out of the housing. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to radius and angle dressers and more particularly pertains to a new quick set radius dresser for making a dressing radius on grinding wheels faster and easier.
2. Description of the Prior Art
The use of radius and angle dressers is known in the prior art. More specifically, radius and angle dressers heretofore devised and utilized are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
Known prior art dressers include U.S. Pat. No. 4,180,046; U.S. Pat. No. 4,274,231; U.S. Pat. No. 5,038,746; U.S. Pat. No. 5,003,730; U.S. Pat. No. 4,299,196; and U.S. Pat. No. 4,073,281.
In these respects, the quick set radius dresser according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of making a dressing radius on grinding wheels faster and easier.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of radius and angle dressers now present in the prior art, the present invention provides a new quick set radius dresser construction wherein the same can be utilized for making a dressing radius on grinding wheels faster and easier.
The general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new quick set radius dresser apparatus and method which has many of the advantages of the radius and angle dressers mentioned heretofore and many novel features that result in a new quick set radius dresser which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art radius and angle dressers, either alone or in any combination thereof.
To attain this, the present invention generally comprises a magnet base having a cylindrical configuration with a circular top face, a circular bottom face, and a periphery formed therebetween. The top face has a threaded bore formed in a central extent thereof. A lever is positioned on the periphery with a first orientation for effecting the magnetization of the bottom face of the magnet base. With the lever in the first orientation, the magnet base is adapted for securing with a metallic recipient surface. In its second orientation, the magnet base serves for demagnetizing the magnet base for allowing the removal thereof from the recipient surface. Also included is a spacer having a cylindrical configuration with a circular top face, a circular bottom face, and a periphery formed therebetween with a diameter less than that of the magnet base. The bottom face has a rectilinear recess for receiving a top extent of a plug having a rectilinear configuration. As shown in FIG. 1, the plug includes a bottom extent having a bolt extending downwardly from the spacer in concentric relationship therewith. This is for screwably coupling with the threaded bore of the magnet base. The spacer further having a central conduit extending between the top face of the spacer and a top surface of the top extent of the plug. For reasons that will soon become apparent, the top face of the plug has a threaded aperture formed therein. Next provided is a handle ring having a cylindrical configuration. Similar to the forgoing components, the handle ring has a circular top face, a circular bottom face, and a periphery formed therebetween with a diameter less than that of the magnet base. The periphery of the handle ring is knurled. The top face of the handle ring has a cylindrical recess formed in a central extent thereof which communicates with a central hole formed through the entire handle ring and has a diameter less than that of the cylindrical recess. A radially extending linear recess is formed between the cylindrical recess and the periphery of the handle ring. A pair of flanking threaded apertures are formed adjacent a periphery of the handle ring at a midpoint of the linear recess. As such, a bolt extends through the central hole of the handle ring and the central conduit of the spacer for screwably engaging with the threaded aperture of the top extent of the plug thereof. As best shown in FIG. 3, an adjustable platform is provided including a horizontal plate. The horizontal plate has a guide post formed on a lower surface thereof which extends downwardly therefrom for slidably engaging the linear recess of the handle ring. A pair of parallel guide slots are formed adjacent opposite side edges of the plate. It is through such guide slots that a pair of retaining bolts pass prior to engaging the flanking threaded apertures of the handle ring. By this structure, the adjustable platform is adapted to slide along a radius of the top face of the handle ring and is further selectively fixed in place by way of the retaining bolts. Mounted on a top surface of the adjustable platform is a diamond holder block. The block has a cutting tip extending from an inboard face thereof and extending in parallel relationship with the radius of the top face of the handle ring. Finally, a gauge pin has an upper portion with a cylindrical configuration, a first diameter, and a first length. Associated therewith is a lower portion with a cylindrical configuration, a second diameter less than the first diameter and equal to the diameter of the cylindrical recess of the handle ring, and a second length less than the first length. The upper portion has a semi-cylindrical cut out formed therein with a length half the first length.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
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 other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
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.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
It is therefore an object of the present invention to provide a new quick set radius dresser apparatus and method which has many of the advantages of the radius and angle dressers mentioned heretofore and many novel features that result in a new quick set radius dresser which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art radius and angle dressers, either alone or in any combination thereof.
It is another object of the present invention to provide a new quick set radius dresser which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new quick set radius dresser which is of a durable and reliable construction.
An even further object of the present invention is to provide a new quick set radius dresser which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such quick set radius dresser economically available to the buying public.
Still yet another object of the present invention is to provide a new quick set radius dresser which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Still another object of the present invention is to provide a new quick set radius dresser for making a dressing radius on grinding wheels faster and easier.
Even still another object of the present invention is to provide a new quick set radius dresser that includes a base removably secured to a recipient surface. Also included is a cutting tip holder rotatable and radially slidable with respect to the base. The holder is selectively fixed with respect to the base. The holder has a cutting tip situated along a radius which remains along a direction in which the cutting tip holder is slidable.
These together with other objects of the invention, along with 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 the specific objects attained by its uses, reference should be made to the accompanying drawings and descriptive matter in which there are illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a side sectional view of a new quick set radius dresser according to the present invention.
FIG. 2 is a side view of the handle ring and mounting platform of the present invention.
FIG. 3 is a top view of the present invention.
FIG. 4 is a side view of the present invention showing the guide pin.
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIGS. 1 through 4 thereof, a new quick set radius dresser embodying the principles and concepts of the present invention and generally designated. by the reference numeral 10 will be described.
The present invention, designated as numeral 10, includes a magnet base 12 having a cylindrical configuration with a circular top face, a circular bottom face, and a periphery formed therebetween. The top face has a threaded bore 14 formed in a central extent thereof. A lever 16 is positioned on the periphery with a first orientation for effecting the magnetization of the bottom face of the magnet base. With the lever in the first orientation, the magnet base is adapted for securing with a metallic recipient surface 18 adjacent a grinding wheel. In its second orientation, the magnet base serves for demagnetizing the magnet base for allowing the removal thereof from the recipient surface. To accomplish this, an electromagnet or a movable high intensity magnet may be employed.
Also included is a spacer 20 having a cylindrical configuration with a circular top face, a circular bottom face, and a periphery formed therebetween with a diameter less than that of the magnet base. The bottom face has a rectilinear recess 22 for receiving a top extent of a plug 24 having a rectilinear configuration. As shown in FIG. 1, the plug includes a bottom extent having a bolt extending downwardly from the spacer in concentric relationship therewith. This is for screwably coupling with the threaded bore of the magnet base. The spacer further having a central conduit 26 extending between the top face of the spacer and a top surface of the top extent of the plug. For reasons that will soon become apparent, the top face of the plug has a threaded aperture 28 formed therein.
Next provided is a handle ring 30 having a cylindrical configuration. Similar to the forgoing components, the handle ring has a circular top face, a circular bottom face, and a periphery formed therebetween. The periphery of the handle ring is knurled. The top face of the handle ring has a cylindrical recess 32 formed in a central extent thereof which communicates with a central hole 34 formed through the entire handle ring and has a diameter less than that of the cylindrical recess.
A radially extending linear recess 36 is formed on the top face of the handle ring between the cylindrical recess and the periphery. A pair of flanking threaded apertures 40 are formed adjacent a periphery of the handle ring at a midpoint of the linear recess. As such, a bolt 42 extends through the central hole of the handle ring and the central conduit of the spacer for screwably engaging with the threaded aperture of the top extent of the plug.
As best shown in FIG. 3, an adjustable platform 44 is provided including a horizontal plate. The horizontal plate has a guide post 46 formed on a lower surface thereof which extends downwardly therefrom for slidably engaging the linear recess of the handle ring. A pair of parallel guide slots 48 are formed adjacent opposite side edges of the plate. It is through such guide slots that a pair of retaining bolts 50 pass prior to engaging the flanking threaded apertures of the handle ring. By this structure, the adjustable platform is adapted to slide along a radius of the top face of the handle ring and is further selectively fixed in place by way of the retaining bolts.
Mounted on a top surface of the adjustable platform is a diamond holder block 52. The block has a cutting tip 54 extending from an inboard face thereof and extended in parallel relationship with the radius of the top face of the handle ring.
Finally, a gauge pin 56 has an upper portion 58 with a cylindrical configuration, a first diameter, and a first length. Associated therewith is a lower portion 60 with a cylindrical configuration, a second diameter less than the first diameter and equal to the diameter of the cylindrical recess of the handle ring, and a second length less than the first length. The upper portion has a semi-cylindrical cut out 62 formed therein with a length half the first length.
In operation, the user first sets the radius of the unit with the gauge pin. The unit is then positioned on the internal grinder or related machine and secured in place by turning the lever on its magnet. The grinding wheel could then be fed past its diamond nib, thereby dressing it. The present invention possesses a high degree of accuracy thus improving the dimensional accuracy of the wheels that it would be used to dress. Further, it is capable of a small compact size for easy storage.
As to a further discussion of the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A radius dresser is provided including a base removably secured to a recipient surface. Also included is a cutting tip holder rotatable and radially slidable with respect to the base. The holder is selectively fixed with respect to the base. The holder has a cutting tip situated along a radius which remains along a direction in which the cutting tip holder is slidable. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority based on U.S. provisional application 60/959,917 filed Jul. 17, 2007.
STATEMENT OF FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to tub filler spouts suitable to control whether flow goes out the spout to fill a tub or alternatively is diverted to a shower outlet. More particularly it relates to compact diverter spouts that have manufacturing, aesthetic and operational advantages.
[0004] Conventional bathrooms typically have a filler spout that supplies water to a bathtub. In most of these installations a mixer control is positioned remote from the filler spout, usually on a wall. In some cases a diverter is directly mounted to the mixer control to select whether water is to flow to the tub or to the shower. In other cases the diverter is mounted on the filler spout itself. The present application relates to the second form of diverter.
[0005] With respect to this latter type of diverter, the diverter control can be placed adjacent the outlet of the spout. This has some cost advantages as the diverter would then not interfere with the connection between the spout and the room plumbing, and the outlet would be available to facilitate the assembly. However, there are some aesthetic concerns with respect to this location. Further, this location makes it more likely that something or someone will accidentally catch on the knob which controls the diverter.
[0006] Placing the diverter closer to the inlet may avoid or reduce these concerns. However, there are problems with respect to this approach as well.
[0007] For example, in U.S. Pat. No. 3,387,816 there was disclosed a diverter valve mounted near the inlet end of a tub filler spout. A lift knob was provided on the spout which connected to a shaft that passed through a small hole in the top rear of the spout. The other parts of the diverter were attached through the rear entry of the spout.
[0008] The valve included a sealing ring which, when moved vertically into alignment with an inlet conduit, sealed along a vertical surface. A problem with this design was that the water pressure was consistently acting against the seal (not assisting it), which placed greater demands on the seal, and which caused seal leakage (and thus lower shower flow and wasted tub water). This could also cause the diverter to accidentally drop down out of the diversion position from time to time when variable flow conditions were experienced (e.g. someone flushed a toilet which caused a pressure drop in the inlet line).
[0009] In U.S. Pat. No. 6,925,662 there was disclosed the idea of using a spring to facilitate movement of a tub diverter. However, water pressure was still acting laterally against a rubber ring which provided the sealing.
[0010] Other examples of prior art tub spouts where the diverter was mounted on the spout itself are U.S. Pat. Nos. 3,656,503, 6,070,280 and 6,449,784.
[0011] In unrelated work the art developed a variety of other valves which relied on ball-like structures to facilitate closure. See e.g. U.S. Pat. Nos. 1,145,252, 3,709,254, 5,109,887 and 5,226,453.
[0012] In any event, it is desired to develop further improved diverter spouts.
SUMMARY OF THE INVENTION
[0013] In one aspect the present invention provides a diverter spout for dividing fluid flow between two flow paths. The spout has a housing defining an internal flow channel with a restricted aperture therein, the aperture having an intake side and outlet side. There is also a carriage transversely movable across the restricted aperture, a linkage between the carriage and a control for causing the carriage to move relative to the aperture when desired, and a rollable gate mounted on the carriage. The gate can be caused to roll along a side of the aperture to thereby facilitate control of diversion of flow between the two flow paths if the spout is linked to a fluid supply and fluid is supplied to the spout.
[0014] In preferred forms the rollable gate can be caused to roll along the intake side of the aperture, the linkage can be a rod (e.g. a lift rod) passing through an upper wall of the spout housing and a knob mounted at an upper end of the rod outside the housing, and a resilient member can bias the carriage towards a position in which it is not completely closing off the aperture. This structure is particularly desirable where the diverter spout is a filler spout suitable to divide water flow between a bathtub when water passes through the spout and a shower outlet when the rollable gate restricts flow through the restricted aperture.
[0015] In other preferred forms the internal flow channel is an axial channel, an adaptor ring is provided at an intake end of the axial channel suitable to link an intake supply line to the spout, an axle is mounted on the carriage, and the rollable gate is mounted on the axle. The axle is mounted in slotted hub structures of the carriage so as to permit the axle to move towards and away from the aperture in a direction transverse to a direction of movement of the carriage.
[0016] Other refinements include that the rollable gate can be made of a resilient material such as rubber, the intake side of the aperture can include a chamfer forming a seat for the rollable gate, the housing can include an aerator at its outlet end, and the rollable gate can be in the form of a ball having a through passage for accepting an axle.
[0017] The present invention is highly advantageous. It provides an exterior appearance which only has minimal aesthetic disruption due to the control knob. Further, the control knob is rearwardly placed to avoid anything catching thereon.
[0018] The sealing assembly uses the flow of the water to assist in securing the seal, and can be easily assembled, largely through the rear of the spout. The overall design is susceptible to low cost manufacturing techniques, reducing the overall cost.
[0019] Yet other advantages include that the rolling action, taken together with the spring return pressure, reduces any tendency for the design to stick once diversion occurs. Further, the design of the hub slots and the use of a rolling mechanism should help insure reliability over long periods of use.
[0020] These and still other advantages of the present invention will become more apparent, and the invention will be better understood by reference to the following description of a preferred embodiment of the present invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is a perspective view of a preferred diverter spout of the present invention installed in a bathroom adjacent a tub and also a mixer control;
[0022] FIG. 2 is an exploded rear perspective view of the diverter spout of FIG. 1 ;
[0023] FIG. 3 is a sectional view taken along line 3 - 3 of FIG. 1 ; and
[0024] FIG. 4 is a view similar to FIG. 3 , but showing the valve in a diversion position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] Referring first to FIG. 1 , there is shown a bathroom generally 10 which includes a bathtub 12 , a spout 14 , and a wall mounted mixing valve 16 suitable to control flow to the spout 14 . A shower outlet (not shown) may be mounted several feet above the filler spout 14 .
[0026] A water supply line extends from the mixing valve 16 to an elbow (not shown) behind the wall adjacent the spout 14 . One branch of the elbow continues to the spout. Another branch of the elbow leads up to the shower outlet. When flow through the spout is not blocked by the diverter, gravity will cause the water to prefer supplying the spout 14 , with no water going to the shower. When an outlet of the spout 14 is blocked off by the diverter, water will follow the only open path and thus feed the shower.
[0027] Referring now more particularly to FIGS. 2-4 , spout 14 has a diverter valve (generally 17 ) and an outer housing 18 defining a flow channel 20 . Flow through the flow channel 20 , and thus out the spout 14 , requires passage through a restricted aperture 22 which has an intake side 24 and outlet side 26 . There may also be a conventional aerator 50 threaded into receiving threads (not shown) at the outlet.
[0028] An adaptor ring 28 is bolted via fasteners 32 to the holes 33 , with an o-ring 30 helping provide a better seal. The adaptor ring then receives the supply pipe.
[0029] There is a vertically movable carriage 34 associated with intake side 24 of the restricted aperture 22 . An axle 36 is mounted to carriage 34 and a rollable ball gate 38 rolls on the axle 36 somewhat like a wheel rolling on the ground.
[0030] Rollable ball gate 38 can be at least partially spherical, as is shown, or have other curvatures. Further, rollable ball gate 38 is preferably comprised of a resilient material, such as rubber.
[0031] Carriage 34 and rollable ball gate 38 are vertically displaceable between a closed position ( FIG. 4 ) in which gate 38 seals and covers restricted aperture 22 , and an open position ( FIG. 3 ) wherein at least a portion of restricted aperture 22 is unobstructed by gate 38 . In the closed position, the fluid source, typically water provides a water force which acts on gate 38 to drive it against a perimeter chamfer 40 on intake side 24 .
[0032] Rollable ball gate 38 rotates on axle 36 as it is linearly displaced between the closed and open position. Carriage 34 includes two slotted hubs 42 in which respective ends of axle 36 are positioned transverse to the linear up and down (closing and opening) motion of carriage 34 . When carriage 34 is moved into the closed position, slotted hubs 42 allow axle 36 and rollable ball gate 38 , which are acted on by the water pressure, to move transversely towards perimeter chamfer 40 on intake side 24 to better seat and seal gate 38 against chamfer 40 . There is reduced friction between intake side 24 and ball gate 38 , and also reduced attendant wear associated therewith, as a result of these structures.
[0033] The carriage may be caused to move by a manual lifting of knob 49 . Knob 49 is linked to rod 44 , which in turn links at its lower end to an acceptor 46 on the carriage. A bolt or other fastener 47 retains the rod 44 in the carriage acceptor 46 . The lower o-ring 48 is provided to prevent leakage up through the top of the spout hole 51 . The upper o-ring is primarily present as a bumper.
[0034] Note that the carriage is preferably installed first before the rod 44 . As a result, the parts can be made to snap together.
[0035] Modifications and variations to the preferred embodiment will be apparent to those skilled in the art, which are intended to be within the spirit and scope of the invention. For example, while an embodiment that is manually activatable is shown, it should be appreciated that electrical, hydraulic, pneumatic or other control systems can be used to move the rod 44 . In another example, the spout need not be for a residential bathtub. Rather, it could be a filler for another type of system requiring a diversion capability (e.g. an industrial vat with a by-pass option).
[0036] Therefore, the present invention is not to be limited to just the described most preferred embodiment. Hence, to ascertain the full scope of the invention, the claims which follow should be referenced.
INDUSTRIAL APPLICABILITY
[0037] The invention provides diverter spouts, particularly those suitable for controlling flow between bathtubs and showers. | A diverter spout for alternatively supplying water to a bathtub or diverting water to a shower is provided with a rolling gate valve. The gate valve uses the force of flowing water to facilitate sealing, and there is a return spring to reset the gate valve. | 5 |
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates in general to sewing machines and in particular to a new and useful sewing machine which includes a mechanism for automatically making edge-parallel seams by using a piston which can be lowered onto a workpiece to either actively rotate the workpiece about an axis of the needle or passively hold the workpiece while the workpiece is moved by a feed dog acting on the bottom of the workpiece.
U.S. Pat. No. 4,526,117 to Willenbacher shows a sewing machine with a pressure piston for the edge-parallel sewing of outer scallops, which is placed on the workpiece and is controlled by a scanning device with the sewing machine running. At that point a feed dog of the machine which continues to operate, rotates the workpiece about the pressure piston serving as brake means and holds it in abutment at the relatively narrow guide ruler. For the edge-paralell sewing of inner scallops, the guide ruler alone serves to perform the rotary movement of the workpiece, in that the workpiece braces itself on the guide ruler and in so doing is pushed away laterally, whereby it executes a clockwise rotation at least in the region of the stitch formation point. With this type of sewing machine, however, only workpieces with alternately straight and arcuate edges can be worked automatically. If, on the contrary, the workpiece has angular edges, the corner-shaped seam section cannot be sewn automatically. Instead, the sewing machine must be stopped with the needle inserted in the corner point of the seam and the workpiece must then be rotated around the needle by hand. It is noted that U.S. Pat. No. 4,526,117 has the same inventor and assignee as the present application.
From U.S. Pat. No. 3,425,369 to Kosrow, a sewing system is known which serves for the automatic edge-parallel sewing of workpieces with workpiece edges meeting at an acute angle. For this purpose, the sewing system comprises a workpiece rotating device with a tappet lowerable onto the workpiece, the size of the angle of rotation being determined by a scanning device responding to the workpiece edge. The workpiece hangs down over the edge of a narrow, substantially arcuate cloth supporting plate, and due to the friction at this edge it experiences during the forward movement a rotational moment or torque by which it is pushed against a guide ruler. Before the stitch formation point, a plate provided with a spring element is arranged at a lever. When resting on the workpiece, the plate and the spring element supplement the action of the presser foot. In addition, the plate has an aligning action on the workpiece. This aligning effect presumably comes about through the fact that the plate exerts on the workpiece passing under it, a brake force which, due to the position of the plate slightly offset laterally relative to the stitch formation point, exerts on the workpiece a rotatational moment which additionally supports the rotational moment caused by the friction at the edge of the cloth supporting plate. By means of such an arrangement, whose aligning action comes about in the case of outer scallops by a relative movement between workpiece and brake means, workpieces with narrow radii can, however, be controlled only quite inaccurately.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a sewing machine which makes possible an automatic guiding and aligning of workpieces with straight, angular and/or arcuate edge pattern, where the arcuate edges may also have narrow radii.
By using a pressure piston both as a passive guide element and as an active control element according to the invention, the various functions are carried out by one and the same structural element, whereby the engineering effort for the machine is reduced.
Another object of the invention is to support the pressure piston so that it is pivotable about the axis of the needle and driven by a second setting mechanism for rotating the pressure piston about the axis of the needle. In this way, the pressure piston can, before being placed on the workpiece, be moved into a position such that after the lowering operation it is located in the radius point of a convexly arcuate edge section, so that the feed dog, continuing to operate with the sewing machine running, can swivel the workpiece about the pressure piston, which in this case forms the axis of rotation.
According to a still further object of the invention, a scanning device for determining the geometric form of the workpiece edge has a measuring field extending crosswise to the feed direction of the workpiece and comprises several measuring points. The scanning device is connected to a microprocessor which evaluates measured data from the scanning device and is operable to control the setting means for moving the pressure piston. This makes it possible to directly determine the geometric form of the edge section of the workpiece present in front of the stitch formation point and the setting means for the operation of the pressure piston are actuated in corresponding manner. Thus workpieces with different edge patterns can be worked successively without transposition, reprogramming or change of sewing programs in direct succession.
A still further object of the invention is to provide a sewing machine with positioning device which is simple in design, rugged in construction and economical to manufacture.
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 a preferred embodiment of the invention is illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is explained with reference to an embodiment illustrated in the drawing, in which:
FIG. 1 is a simplified partial view of a sewing machine with the pressure piston and the setting means associated with it;
FIG. 2 is a simplified top view of a part of the sewing machine and the setting means;
FIG. 3 is a schematic representation of various elements of the sewing machine, of the guiding and scanning devices and their mutual connection; and
FIG. 4 is a top view of the sole of the sewing foot and the guide ruler.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The sewing machine, shown only in part in FIG. 1, has an arm 1 and a head 2. A main shaft 3 mounted in arm 1 drives in known manner, via a crank, (not shown) a needle bar 4, which carries a thread guiding needle 5. Cooperating with needle 5 is a looper or shuttle (not shown) which is arranged in the base plate 6 of the sewing machine below a stitch plate 7. A sewing foot 9 is fastened on a presser bar 8 mounted in head 2. The sole 10 of foot 9 has, according to FIG. 4 a lateral cutout 11. On the base plate 6 a guide ruler 12 is adjustably fastened, whose one end engages in the cutout 11.
In the base plate 6 a feed dog 13 is disposed, to which rectangular movements are imparted in known manner by a transmission (not shown). The transmission corresponds to the transmission of the sewing machine according to German OS No. 32 16 993 composed of the elements 27 to 41. Connected to the transmission is a known stitch setting device 14 shown in FIG. 3 which has a setting wheel 15 with spiral setting cam 16, a rocker lever 18 engaging by a projection 17 into the setting cam 16, a link 19, and a crank 20. Crank 20 is arranged on a setting shaft 21 of the stitch-setting device 14.
The circumference of the setting wheel 15 is provided with a worm gear serration 22, into which a worm 23 engages. Worm 23 is secured on the shaft 24 of a step motor 25, which is arranged adjustably on a plate 26 fastened on the sewing machine.
Axially of the setting shaft 21 there is arranged on the sewing machine a potentiometer 27 whose setting element 28 is fastened in an axial bore of the setting shaft 21. Potentiometer 27 is connected via a line 29 to an input of a microcomputer 30.
On the top side of head 2 a plate 31 extending substantially horizontally is fastened, which carries a vertically running stud 32 and spaced therefrom a vertically extending plate 33. On stud 32, which is aligned with the axis of needle 5, a fork type support 34 is rotatably mounted. Support 34 has an upper forked projection 35 and a lower forked projection 36.
Between the upper leg 37 and the lower leg 38 of support 34, a worm gear 39 is rotatably mounted on stud 32. The worm gear 39 is secured on a flat eye 40 of the lower leg 38 and is thus non-rotationally connected with the support 34. Engaging into the worm gear 39 is a worm 41 which is fastened on the shaft 42 of a step motor 43 arranged on plate 33.
In the lower projection, on a stud 44, a lever 45 is pivotably mounted. In the lower bent end 46 of lever 45 a double action cylinder 47 is arranged. At the piston rod 48 of the pneumatic cylinder 47 a pressure piston 49 coming to a point at the lower end is fastened.
In the upper end 50 of lever 45 which widens to an eye (or lug), a spherical threaded bushing 51 is pivotably mounted. In the threaded bushing 51 a threaded spindle 52 is received, which is rotationally connected to the shaft 53 of a step motor 54. The step motor 54 is mounted pivotably in the upper projection 35 by means of two bolts 55.
The microcomputer 30 is connected on the output side, via lines 56, 57 and 58, to control circuits (not shown) of the step motors 25, 43 and 54. Another output of microcomputer 30 is connected via an amplifier (not shown) and a line 59 to the switching magnet of a 4/2-way valve 60. The multi-way valve 60 is connected via two hose lines 61, 62 to the pneumatic cylinder 47. The compressed air source is marked 63.
On lever 45 a switching lug 64 is fastened which cooperates with a slit initiator 65. The initiator 65 is arranged on an angle plate 66 fastened on the support 34 and is connected via a line 67 to an input of microcomputer 30. At the support 34 a switching lug 68 is fastened, which cooperates with a slit initiator 69. The latter is arranged on an angle plate 70 fastened on plate 31 and is connected via a line 71 to another input of the microcomputer 30.
On an L-shaped support 72, which is arranged on a cranked angle plate 73 fastened on arm 1, a sensor 74 is fastened in spaced relation before the needle bar 4. The sensor 74 consists in known manner of a light transmitter and a light receiver. It cooperates with a reflection foil 75 fastened on the base plate 6 (FIG. 2) and is connected via a line 76 to an input of microcomputer 30. Spaced from the sensor 74 there is arranged on support 72 a second, similar sensor 77, which is connected via line 78 to an input of microcomputer 30 and together with sensor 74 forms part of a feed measuring device 79. In spaced relation before sensor 77 there is arranged on support 72 a third, similar sensor 80, which is connected via a line 81 to an input of microcomputer 30. Sensors 74,77 and 80 are aligned with the feed direction V and with the needle 5.
On support 72, laterally of sensor 74, there are arranged further, on a line 82 extending crosswise to the feed direction V, five similar sensors 83 to 87, which are spaced from each other and are connected via lines 88 to 92 to corresponding inputs of microcomputer 30. The sensors 83 to 87 form a scanning device 104 for the edges of the workpiece W.
A pulse generator 93 illustrated schematically in FIG. 3 contains a strobe disc 95 fastened on the main shaft 3 and provided with a plurality of stroke marks 94 as well as a light-scanning head 96 responding to the stroke marks 94. The pulse generator 93 is connected via a line 97 to an input of microcomputer 30. The stroke marks 94 are present only on a portion of the strobe disc 95, namely that portion which during the transport phase of the feed dog 13 passes through the light scanning head 96.
At the microcomputer 30, an input equipment shown schematically in FIG. 3, equipped with a keyboard for input of data, is connected via a line 98. An output of microcomputer 30 is connected via a line 100 to a known control circuit (not shown) of a positioning motor 101, which is in drive connection with the main shaft 3 via a belt drive 102.
The microcomputer 30, the sensors 74, 77, 80, 83 to 87, the pulse generator 93 and the step motor associated with the stitch setting device 14 are components of a corner stop system 103 which makes it possible to stop the sewing machine with the needle 5 inserted in a predetermined seam corner point.
The sewing machine operates as follows:
Before sewing is started, the seam spacing from the workpiece edge is fixed, if desired, by adjusting the lateral distance of the guide ruler 12 from the needle 5, and the selected value is entered in the microcomputer 30 via the input equipment 99. Also entered in the microcomputer 30 via the input equipment 99 is the size of the stitch length with which the seam is to be formed. Thereupon the microcomputer 30 gives the step motor 25 respective control commands, whereby the latter rotates the setting wheel 15 of the stitch-setting device 14 and in this manner adjusts the respective feed movement of the feed dog 13. The rotary movement of the setting shaft 21 occurring upon adjustment of the stitch length brings about an analogous variation of the resistance of the potentiometer 27 connected with the setting shaft 21. This value, which simulates the adjusted value, is sent to the microcomputer 30 also.
During sewing, the workpiece W is continuously scanned by the sensors 74,77,80 and 83 to 87. As long as the workpiece edge present in the scanning region of the sensors is straight, the reflection foil 75 remains covered at the scanning points. The pneumatic cylinder 47 with the pressure piston 49, the step motor 43 with the support 34, and the step motor 54 with the lever 45 remain in the starting position shown in the drawing.
Due to the slight friction of the workpiece on the base plate 6 or respectively on the surface of a sewing table (not shown) carrying the sewing machine, the feed dog 13 executing the feed movement causes at the workpiece a rotational moment or torque, whereby the workpiece edge to be worked is automatically held in abutment at the guide ruler 12. According to the same principle also concavely arcuate sections of the workpiece edge are controlled automatically.
When a straight follow-up edge of the workpiece W extending at an angle to the edge being worked approaches the sewing foot 9, the follow-up edge first passes under the front sensor 80. As soon as the reflection foil 75 is exposed in the scanning point of sensor 80, the sensor 80 delivers a switching pulse to the microcomputer 30. Thereupon the latter switches the positioning motor 101 to a predetermined low speed, at which the sewing machine can later be stopped without delay.
Thereafter the follow-up edge of workpiece W passes under the sensor 77. The switching pulse of sensor 77 brings about that from this time on the pulses, generated by the pulse generator 93 always only during the transport phases, are added in a register of the microcomputer 30, and this continues until the follow-up or trailing edge of the workpiece passes under the rear sensor 74 and the latter delivers a switching pulse to the microcomputer 30 upon clearing of the reflection foil 75 in the scanning point. The sum of the pulses of pulse generator 93 thus determined, which corresponds to the actual movement of the workpiece W, is compared with a number of pulses calculated by the microcomputer 30 at the same time, which results by dividing the distance between the scanning points of the sensors 74,77 by a factor permanently stored in the micrcomputer 30 and depending on the adjusted stitch length. In this way the actual forward step size of the workpiece W per stitch is determined.
Subsequently the follow-up edge of workpiece W passes through the scanning points of the sensors 83 to 87. If the follow-up edge is oriented at right angles to the workpiece edge being worked, the sensors 83 to 87 deliver a switching pulse simultaneously. But if the follow-up edge extends at an obtuse or an acute angle to the workpiece edge being worked, the sensors 83 to 87 deliver their switching pulses one after the other at intervals of time. The size of the angle between the two workpiece edges corresponds to the particular sum of the pulse generator 93 registered between the response of two adjacent sensors 83, 84; 84, 85; 85, 86; 86, 87. If the singly formed sums of the pulses are equal, it follows that the follow-up edge is rectilinear in the scanning region.
After determination of the geometric form of the section of workpiece W present in front of the sewing foot 9 and of the direction or orientation of the follow-up edge, the microcomputer 30, taking into consideration the selected seam spacing, the adjusted stitch length, and the previously determined actual forward step size of the workpiece W calculates the number of stitches still to be sewn as well as the stitch length required so that the last stitch of the seam section being worked will lie in the desired seam corner point. Approach of the seam corner point here takes place similarly as described in German OS No. 32 16 993.
When the seam corner point is reached, the sewing machine is stopped with the needle 5 inserted in the workpiece W, by signal delivery of microcomputer 30 to the positioning motor 101. Thereafter the microcomputer 30 brings about a switching of the multi-way valve 60, whereupon the pneumatic cylinder 47 lowers the pressure piston 49 onto the workpiece W. Following this, the micrcomputer 30 actuates the step motor 43, whereupon the latter, by way of the worm 41 and worm gear 39, swivels the support 34 with the lever 45 and the pressure piston 49 around the stud 32. The swivel movement of the pressure piston 49 is transmitted to the workpiece W, owing to which the latter rotates about the axis of needle 5. The swivel movement of the pressure piston 49 is such, as a function of the previously measured angle between the two workpiece edges converging in the corner point, that after completed rotary movement of the support 34 or of the pressure piston 49 the follow-up edge of workpiece W applies against the guide ruler 12 and runs parallel to the feed direction V.
To enable the workpiece W to follow the rotary motion of pressure piston 49 unrestrictedly, it may be desirable to slightly raise the sewing foot 9 during this time or to reduce the pressing force of foot 9.
After rotation of the workpiece W, the pressure piston 49 is raised again and support 34 is pivoted back to the starting position determined by the slit initiator 69. After the lifting of the pressure piston 49 the positioning motor 101 is turned on again by the microcomputer 30 and thus the sewing process is continued.
If now a convexly arcuate edge section of workpiece W approaches the sewing foot 9, this edge section again passes first under sensor 80, whereupon the positioning motor 101 is switched back to the predetermined low speed. Thereafter the arcuate edge section passes successively under the two sensors 77, 74, whereby again the actual forward step size of workpiece W per stitch is measured.
Subsequently the arcuate edge section passes under sensors 83 to 98. Due to the arched form of the edge pattern, the sensors 83 to 87 will now send their switching pulses after the passage of different feed distances, whereupon the microcomputer 30 calculates the geometric form, i.e. the size of the radius of the arc as well as the arc length, from the size of the individual pulse sums formed between the response of the first and following sensors 83 to 87. In accordance with the size of the radius thus determined, the microcmputer 30 now actuates the step motor 54, whereupon the latter, via the threaded spindle 53, displaces the lever 45 in such a way that the distance between the set-down point of the pressure piston 49 on the workpiece W and the axis of needle 5 is somewhat greater than the result from the subtraction between the previously determined radius of the arc and the seam spacing.
As soon as the workpiece W has been advanced so far that the radius point of the arcuate edge section is under the pressure piston 49, the latter is set down on the workpiece W in the manner already described above. With the sewing machine continuing to run, the cloth feed dog 13 brings about a rotary movement of workpiece W, the tip of piston 49 forming the center of rotation. Since the adjusted distance between the set-down point of piston 49 and the axis of needle 5 had been selected somewhat greater than would correspond to the theoretical value, the workpiece edge is pressed lightly against the guide ruler 12 during the rotation. Owing to this, disturbing influences, which are caused for example by friction, can have no adverse effect on the alignment result.
The period during which the pressure piston 49 rests on the workpiece W as center of rotation depends on the previously determined length of the arcuate edge section. As soon as the feed dog 13 has moved the workpiece by a corresponding amount, i.e. rotated in the seam region, the microcomputer 30 causes the pressure piston 49 to be pulled back into its starting position again. If the convexley arcuate edge section is followed by a straight or a concavely arcuate edge section, sewing can continue without interruption at normal speed. The step motor 54 then moves the lever 45 back into the starting position determined by the slit initiator 65.
The geometric form of the workpiece edge can be determined more accurately, the more sensors are used therefor and the closer their scanning points are together. A further possibility for determining the geometric form consists in using so-called image sensors, which are designed either as line or as area image pickup sensors and create an exact reproduction, consisting of a plurality of electrical signals, of the workpiece edge to be observed, which reproduction is then evaluated by the microcomputer 30.
While a specific embodiment of the invention has 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 sewing machine for automatically making edge-parallel seams comprises a scanning device for recognizing the geometric form of the workpiece edge and a pressure piston lowerable laterally of the stitch formation point. For straight workpiece edges extending at an angle to each other, the pressure piston, having been lowered onto the workpiece with the sewing machine stopped, is rotated around the needle which is inserted in the workpiece, the workpiece being taken along accordingly. For a convexly arcuate edge pattern, first the lateral distance of the pressure piston from the needle is readjusted in such a way that it corresponds to the radius of the edge arc (e.g. scallop). Thereafter, with the sewing machine continuing to run, the pressure piston is lowered, whereupon the feed dog of the sewing machine rotates the workpiece around the pressure piston. | 3 |
TECHNICAL FIELD
[0001] The present invention relates generally to the field of ovens and dryers, and more particularly to an improved oven for processing fiber bundles or tows.
BACKGROUND
[0002] Convection ovens and dryers that process continuous streams of product are in wide use. In many ovens the product moves horizontally at one or more levels, either carried on parallel moving conveyors or, in the case of textiles or webs, suspended under tension between external drives. A circulating hot air flow is brought in contact with the product for heating or drying. A technically important class of ovens treats polymeric or organic carbon fiber precursors in air to provide thermoplastic properties prior to carbonization.
[0003] Ovens for providing oxidative heat treatment to carbon fiber precursor materials such as polyacrylonitrile (PAN) are known in the industry. U.S. Pat. No. 6,776,611 describes an oven in which the heating airflow is circulated around the PAN in tow format and contacts the fiber in a direction perpendicular to the direction of tow travel. U.S. Pat. No. 4,515,561 discloses an oven in which the heating airflow is circulated around the PAN in tow format and contacts the fiber in a direction parallel to the direction of tow travel.
BRIEF SUMMARY OF THE INVENTION
[0004] With parenthetical reference to corresponding parts, portions or surfaces of the disclosed embodiment, merely for the purposes of illustration and not by way of limitation, the present invention provides an improved oven ( 1 ) comprising a conveyor configured and arranged to move a product ( 11 ) to be processed through an oven, a primary air delivery system ( 45 ) configured and arranged to provide a heated primary air flow ( 47 ), a secondary air delivery system configured and arranged to provide a heated secondary air flow ( 48 ), a processing enclosure ( 21 ) configured and arranged to receive and contain the product and the primary air flow, an insulated enclosure ( 2 ) configured and arranged to receive the heated secondary air flow, the processing enclosure configured and arranged to extend through the insulated enclosure and the heated secondary air flow and to separate the primary air flow from the secondary air flow.
[0005] The conveyor may be configured to move the product through the processing enclosure in a first direction ( 49 ), with individual passes moving either forward or backward, the processing enclosure may have a longitudinal enclosure axis ( 50 ) substantially parallel to the first direction, the primary air flow in the processing enclosure ( 47 ) may be substantially parallel to the first direction and the secondary air flow in the insulated enclosure ( 48 ) proximal to the processing enclosure may be substantially perpendicular to the first direction.
[0006] The primary air delivery system may comprise an input chamber ( 10 ) configured and arranged to receive the primary air flow and the conveyed product and to output the primary air flow and the conveyed product to the processing enclosure. The conveyor may be configured and arranged to move the product through the processing enclosure in a first direction and the chamber may output the heated primary air flow and the conveyed product to the processing enclosure in the first direction. The input chamber may comprise an air input opening ( 38 ), a product input opening ( 39 ) different from the air input opening, an output opening ( 43 ) to the processing enclosure opposite the product input opening, and an airflow directional ( 37 ) configured and arranged to direct airflow from the air input opening to the output opening. The air input opening may be orientated substantially perpendicular to the output opening and the airflow directional may be configured and arranged to turn the airflow from a direction substantially perpendicular to the first direction to a direction substantially parallel to the first direction. The output opening may be larger in size than the product input opening. The chamber may further comprises a product input opening size adjustment mechanism, and the opening size adjustment mechanism may comprise a first plate ( 29 ) and a second plate ( 30 ), the first and second plates adjustable relative to each other so as to provide a variable gap ( 39 ) there between. A locking mechanism may be configured and arranged to adjustably lock the plates in a position relative to the chamber so as to vary the size of the product opening, and the locking mechanism may comprise locking screws ( 31 ).
[0007] The oven may further comprise an output chamber ( 18 ) configured and arranged to receive the product and the primary air flow from the enclosure and to exhaust the primary air flow and discharge the product. The output chamber may comprise an input opening ( 44 ) from the processing enclosure, a product discharge opening ( 41 ) opposite the input opening and an air exhaust opening ( 42 ) different from the product discharge opening. The air exhaust opening may be orientated substantially perpendicular to the input opening. The output chamber may further comprise a product input opening size adjustment mechanism, and the opening size adjustment mechanism may comprise a first plate and a second plate, the first and second plates adjustable relative to each other so as to provide a variable gap ( 41 ) there between. A locking mechanism may be configured and arranged to adjustably lock the plates in a position relative to the chamber so as to vary the size of the product discharge opening, and the locking mechanism may comprise locking screws.
[0008] The primary air delivery system may comprise one or more devices selected from a group consisting of a fan ( 3 ), a heater ( 4 ), a thermometer ( 6 ), a manifold ( 7 ), a valve ( 8 ), a flow meter ( 9 ) and a pipe ( 5 ). The primary air delivery system may comprise a single regenerative fan, a single in-line heater, a thermometer, a single manifold configured and arranged to split airflow into a plurality of downstream paths, each of the paths comprising a valve and a flow meter, wherein the primary air flow is generated and circulated through the heater, the manifold and the valve no more than once before being brought into contact with the product. The primary air delivery system may comprise a single regenerative fan, a manifold configured and arranged to split airflow into a plurality of downstream paths, each of the paths comprising a valve, a flow meter, an in-line heater and a thermometer, before being brought into contact with the product. The primary air delivery system may not re-circulate, in whole or in part, primary air flow exiting the processing enclosure.
[0009] The secondary air delivery system may comprise a fan ( 12 ), a heater ( 13 ), a thermometer ( 35 ), a recirculating inlet ( 26 ) for receiving used air from the insulated enclosure, an air exhaust outlet ( 16 ) having a flow control valve ( 17 ) for exhausting air from the insulated enclosure, and a make-up air inlet ( 14 ) having a flow control valve ( 15 ) for receiving make-up air, wherein the secondary air flow may comprise a mix of the used air and the make-up air. The make-up air flow and the exhaust air flow may be controlled by the valves ( 15 , 17 ) to vary the amount of the make-up air and the used air in the secondary air flow. The secondary air delivery system may comprise a plug fan ( 12 ) with an axis perpendicular to the processing enclosure axis ( 50 ), located on an insulation enclosure wall approximately midway along a product travel dimension of the oven, the fan having an upstream inlet cone ( 26 ) for receiving air and a discharge plenum ( 32 ) that directs flow downwards, a heater ( 13 ) positioned downstream and near the fan discharge port, a thermometer ( 35 ) positioned downstream and near the heater, a set of directing vanes ( 28 ) positioned near the heater and near a floor of the insulated enclosure that turn the flow 90 degrees to flow adjacent to the floor of the insulated enclosure, a second set of vanes ( 23 ) that split the flow approximately in half and turn a first half portion of the flow 90 degrees to be aligned with the first direction and turn the second half portion of the flow 90 degrees to be opposite the first direction, a third set of vanes ( 24 a ) that turn the first portion of the flow 90 degrees to flow upwards in a direction perpendicular to the enclosure axis, a fourth set of vanes ( 24 b ) that turn the second portion of the flow 90 degrees to flow upwards in a direction perpendicular to the enclosure axis, a flow conditioning device ( 22 ) that spans a length of the oven and is wider than a widest dimension of the processing enclosure and through which the upward air flow passes before contacting the processing enclosure, an upper perforated plate ( 27 ) above the processing enclosure, and an air collection plenum ( 36 ) separating air that flows through the upper perforated plate and into the fan inlet cone from air that is discharged from the fan and flows through the heater, turning vanes, flow conditioner and over the processing enclosure. The flow conditioning device may comprise two perforated plates with a cellular structures located there between, and the cellular structure may be a honeycomb structure.
[0010] The primary air delivery system and the secondary air delivery system may be configured and arranged to deliver the primary air flow to the inside of the processing enclosure and to deliver the secondary air flow to the outside of the processing enclosure at a temperature range that is about the same.
[0011] The processing enclosure may have a length and a cross-sectional characteristic dimension and the length may be at least about fifty times the cross-sectional characteristic dimension. The processing enclosure may have a cross-sectional shape that is circular, square, rectangular, oval or elliptical.
[0012] The oven may comprise multiple processing enclosures configured and arranged to receive and contain the product and the primary air flow and extending through the insulated enclosure. The oven may further comprise multiple input chambers and output chambers communicating with the respective multiple processing enclosures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a perspective view of an oven in accordance with one embodiment of the present invention.
[0014] FIG. 2 is an enlarged detailed view of the embodiment shown in FIG. 1 , taken within the indicated area A of FIG. 1 , with the top sheet metal of the end chamber removed for clarity.
[0015] FIG. 3 is a rear perspective view of the embodiment shown in FIG. 1 , with one wall of the insulating enclosure removed for clarity.
[0016] FIG. 4 is a vertical transverse cross-sectional view of the embodiment shown in FIG. 1 , taken generally on line B-B of FIG. 1 .
[0017] FIG. 5 is a cross-section view of a second embodiment of the oven shown in FIG. 4 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] At the outset, it should be clearly understood that like reference numerals are intended to identify the same structural elements, portions or surfaces consistently throughout the several drawing figures, as such elements, portions or surfaces may be further described or explained by the entire written specification, of which this detailed description is an integral part. Unless otherwise indicated, the drawings are intended to be read (e.g., cross-hatching, arrangement of parts, proportion, degree, etc.) together with the specification, and are to be considered a portion of the entire written description of this invention. As used in the following description, the terms “horizontal”, “vertical”, “left”, “right”, “up” and “down”, as well as adjectival and adverbial derivatives thereof (e.g., “horizontally”, “rightwardly”, “upwardly”, etc.), simply refer to the orientation of the illustrated structure as the particular drawing figure faces the reader. Similarly, the terms “inwardly” and “outwardly” generally refer to the orientation of a surface relative to its axis of elongation, or axis of rotation, as appropriate.
[0019] Referring to the drawings, and more particularly to FIG. 1 thereof, this invention provides an improved oven for fiber heat treatment, of which a first embodiment is generally indicated at 1. While this invention has many applications for providing an efficient and high quality fiber heat treatment, it is described in this embodiment with regard to its application to an oxidative stabilization oven for carbon fiber precursor.
[0020] As shown in FIG. 1 , oven 1 includes rectangular insulation enclosure 2 , which is of conventional construction using structural and sheet steel and mineral or glass insulation. Product layers 11 are arranged and move in parallel horizontal planes through oven 1 . In the case of carbon fiber precursors in tow format, product layers 11 are tows arranged side-by-side in one horizontal layer and rollers or other pass-back devices are used to create one continuous serpentine path through the entire oven.
[0021] The product contact air, or process air, is pressurized at fan 3 and passes through in-line heater 4 . Fan 3 may be any conventional fan capable of the required flow and pressure drop, and is preferably of a regenerative type. It is preferable that fan 3 draw air from a filtered source or that fresh air is drawn from outside the plant environment. In-line heater 4 may be either electric or fossil-fuel driven, and should be capable of raising the air to the desired process temperature in a single pass of air. Temperature ranges of the process air are preferably between about 100 and 600 degrees Celsius (C), more preferably between about 200 and 400 degrees C. The temperature of the air exiting heater 4 is controlled via a conventional electronic feedback loop using thermometer 6 to measure the temperature and a thyristor or gas flow control valve to modulate the power to heater 4 .
[0022] The heated air enters manifold 7 and is split into a plurality of paths prior to entering oven 1 . Each such gas path through inlet piping 5 includes valve 8 and flow meter 9 , which measure and control the flow rate of heated air. Valves 8 may be any conventional control valve designed for the desired temperature range. While not shown on the figure, heater 4 , the downstream piping and manifold 7 are thermally insulated, preferably with fiberglass or mineral wool of about 50 mm or greater thickness. Alternative configurations for the process air inlet train may be used. For example, a separate heater could be installed in each gas inlet path 5 downstream of flow control valve 8 .
[0023] Referring now to FIG. 2 , in this embodiment the plurality of process gas inlets are directed via piping 5 through opening 38 in the side wall of end chamber 10 , where the gas is then directed by deflector 37 into tubular enclosures 21 , which are connected through opening 43 to the back wall of chamber 10 and pass through holes in insulation enclosure 2 and into oven 1 . Deflector 37 turns the flow 90 degrees from a lateral direction to a direction normal to the direction of travel of product 11 . Air is prevented from flowing out product entrance 39 of chamber 10 by having product entrance 39 of a reduced area. Product opening 39 is defined by an upper product slot plate 29 and a lower product slot plate 30 . The size of product slot or opening 39 may be adjusted by sliding the slot plates 29 and 30 vertically, with plates 29 and 30 locked in place or allowed to travel by means of locking screws 31 . In PAN oxidation ovens, thickness of product layer 11 varies but is generally about 3 mm or less. The gap 39 between plates 29 and 30 during operation is preferably between about 2 and 20 mm, and more preferably between about 6 and 10 mm. The maximum adjusted gap between plates 29 and 30 , for cleaning or other maintenance, is at minimum about equal to the height dimension of product enclosures 21 . Other means for fixing the position of plates 29 and 30 may be used. For example, spring loaded bolts may be employed.
[0024] Process air enclosures 21 have a relatively small cross section compared to the oven dimensions, and are preferably tubes having a diameter between about 0.01 and 0.40 meters, and more preferable between 0.02 and 0.10 meters. The velocity of the product air flow within enclosures 21 is preferable between about 0.1 and 10 m/sec, and more preferably between about 1 and 6 m/sec. The ratio of the cross-sectional characteristic dimension (diameter in the case of a cylindrical tube) to the length of enclosures 21 is preferable greater than about 10 and more preferably greater than about 50. The high ratio of the cross-sectional characteristic dimension to the length ensures that the flow of air occurs along the direction of travel of product layers 11 . While enclosures 21 in the embodiment shown are round tubes, other cross-section tube shapes, such as square, rectangular, elliptical or oval, could be used as an alternative. It should be understood by those skilled in the art that, depending on the cross-sectional moment of inertia and length of enclosures 21 , they may require mechanical support along the length of the oven to prevent downward bowing or creeping. These supports can be positioned under enclosures 21 at regular intervals along the oven length and welded or bolted to the inside surface of insulation enclosure 2 .
[0025] Referring now to FIG. 3 , the plurality of process enclosures 21 and product layers 11 traverse the oven and pass through insulation enclosure 2 and into exit end chamber 18 through opening 44 in chamber 18 . Product 11 exits end chamber 18 through a slot 41 between a set of adjustable slot plates similar to plates 29 and 30 described with entrance end chamber 10 . The process air flows inside enclosures 21 as shown by arrows 47 and exits in the transverse direction through opening 42 in chamber 18 and a plurality of exhaust piping 40 that includes valve 19 . The exhausted air is then collected in exhaust header 20 , which is connected to an appropriate air discharge system.
[0026] Referring again to FIG. 1 , process air travels once through the oven system. It enters at fan 3 , and is heated and set to a control flow with heater 4 , valve 8 and flow meter 9 . Entrance end chamber 10 directs both product 11 and almost all the process air into process enclosures 21 , where the air transfers heat and mass with product layers 11 . The air and product 11 exit the oven through exit end chamber 18 , where the exhaust process air is directed through control valves 19 and into exhaust header 20 . The pressure inside of process enclosures 21 is preferably very close to ambient pressure, and most preferably within about 1 mbar and even more preferably within about 0.1 mbar. Valves 8 and 19 and the height of slot openings 39 and 41 in end chambers 10 and 18 , respectively, are the means for adjusting this pressure. The near ambient pressure ensures that very little air actually exits or enters process enclosures 21 through the product slots, which means that almost all of the process air, typically about 98% or more, contacts product layers 11 . The degree of control can be further increased if exhaust manifold 20 connects to an exhaust handling system with draw or negative pressure. In this case, the oven may be operated such that enclosures 21 have a slight negative pressure, virtually eliminating the escape of process gas at the product slots.
[0027] The process air system described has the benefit that the gas contacting the product enters product enclosures 21 free from contaminants and picks up process contaminants only during a single air pass. For example, an oven such as shown in FIG. 1 , heat treating 24000 filaments of 1.0 dTex PAN moving at 0.25 m/min, will generate about 1.1 gr/hr of hydrogen-cyanide (HCN) gas. With six oven enclosures 21 , each with a 50 mm diameter, and at an air velocity of 4.0 msec and temperature of 250 degrees C., the calculated maximum concentration of HCN in the air stream is about 8 ppm. This compares favorably to HCN concentrations seen inside typical industrial ovens that are between about 40 and 80 ppm.
[0028] Referring again to FIG. 1 , a secondary air flow is also provided to enclosures 21 . Secondary air flow is pressurized by fan 12 and heated by heater 13 . Fan 12 may be any conventional fan capable of the required flow, temperature and pressure drop, and is preferably of a plug type configuration. Heater 13 may be either electric or fossil-fuel powered, and should be capable of heating a circulating stream of air to the desired process temperature. The secondary air temperature is controlled via a conventional electronic feedback loop using thermometer 35 to measure the temperature and a thyristor or gas flow control valve to modulate the power of heater 13 . The purpose of the secondary air loop is to prevent heat loss or gain to the process air or product layers as they traverse the oven, so the temperature of the secondary air is set and controlled at a temperature substantially the same as the setting of the process air temperature.
[0029] Referring to FIGS. 2 , 3 and 4 , secondary air flows vertically downwards from fan wheel 32 through heater 13 . It is turned 90 degrees to flow horizontally and transversally towards the back of oven 1 by a set of turning vanes 28 . The secondary airflow is then split in half and redirected horizontally and longitudinally, either toward the entrance or exit end of oven 1 by turning vanes 23 . The secondary airflow is then directed upwards vertically by turning vanes 24 a and 24 b and enters flow conditioner 25 . Flow conditioner 25 is designed to straighten the flow and make the air velocity uniform, and is preferably a device that contains a perforated steel plate and cellular honeycomb structures as described in U.S. patent application Ser. No. 13/180,215, entitled “Airflow Distribution System,” the entire disclosure of which is incorporated herein by reference. Flow conditioner 25 includes a second perforated plate 22 on top, through which the air flows at a uniform velocity and uniform vertical direction. The airflow just above plate 22 has velocity characteristics such that the ratio of the standard deviation to the mean is less than about 10%, and more preferably less than about 3%. The direction of flow just above plate 22 is preferably within about 10 degrees of vertical and more preferable within about 3 degrees of vertical. The mean velocity of the vertical flow is preferably between about 1 and 10 m/sec, and more preferably between about 3 and 6 m/sec.
[0030] Referring again to FIGS. 2 , 3 and 4 , the secondary air flows upward over and around process air enclosures 21 and then continues upward through perforated plate 27 . The air then enters collection plenum volume 36 . Plenum 36 is separated from the airstream that flows upwards over process tubes 21 by vertical wall 33 and is separated from the flow that travels along the oven floor by horizontal wall 34 . The recirculating secondary airflow path is shown with arrows 48 in FIGS. 3 , 4 and 5 . The majority of the secondary airstream re-circulates through fan 12 by entering fan inlet cone 26 . A portion of the secondary air is exhausted at secondary oven air exhaust opening 16 and this flow is regulated by secondary air exhaust valve 17 . Make-up airflow for the secondary airstream enters the oven at secondary air inlet 14 and is regulated by make-up air valve 15 . Since the secondary airstream does not contact the product, it remains essentially clean, and therefore, at steady conditions, very little exhaust or make-up air is required. When it is desired to lower the oven temperature, however, the make-up air flow is useful for introducing cold room air into the oven.
[0031] The secondary airstream keeps the temperature of the process air uniform as it flows along the interior length of the process air enclosures 21 . For example, if there were no secondary air flow, the temperature of the process air would, depending on velocity, drop by between about 20 to 50 degrees C. between the entrance and exit of the oven, with the largest temperature drops corresponding to the lowest air velocities. With a secondary airflow of about 3 m/sec or greater, the process air temperature change over the length of the oven is less than about 2 degrees C.
[0032] The response time to a change in oven desired operation temperature, or setpoint, is determined in practice by the response time of the secondary airstream. This is because the process air consists of a once-through airflow that contacts only product layers 11 and the relatively small air enclosures 21 , and so has much lower thermal inertia than the secondary air system. The secondary air contacts the inside of the relatively large insulation enclosure 2 as well as the plug fan wheel 32 and all the other metal components inside the oven. For example, an oven similar to the embodiment shown in FIGS. 1-4 with an insulation enclosure of dimensions of 5.0 m long×2.5 m high×1.0 m wide has a thermal inertial of about 800,000 Joules per degree C. If the oven is operating at a temperature of about 300 degrees C., there will be heat losses through the enclosure and ends of about 10 kW. In this example, heating element 13 with 30 kW of power capacity will thus have 20 kW power available to raise the temperature of the oven, which will result in a time of about 10 minutes to raise the oven temperature by about 15 degrees C. In this example it is assumed that valves 15 and 17 are closed to prevent makeup air from drawing power. Another example, using the same oven parameters just described, would be a lowering of the oven setpoint by about 15 degrees C. In this case, valves 15 and 17 are opened and heater 13 is shut off. In this example, a makeup airflow of about 170 Nm̂3/hr (100 scfm) results in about a 15 degree C. drop occurring in about 7 minutes.
[0033] A calculation of the maximum temperature rise in product enclosure 21 during an exothermic runaway of PAN precursor will illustrate that the present invention does not require water quenching systems. The conditions assumed are 4×12,000 filament tows of 1.0 dTex at 1 m/min (mass rate of 0.288 kg/hr) in a single 51 mm diameter round enclosure 21 , and an air velocity of 1.0 m/sec at 250 degrees C. (mass rate of 6.2 kg/hr). Assuming PAN heat of reaction equals 2425 Joules per gram, and that all the reaction energy is absorbed by the flowing air, the calculated air temperature rise is about 110 degrees C. Thus, even with airflow near the bottom of the typical range, enclosure 21 should not experience a temperature above about 360 degrees C.
[0034] While in principle enclosures 21 can be made of many different materials, the preferred materials are austenitic stainless steels such as 304 which maintain mechanical strength until above about 500 degrees C. and can therefore readily withstand this degree of exothermic runaway. The once-through airflow of the present invention promotes removal of the ash or other debris remaining after an exothermic runaway because the airflow itself tends to carry out lighter materials and is constantly being replaced by fresh air. Since the process air stream can be cooled rapidly, for example by about 100 degrees C. in less than about 5 minutes, the end chambers 10 and 18 can be opened within a short time after the exothermic event to facilitate inserting push rods or the like to remove any remaining debris.
[0035] FIG. 5 shows a cross-section of another embodiment of the present invention. In this embodiment, the process air enclosure tubes 21 containing product layers 11 are arranged in multiple vertical rows and columns where the horizontal spacing is delineated by X and the vertical spacing delineated by Y. It is preferable that the ratio of vertical and horizontal spacing, Y/X, of enclosures 21 follows the principles used for conventional tube bundles in heat exchangers. In PAN fiber processing, the vertical spacing Y is established from tow transport considerations outside of the oven, with typical product layer spacing preferably between about 0.1 and 0.4 meters, and more preferably between about 0.15 and 0.20 meters.
[0036] The described improvements provide a number of benefits. The oven provides uniform air velocity and consistent contact angle between the air and the fiber product throughout the heated length over a wide range of air velocities. Further, the temperature of the air is uniform for the entire heating length, independent of the velocity. Further, a uniform, stead-state temperature can be achieved rapidly, a benefit because delay in establishment of temperature wastes both time and process material. Further, the process contact air is introduced free of moisture, fiber fly, particulate, and process off-gas chemicals that can degrade the quality of the product. Also, the ability to control the process pressure prevents the escape of process off-gases. In particular, PAN based carbon fiber precursors are known to give off toxic hydrogen cyanide (HCN) which poses an inhalation hazard if allowed to concentrate outside the oven.
[0037] Further, for carbon fiber precursors, the oven makes possible handling process upsets in an efficient manner. One type of process upset occurs when precursor tows break inside the oven. The broken tow ends can entangle with other tows, and other passes of tows at different elevations, either right after the break, or later when the broken tow is pulled out of the oven, until the entire process must be stopped and the oven cooled to ambient to allow internal access. With the design of oven 1 a tow break is contained within one minimum cross-sectional area enclosure 21 . The tow cannot fall far away from its normal path because of the enclosure, and is therefore unlikely to snag on oven parts or other tows. Oven 1 also facilitates pulling a broken tow out of the oven because the removal path is essentially a straight line and the tow removal point is from the ends outside of the oven and so does not require entering the oven or cooling the oven to ambient temperature.
[0038] Another type of process upset occurs when carbon fiber precursor experiences an exothermic runaway reaction resulting in a fire. The oven limits fires from spreading throughout the entire oven volume. In the event of an exothermic process runaway, the heat generated is thus limited. The once-through process air stream carries products of combustion and generated heat out of the oven and there is no need to employ deluge water systems. After an exothermic event or fire, there is no need to stop the secondary air flow, no need to cool the oven to ambient temperature, and no need to enter the oven. Further, the oven limits fires from spreading without resorting to deluge water systems that are expensive to install and maintain, and which, when activated, require a time consuming cleanup inside an ambient temperature oven before the process can be restarted. This means the overall process upset due to an exothermic runaway or fire can be a matter of minutes, as compared to hours with conventional carbon fiber precursor ovens.
[0039] The design of oven 1 provides uniform air velocity and consistent contact angle, temperature uniformity, short temperature response time, clean process gas, reduces or eliminates the need for post process treatment of the off gas, and makes possible efficient handling of process upsets. The fiber passes through the oven within enclosure 21 that are essentially the minimum possible cross-sectional area considering fiber catenary and natural vibrations. This small cross-section means that the ratio of the process enclosure length to its cross-sectional characteristic dimension is very large, creating boundary conditions that ensure the airflow is nearly exactly parallel to the fiber. The small cross-section area has the additional advantage that, for a given air velocity, the required amount of process air is kept to a minimum, thereby requiring minimum energy for pressurization and heating.
[0040] The air passed through these product enclosures is filtered, pressurized, heated to the desired process temperature, and flow modulated upstream, flows parallel to the fiber through the enclosure, and exits to an exhaust system. Air only touches each element of the system one time. This means that the process air does not accumulate moisture, fiber fly, particulate, or other process off-gas chemicals that can degrade the quality of the product. Because there is no concentrating of process volatiles, the exhausted process air from PAN carbon fiber precursor does not necessarily require expensive incineration or other means of post treatment to destroy HCN.
[0041] The once-through heating process is very fast thermally and thus the temperature of the process air can be changed rapidly, for example by 100 degrees C. in less than 5 minutes. This substantially reduces lost time and facilitates operator safety during tow removal. Tow removal can be done without changing the secondary air flow or temperature, so that once the broken tow is removed, the process air flow and temperature can be rapidly reestablished. This means the overall process upset due to a tow break can be a matter of minutes, as compared to hours with conventional carbon fiber precursor ovens. A benefit of the secondary air flow outside the process enclosures, and therefore not in contact with the fiber, is that it maintains a high degree of temperature uniformity within oven 1 . This re-circulated air flow is pressurized and heated to the desired process temperature with a dedicated fan and heater located integral to the oven casing. This air flows over and around the process air enclosures, keeping the outside surface at the desired process temperature, and thus preventing heat loss from the process air flowing parallel to the fiber. This affect provides temperature uniformity of the process contact air even at very low process air velocities, which is inherently difficult since in that case small heat loss or gain will tend to produce large temperature differences. The secondary air flow is provided with a modulated supply of cold fresh air. The secondary air temperature can be raised with increased heating power or lowered by increasing the intake of cold fresh air. This means that the secondary air temperature can be brought to equilibrium quickly whether the temperature change is an increase or a decrease.
[0042] The present invention contemplates that many changes and modifications may be made. Therefore, while the presently-preferred form of the oven for fiber heat treatment has been shown and described, and several modifications and alternatives discussed, persons skilled in this art will readily appreciate that various additional changes and modifications may be made without departing from the spirit and scope of the invention, as defined and differentiated by the following claims. | An improved oven ( 1 ) comprising a conveyor configured and arranged to move a product ( 11 ) to be processed through an oven, a primary air delivery system ( 45 ) configured and arranged to provide a heated primary air flow ( 47 ), a secondary air delivery system configured and arranged to provide a heated secondary air flow ( 48 ), a processing enclosure ( 21 ) configured and arranged to receive and contain the product and the primary air flow, an insulated enclosure ( 2 ) configured and arranged to receive the heated secondary air flow, the processing enclosure configured and arranged to extend through the insulated enclosure and the heated secondary air flow and to separate the primary air flow from the secondary air flow. | 3 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims the priority of Chinese patent application No. 201410198249.8, filed on May 12, 2014, the entirety of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention generally relates to the field of semiconductor technology and, more particularly, relates to chip packaging structures and treatment processes thereof.
BACKGROUND
[0003] In an IC chip packaging process, after certain steps, metal and/or metal ions may be deposited on the insulation layer between adjacent electrical connect structures, such as soldering balls (bumps), and soldering pads, etc. Such metal ions are generated by plasma etching processes, and/or wet etching processes, etc. For example, tin and/or tin ions may be deposited on the insulation layer between the adjacent tin soldering balls. Such metal and/or metal ions are able to cause a leakage current issue between the two adjacent electrical contact structures. Thus, the final test (FT) may fail.
[0004] In order to solve the FT failure caused by the deposition of the metal and/or metal ions, some technical approaches have been developed. For example, an argon plasma treatment process is performed on the insulation layer to remove the metal and/or the metal ions; and then the removed metal and/or metal ions are pumped away by the vacuum system of the plasma instrument.
[0005] However, in practical processes, using the argon plasma to remove the metal and/or metal ions has certain limitations because it is a physical process. The metal and/or metal ions may not be entirely removed. Further, the argon plasma may damage the surface of the dielectric layer. Thus, the leakage current may still be generated between adjacent electrical connect structures. The disclosed device structures and methods are directed to solve one or more problems set forth above and other problems.
BRIEF SUMMARY OF THE DISCLOSURE
[0006] One aspect of the present disclosure includes a method for treating a chip packaging structure. The method includes providing a chip packaging structure having at least a first electrical connect structure and a second electrical connect structure, and an insulation layer insulating the first electrical connect structure and the second electrical connect structure and also exposing portions or all of the first electrical connect structure and the second electrical connect structure; and selecting a plasma gas based on materials of the first electrical connect structure and the second electrical connect structure and a type of process forming the first electrical connect structure and the second electrical connect structure, wherein metal cations are left on the insulation layer. Further, the method also includes performing a plasma treatment process using the selected plasma gas including one of at least oxygen and nitrogen on the first electrical connect structure, the second electrical connect structure and the insulation layer, causing reaction of the metal cations to substantially convert the metal cations into electrically neutral materials; and removing the reacted metal cations from the insulation layer.
[0007] Another aspect of the present disclosure includes a chip packaging structure. The chip packaging structure includes a substrate having a plurality of devices; and a metal interconnect structure electrically connecting with the devices formed on the substrate. Further, the chip packaging structure also includes at least one first electrical connect structure and one second electrical connect structure electrically connecting with the metal interconnect structure formed over the metal interconnect structure; and an insulation layer insulating the first electrical connect structure and the second electrical connect structure and also exposing portion or all of the first electrical connect structure and the second electrical connect structure, wherein the insulation has a material structure being treated by a plasma treatment process using a plasma gas, selected based on materials of the first electrical connect structure and the second electrical connect structure and a type of process forming the first electrical connect structure and the second electrical connect structure.
[0008] Other aspects of the present disclosure can be understood by those skilled in the art in light of the description, the claims, and the drawings of the present disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 illustrates a structure corresponding to certain stages of an exemplary treatment process of a chip packaging structure consistent with the disclosed embodiments;
[0010] FIG. 2 illustrates another structure corresponding to certain stages of the exemplary treatment process of a chip packaging structure consistent with the disclosed embodiments;
[0011] FIG. 3 illustrates another structure corresponding to certain stages of the exemplary treatment process of a chip packaging structure consistent with the disclosed embodiments; and
[0012] FIG. 4 illustrates the exemplary treatment process of a chip packaging structure.
DETAILED DESCRIPTION
[0013] Reference will now be made in detail to exemplary embodiments of the invention, which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
[0014] FIG. 4 illustrates an exemplary treatment process of a chip packaging structure; and FIG. 1 illustrates a structure corresponding to certain stages of the exemplary treatment process of a chip packaging structure.
[0015] At the beginning of the treatment process, a chip packaging structure is provided (S 101 ). As shown in FIG. 1 , a chip packaging structure 1 is provided. The chip packaging structure 1 may include a semiconductor substrate (not labeled), a metal interconnect structure 11 , an insulation layer 13 , a first electrical connect structure 121 and a second electrical connect structure 122 . In one embodiment, the first electrical connect structure 121 is a first solder pad 121 ; and the second electrical connect structure 122 is a second soldering pad 122 . A portion of the first soldering pad 121 and a portion of the second soldering pad 122 may be exposed by the insulation layer 13 . In certain other embodiments, the chip packaging structure 1 may have one electrical connect structure, or more than two electrical connect structures.
[0016] A plurality of semiconductor devices, such as transistors, resistors and inductors, etc., may be formed in and/or on the substrate. The first soldering pad 121 and the second soldering pad 122 may be electrically connected with the semiconductor devices through the metal interconnect structure 11 . The first soldering pad 121 and the second soldering pad 122 may be electrically insulated by the insulation layer 13 .
[0017] The substrate may be made of any appropriate material, such as Si, Ge, SiGe, or glass, etc. The insulation material of the metal interconnect structure 11 may be made of silicon oxide, silicon nitride, or silicon oxynitride, etc. The metal material of the metal interconnect structure 11 may be made of Cu, W, or Al, etc.
[0018] The insulation layer 13 may be made of any appropriate material, such as silicon oxide, silicon nitride, or silicon oxynitride, etc. In one embodiment, the insulation layer 13 may be a passive layer to prevent moisture, or contaminations, etc. Thus, the insulation layer 13 may be made of silicon nitride.
[0019] In certain other embodiments, the metal of the soldering pads may have a relatively large stress. The stress may cause the dielectric layer of the metal interconnect structure 11 to crack. Thus, in order to avoid the crack, the insulation layer 13 may be made of polyimide.
[0020] The first soldering pad 121 and the second soldering pad 122 may be formed by any appropriate process. In one embodiment, the first soldering pad 121 and the second soldering pad 122 may be formed by forming a metal layer (not labeled) on the metal interconnect structure 11 . The metal layer may be made of any appropriate material, such as Cu, or Al, etc. The metal layer may electrically connect with the metal interconnect structure 11 . After forming the metal layer, the metal layer may be patterned by any appropriate processes to form the first soldering pad 121 and the second soldering pad 122 . In one embodiment, the metal layer may be patterned by a dry etching process.
[0021] During the dry etching process, the by-products may not be entirely removed. Thus, the copper cations, metal losing a certain number of electrons, or the aluminum cations may be deposited on the insulation layer 13 . The metal cations deposited on the insulation layer 13 may cause a leakage current issue between the first soldering pad 121 and the second soldering pad 122 when the IC chip is in operation.
[0022] Returning to FIG. 4 , after providing the chip packaging structure 1 , a plasma gas may be selected for performing a plasma treatment process to remove the metal cations left on the insulation layer 13 (S 102 ). The plasma gas may selected based on materials of the first soldering pad 121 and the second soldering pad 122 and a type of process forming the first soldering pad 121 and the second soldering pad 122 . For example, if the first soldering pad 121 and the second soldering pad 122 are made of Cu, O 2 may be selected as the plasma gas. If the first soldering pad 121 and the second soldering pad 122 are made of Al, N 2 may be selected as the plasma gas.
[0023] Further, after selecting the plasma gas, a plasma treatment process may be performed (S 103 ). The corresponding structure is referred to FIG. 1 .
[0024] Referring to FIG. 1 , a plasma treatment process is performed on the first soldering pad 121 , the second soldering pad 122 , and the insulation layer 13 to remove the metal cations left on the insulation layer 13 . Specifically, selected plasma, i.e., plasma using the selected plasma gas may be used to bombard the first soldering pad 121 , the second soldering pad 122 , and the insulation layer 13 exposing the first soldering pad 121 and the second soldering pad 122 to remove the metal cations.
[0025] In one embodiment, the plasma gas is O 2 . Thus, the plasma may be referred as oxygen plasma. The O 2 pressure in the reaction chamber of the oxygen plasma may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the oxygen plasma may be in a range of approximately 900V˜1100V. The frequency of the oxygen plasma may be in a range of approximately 45 Hz˜55 Hz.
[0026] During the oxygen plasma treatment process, O 2 may be ionized into O ions and electrons “e”, etc. The O ions and the electrons may neutralize, and/or react with metal cations. The following reactions may happen:
[0000] Cu 2+ +O+2 e →Cu+O
[0000] Cu e+ +O+2 e →CuO
[0027] The metal Cu and the CuO may be electrically neutral. Thus, the metal Cu and the CuO may not have an electrostatic attraction with the insulation layer 13 ; and the metal Cu and the CuO may be easy to be removed from the surface of the insulation layer 13 . Further, the metal Cu and the CuO is not re-deposited on the insulation layer 13 . Thus, it may only need to pump the reaction chamber to remove the metal Cu and the CuO out the reaction chamber.
[0028] In one embodiment, the flow rate of O 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate may aid the generated O ions and/or electrons to react with the metal cations to form metal and/or metal compounds.
[0029] The plasma treatment time may be in a range of approximately 100 s˜150 s. In one embodiment, the treatment time is 120 s. Such a treatment time may not only entirely neutralize the metal cations to form metal and/or metal compounds, but also avoid damage to the surface of the insulation layer 13 during the bombarding process on the surfaces of the first soldering pad 121 , the second soldering pad 122 , and the insulation layer 13 .
[0030] In certain other embodiments, the plasma gas is N 2 . Thus, the plasma may be referred as nitrogen plasma. The pressure of N 2 in the reaction chamber of the nitrogen plasma may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the nitrogen plasma may be in a range of approximately 900V˜1100V. The frequency of the nitrogen plasma may be in a range of approximately 45 Hz˜55 Hz. The power of the nitrogen plasma may be in a range of approximately 270 W˜330 W.
[0031] In the nitrogen plasma treatment process, N 2 may be ionized into N ions and electrons “e”, etc. The N ions and the electrons “e” may have following reactions with the metal cations on the surface of the insulation layer 13 :
[0000] Al 3+ +N+3 e →Al+N
[0000] Al 3+ +N+3 e →AlN
[0032] The metal Al and the AlN may be electrically neutral. Thus, the metal Al and the AlN may have no electrostatic attraction with the insulation layer 13 ; and it may be easy for the metal Al and the AlN to leave the surface of the dielectric layer 13 . Further, the metal Al and the AlN is not re-deposited on the surface of the dielectric layer 13 . Thus, it may only need to pump the reaction chamber to remove the metal Al and the AlN out the reaction chamber.
[0033] In one embodiment, the flow rate of N 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate of N 2 may aid the N ions and the electrons generated by the plasma to react with the metal cations to form the metal Al and/or the AlN to remove the metal cations.
[0034] In one embodiment, the nitrogen plasma treatment time may be in a range of approximately 100 s˜150 s. Such a treatment time may not only neutralize the metal cations to form the metal and/or the metal compounds; but also avoid damage to the surface of the insulation layer 13 during the nitrogen plasma treatment process.
[0035] Returning to FIG. 4 , when the plasma treatment process is being performed, the reacted metal cations may be removed (S 104 ). The reacted metal cations are removed by pumping the reaction chamber.
[0036] After the plasma treatment process using one or more of O 2 and N 2 , the metal cations may be removed. Thus, the leakage issue between the first soldering pad 121 and the second soldering pad 122 may be overcome. Further, by using the oxygen plasma or the nitrogen plasma, the damage to the surface of the insulation layer 13 and the metal interconnect structure 11 may be avoided. Therefore, the reliability of the chip packaging structure 1 may be improved.
[0037] FIG. 2 illustrates another structure corresponding to a certain stage of the exemplary treatment process of a chip packaging structure illustrated in FIG. 4 . At the beginning of the treatment process, a chip packaging structure is provided (S 101 ).
[0038] As shown in FIG. 2 , a chip packaging structure 2 is provided. In one embodiment, the chip packaging structure 2 is formed by forming a second metal interconnect structure 14 on the chip packaging structure 1 illustrated in FIG. 1 ; and then forming a first electrical connect structure 151 and a second electrical connect structure 152 on the second metal interconnect structure 14 . In one embodiment, the first electrical connect structure 151 is a first re-distribution layer 151 ; and the second electrical connect structure 152 is a second re-distribution layer 152 . The first re-distribution layer 151 may be electrically connected with the first soldering pad 121 through the second metal interconnect structure 14 . The second re-distribution layer 152 may be electrically connected with the second soldering pad 122 through the second metal interconnect structure 14 .
[0039] Further, portions of the first re-distribution layer 151 and the second re-distribution layer 152 may be exposed by the insulation layer 13 . The insulation layer 13 may also electrically insulate the first redistribution layer 151 and the second re-distribution layer 152 . In certain other embodiments, the chip packaging structure 2 may include one re-distribution layer, or more than two re-distribution layers.
[0040] The first re-distribution layer 151 and the second re-distribution layer 152 may be used to electrically re-distribute the first soldering pad 121 and the second soldering pad 122 . Specifically, the positions of the first soldering pad 121 and the second soldering pad 122 and the distance between the first soldering pad 121 and the second soldering pad 122 may be re-arranged by the first re-distributing pad 151 and the second re-distributing pad 152 . Such as re-distribution may increase the device density in the chip packaging structure 2 .
[0041] The insulation material of the second metal interconnect structure 14 may be made of silicon oxide, silicon nitride, or silicon oxynitride, etc. The metal material of the second metal interconnect structure 14 may be made of Cu, W, or Al, etc.
[0042] The insulation layer 13 may be made of any appropriate material, such as silicon oxide, silicon nitride, or silicon oxynitride, etc. In one embodiment, the insulation layer 13 may be a passive layer to prevent moisture, or contaminations, etc. Thus, the insulation layer 13 may be made of silicon nitride.
[0043] In certain other embodiments, the metal of the soldering pads may have a relatively large stress. The stress may cause the dielectric layer in the metal interconnect structure 13 to crack. Thus, in order to avoid the crack, the insulation layer 13 may be made of polyimide.
[0044] The first re-distribution layer 151 and the second re-distribution layer 152 may be formed by any appropriate process. In one embodiment, the first re-distribution layer 151 and the second re-distribution layer 152 may be formed by forming a metal layer (not labeled) on the second metal interconnect structure 14 . The metal layer may be made of one of Cu and Al, etc. The metal layer may be electrically connected with the second metal interconnect structure 14 . After forming the metal layer, the metal layer may be patterned by any appropriate processes to form the first re-distribution layer 151 and the second re-distribution layer 152 . In one embodiment, the metal layer may be patterned by a dry etching process.
[0045] During the dry etching process, the by-products may not be entirely removed. Thus, copper cations or aluminum cations may be deposited on the insulation layer 13 . The metal cations deposited on the insulation layer 13 may cause a leakage issue between the first re-distribution layer 151 and the second re-distribution layer 152 .
[0046] Returning to FIG. 4 , after providing the chip packaging structure 1 , a plasma gas may be selected for performing a plasma treatment process to remove the metal cations left on the insulation layer 13 (S 102 ). The plasma gas may selected based on materials of the first re-distribution layer 151 and the second redistribution layer 152 and a type of process forming the first re-distribution layer 151 and the second re-distribution layer 152 . For example, if the first re-distribution layer 151 and the second re-distribution layer 152 are made of Cu, O 2 may be selected as the plasma gas. If the first re-distribution layer 151 and the second re-distribution layer 152 are made of Al, N 2 may be selected as the plasma gas.
[0047] Further, after selecting the plasma gas, a plasma treatment process may be performed (S 103 ). The corresponding structure is referred to FIG. 2 .
[0048] Referring to FIG. 2 , after providing the chip packaging structure 2 , a plasma treatment process is performed on surface of the chip packaging structure 2 . Specifically, selected plasma may be used to bombard the first re-distribution layer 151 , the second re-distribution layer 152 and the insulation layer 13 exposing first re-distribution layer 151 and the second re-distribution layer 152 .
[0049] In one embodiment, the plasma gas is O 2 . Thus, the plasma may be referred as oxygen plasma. The O 2 pressure in the reaction chamber of the oxygen plasma treatment process may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the plasma may be in a range of approximately 900V˜1100V. The frequency of the oxygen plasma may be in range of approximately 45 Hz˜55 Hz.
[0050] During the oxygen plasma process, the O 2 may be ionized into O ions and electrons “e”, etc. The O ions and the electrons “e” may react with metal cations. The following reactions may happen:
[0000] Cu 2+ +O+2 e →Cu+O
[0000] Cu 2+ +O+2 e →CuO
[0051] The metal Cu and the CuO may be electrically neutral. Thus, the metal Cu and the CuO may not have an electrostatic attraction with the insulation layer 13 ; and the metal Cu and the CuO may be easy to be removed from the surface of the insulation layer 13 . Further, the metal Cu and the CuO is not re-deposited on the insulation layer 13 . Thus, it may only need to pump the reaction chamber to remove the Cu and the CuO out the reaction chamber.
[0052] In one embodiment, the flow rate of O 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate may aid the generated O ions and/or electrons to react with the metal cations to form the metal and/or the metal compounds.
[0053] The oxygen plasma treatment time may be in a range of approximately 100 s˜150 s. In one embodiment, the oxygen plasma treatment time is 120 s. Such a treatment time may not only entirely neutralize the metal cations to form metal and/or metal compounds, but also avoid damage to the surface of the insulation layer 13 during the bombarding process on the surface of the insulation layer 13 .
[0054] In certain other embodiments, the gas of the plasma is N 2 . Thus, the plasma may be referred as nitrogen plasma. The pressure of N 2 in the reaction chamber may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the nitrogen plasma may be in a range of approximately 900V˜1100V. The frequency of the nitrogen plasma may be in a range of approximately 45 Hz˜55 Hz. The power of the nitrogen plasma may be in a range of approximately 270 W˜330 W.
[0055] In the nitrogen plasma treatment process, N 2 may be ionized in to N ions and electrons “e”, etc. The N ions and the electrons “e” may have following reactions with the metal cations on the surface of the insulation layer 13 :
[0000] Al 3+ +N+3 e →Al+N
[0000] Al 3+ +N+3 e →AlN
[0056] The metal Al and the AlN may be electrically neutral. Thus, the metal Al and the AlN may have no electrostatic attraction with the insulation layer 13 ; and it may be easy for the metal Al and the AlN to leave the surface of the dielectric layer 13 . Further, the metal Al and the AlN may not be re-deposited on the surface of the dielectric layer 13 . Thus, it may only need to pump the reaction chamber to remove the metal Al and the AlN out the reaction chamber.
[0057] In one embodiment, the flow rate of N 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate of N 2 may aid the N ions and the electrons generated by the nitrogen plasma to react with the metal cations to form the metal Al and/or the AlN.
[0058] In one embodiment, the nitrogen plasma treatment time may be in a range of approximately 100 s˜150 s. Such a treatment time may not only neutralize the metal cations to form the metal and/or the metal compounds; but also avoid the damage to the surface of the insulation layer 13 during the nitrogen plasma treatment process.
[0059] Returning to FIG. 4 , when the plasma treatment process is being performed, the reacted metal cations may be removed ( 104 ). The reacted metal cations is removed by pumping the reaction chamber
[0060] After the plasma treatment process using one of O 2 and N 2 , the metal cations on the insulation layer 13 may be removed. Thus, the leakage current issue between the first re-distribution layer 151 and the second re-distribution layer 152 may be overcome. Further, by using the O 2 plasma or the N 2 plasma, the damage to the surface of the insulation layer 13 may be avoided. Therefore, the reliability of the chip packaging structure 2 may be improved.
[0061] FIG. 3 illustrates another structure corresponding to certain stages of the exemplary treatment process of a chip packaging structure illustrated in FIG. 4 . At the beginning of the treatment process, a chip packaging structure is provided (S 101 ).
[0062] As shown in FIG. 3 , a chip packaging structure 3 having a first electrical connect structure 171 and a second electrical connect structure 172 is provided. In one embodiment, the first electrical connect structure 171 may be a first soldering ball 171 ; and the second electrical connect structure 172 may be a second soldering ball 172 . In certain other embodiments, the number of the soldering balls may be more than two.
[0063] In one embodiment, the chip packaging structure 3 may be formed by forming certain structures on the chip packaging structure 1 illustrated in FIG. 1 . Referring to FIG. 1 and FIG. 3 , a first under-ball metal (UBM) layer 161 may be formed on the first soldering pad 121 and a portion of the insulation layer 13 . Further, a second under ball metal (UBM) layer 162 may be formed on the second soldering pad 122 and a portion of the insulation layer 13 . Further, after forming the first UBM layer 161 and the second UBM layer 162 , a first soldering ball (bump) 171 may be formed on the first UBM layer 161 ; and a second soldering ball 172 may be formed on the second UBM layer 162 .
[0064] The first soldering ball 171 may be electrically connected with the first solder pad 121 through the first UBM layer 161 ; and the second soldering ball 172 may be electrically connected with the second soldering pad 122 through the second UBM layer 162 . The insulation layer 13 may electrically insulate the first soldering pad 121 and the second solder pad 122 , the first UBM layer 161 and the second UBM layer 162 ; and the first soldering ball 171 and the second soldering ball 172 .
[0065] The insulation layer 13 may be made of any appropriate material, such as silicon oxide, silicon nitride, or silicon oxynitride, etc. In one embodiment, the insulation layer 13 may be a passive layer to prevent moisture, or contaminations, etc. Thus, the insulation layer 13 may be made of silicon nitride.
[0066] In certain other embodiments, the metal of the soldering pads may have a relatively large stress. The stress may cause the dielectric layer of the metal interconnect structure 13 to crack. Thus, in order to avoid the crack, the insulation layer 13 may be made of polyimide.
[0067] The first UBM layer 161 and the second UBM layer 162 may be formed by any appropriate process. In one embodiment, the UBM layer 161 and the second UBM layer 162 may be formed by forming a metal layer (not labeled) on the first soldering pad 121 , the second soldering pad 122 and the insulation layer 13 . The metal layer may electrically connect with the first soldering pad 121 and the second soldering pad 122 . After forming the metal layer, the metal layer may be patterned by any appropriate processes to form the first UBM layer 161 and the second UBM layer 162 . In one embodiment, the metal layer may be patterned by a dry etching process.
[0068] The metal layer may be made of Ti or Cu, etc. During the dry etching process, the by-products may not be entirely removed. Thus, Ti cations or Cu cations may be deposited on the surface of the insulation layer 13 . Further, the first soldering ball 171 and the second soldering ball 172 may be made of Cu, Sn, or Ag, etc. Thus, during the process for forming the first soldering ball 171 and the second soldering ball 172 , Cu cations, Sn cations, or Ag cations may also be formed on the insulation layer 13 . The metal cations deposited on the insulation layer 13 may cause a leakage issue between the first soldering ball 171 and the second soldering ball 172 .
[0069] In certain other embodiments, the first soldering ball 171 and the second soldering ball 172 may be formed on the chip packaging structure 2 illustrated in FIG. 2 . Correspondingly, the first UBM layer 161 may be formed on the first re-distribution layer 151 ; and the second UBM layer 162 may be formed on the second re-distribution layer 152 . Then, the first soldering ball 171 may be formed on the first UBM layer 161 ; and the second soldering ball 172 may be formed on the second re-distribution layer 152 . Such a chip packaging structure may increase the device density. Similarly, metal cations may be formed on the insulation layer 13 during the processes for forming the first UBM layer 161 , the second UBM layer 162 , the first soldering ball 171 and the second soldering ball 172 . The metal cations may cause a leakage current issue between the first soldering ball 171 and the second soldering ball 172 .
[0070] Returning to FIG. 4 , after providing the chip packaging structure 1 , a plasma gas may be selected for performing a plasma treatment process to remove the metal cations left on the insulation layer 13 (S 102 ). The plasma gas may selected based on materials of the first UBM layer 161 , the second UBM 162 , the first soldering ball 171 and the second soldering ball 172 and a type of process forming the first UBM layer 161 , the second UBM 162 , the first soldering ball 171 and the second soldering ball 172 . For example, if the first UBM layer 161 , the second UBM 162 , the first soldering ball 171 and the second soldering ball 172 are made of Cu, Sn, Ti or Ag, O 2 may be selected as the plasma gas. If the first UBM layer 161 , the second UBM 162 , the first soldering ball 171 and the second soldering ball 172 are made of Al, or Ti, N 2 may be selected as the plasma gas.
[0071] Further, after selecting the plasma gas, a plasma treatment process may be performed ( 103 ). The corresponding structure is referred to FIG. 2 .
[0072] Referring to FIG. 3 , a plasma treatment process is performed on the surface of the chip packaging structure 3 to remove the metal cations. Specifically, selected plasma, i.e., plasma using the selected plasma gas, may be used to bombard the first soldering ball 171 , the second soldering ball 172 , and the insulation layer 13 .
[0073] In one embodiment, the plasma gas is O 2 . Thus, the plasma may be referred as oxygen plasma. The O 2 pressure in the reaction chamber of the oxygen plasma treatment process may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the oxygen plasma may be in a range of approximately 900V˜1100V. The frequency of the oxygen plasma may be in range of approximately 45 Hz˜55 Hz.
[0074] During the oxygen plasma process, the O 2 may be ionized into O ions and electrons “e”, etc. The O ions and the electrons “e” may react with metal cations. The following reactions may happen:
[0000] Cu 2+ +O+2 e →Cu+O
[0000] Cu 2+ +O+2 e →CuO
[0075] The metal Cu and the CuO may be electrically neutral. Thus, the metal Cu and the CuO may not have an electrostatic attraction with the insulation layer 13 ; and the metal Cu and the CuO may be easy to be removed from the surface of the insulation layer 13 . Further, the metal Cu and the CuO are not re-deposited on the insulation layer 13 . Thus, it may only need to pump the reaction chamber to remove the Cu and the CuO.
[0076] In certain other embodiments, if the first soldering ball 171 and the second soldering ball 172 are made of Sn, or Ag, corresponding metal and metal oxide may be formed during the plasma treatment process; and may be removed by pumping the reaction chamber. Further, the Ti cations caused by the process for forming the first UBM layer 161 and the second UBM layer 162 may be also be removed by the oxygen plasma treatment process.
[0077] In one embodiment, the flow rate of O 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate may aid the generated O ions and electrons to react with the metal cations to form the metal and/or the metal compounds.
[0078] The oxygen plasma treatment time may be in a range of approximately 100 s˜150 s. In one embodiment, the treatment time is 120 s. Such a treatment time may not only ensure entirely neutralize the metal cations to form metal and/or metal compounds, but also avoid damage to the surface of insulation layer 13 during the process for bombarding first soldering ball 171 , the second soldering ball 171 , and the insulation layer 13 .
[0079] In certain other embodiments, the gas of the plasma is N 2 . Thus, the plasma may be referred as nitrogen plasma. The pressure of N 2 in the reaction chamber may be in a range of approximately 1E10 −9 Pa˜1E10 −6 Pa. The voltage of the nitrogen plasma may be in a range of approximately 900V˜1100V. The frequency of the nitrogen plasma may be in a range of approximately 45 Hz˜55 Hz. The power of the nitrogen plasma may be in a range of approximately 270 W˜330 W.
[0080] In the nitrogen plasma treatment process, N 2 may be ionized into N ions and electrons “e”, etc. The N ions and the electrons “e” may neutralize the Sn ions, Cu ions, Ti ions or Ag ions, etc., to form neutral metal or metal nitride, etc. The metal and the metal nitride may have no electrostatic attraction with the insulation layer 13 ; and it may be easy for the metal and the metal nitride to leave the surface of the insulation layer 13 . Further, the metal and the metal nitride are not re-deposited on the surface of the insulation layer 13 . Thus, it may only need to pump the reaction chamber to remove the metal and the metal nitride out the reaction chamber.
[0081] In one embodiment, the flow rate of N 2 may be in a range of approximately 5 sccm˜25 sccm. Such a flow rate of N 2 may aid the N ions and the electrons generated by the nitrogen plasma process to react with the metal cations to form the metal and the metal nitride.
[0082] In one embodiment, the nitrogen plasma treatment time may be in a range of approximately 100 s˜150 s. Such a treatment time may not only neutralize the metal cations to form the metal and/or the metal compounds; but also avoid damage to the surface of insulation layer 13 during the plasma treatment process.
[0083] Returning to FIG. 4 , when the plasma treatment process is being performed, the reacted metal cations may be removed ( 104 ). The reacted metal cations are removed by pumping the reaction chamber
[0084] After the plasma treatment process using one of O 2 and N 2 , the metal cations may be removed. Thus, the leakage current issue between the first soldering ball 171 and the second soldering ball 172 may be overcome. Further, by using the oxygen plasma or the nitrogen plasma, the damage to the surface of the insulation layer 13 may be avoided. Therefore, the reliability of the chip packaging structure may be improved.
[0085] Returning FIG. 4 , after the plasma treatment process, further processes may be performed, such as a wire bonding process, or a soldering process, etc. Then, molding compound may be applied on the chip packaging structure to sealing the devices, the wire, and soldering structures, etc.
[0086] Thus, a chip packaging structure may be formed by the above disclosed processes and methods; and the corresponding semiconductor structure is illustrated in FIG. 3 . As shown in FIG. 3 , the chip packaging structure may include a substrate (not labeled) and a metal interconnect structure 11 electrically connecting with devices in the substrate formed on the substrate. The chip packaging structure may also include a first soldering pad 121 and a second soldering pad 122 electrically connecting with the metal interconnect structure 11 formed on the first interconnect structure 11 ; and an insulation layer 13 electrically insulating the first soldering pad 121 and the second soldering pad 122 formed on the first metal interconnect structure 11 . The insulation layer 13 is treated by oxygen plasma or nitrogen plasma to remove the metal cations on the surface. Further, the chip packaging structure may include a first UBM layer 161 formed on the first soldering pad 121 , and a second UBM layer 162 formed on the second soldering pad 122 . Further, the chip packaging structure may also include a first soldering ball 171 formed on the first UBM layer 161 ; and a second soldering ball 172 formed on the second UBM layer 162 . The detailed structures and intermediate structures are described above with respect to the fabrication and treatment processes.
[0087] Therefore, according to the disclosed methods and structures, instead of using ordinary argon plasma, oxygen plasma or nitrogen plasma may be used to bombard the plurality of electrical connect structures and the insulation layer exposing the electrical connect structure. During the plasma treatment process, oxygen ions and electrons or nitrogen ions and electrons may neutralize and/or react with the metal cations deposited on the insulation layer during the packaging process. Thus, metal atoms and/or metal compounds may be formed. The metal atoms and the metal compounds may be electrically neutral. Thus, the metal atoms and/or the metal compounds may have no electrostatic attraction with the insulation layer; and it may be easy for the metal atoms and/or the metal compounds to leave the surface of the insulation layer. Further, it is not easy for the metal and/or the metal compounds to be re-deposited on the insulation layer. Thus, it may only need to pump the reaction chamber to remove the metal atoms and/or the metal compounds out the reaction chamber.
[0088] Further, the electrical connect structures may include any appropriate structures, such as soldering pads, re-distribution layers, under-ball metal layers, and soldering balls, etc. Metal ions may be formed on the insulation layer during the process for forming any of such structures. Thus, the plasma treatment process may be performed on one or more of such structures and the insulation layer to neutralize the metal cations to form metal atoms and/or metal compounds. After the plasma treatment process using the oxygen plasma or the nitrogen plasma, the metal cations formed on the insulation layers may be removed; and the surface of the insulation layer may not be damaged. Therefore, the leakage current issue between the electrical connect structures may be overcome; and the reliability of the chip packaging structure may be improved.
[0089] The above detailed descriptions only illustrate certain exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention. Those skilled in the art can understand the specification as whole and technical features in the various embodiments can be combined into other embodiments understandable to those persons of ordinary skill in the art. Any equivalent or modification thereof, without departing from the spirit and principle of the present invention, falls within the true scope of the present invention. | A method for treating a chip packaging structure includes providing a chip packaging structure having at least a first electrical connect structure and a second electrical connect structure, and an insulation layer exposing portions of the first electrical connect structure and the second electrical connect structure; selecting a plasma gas based on materials of the first electrical connect structure and the second electrical connect structure and a type of process forming the first electrical connect structure and the second electrical connect structure, wherein metal cations are left on the insulation layer; performing a plasma treatment process using the selected plasma gas on the first electrical connect structure, the second electrical connect structure and the insulation layer, causing reaction of the metal cations to substantially convert the metal cations into electrically neutral materials; and removing the reacted metal cations from the insulation layer. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to computer software. More specifically, the present invention relates to computer software applications configured to facilitate the interactive design of three-dimensional (3D) models of utility networks.
2. Description of the Related Art
Currently, computer aided design (CAD) applications allow a designer or engineer to compose graphical representations of utility networks. For example, a user interacting with a CAD application may generate a model of a utility network by drawing simple 2D objects to represent components such as pipes, conduits, manhole covers, etc. Common 2D drawing objects include simple lines and arcs, etc. Additionally, some CAD applications may provide groupings of 2D objects used to model certain real-world structures (e.g., a collection of lines and ellipses to represent a cylinder). The user positions these 2D drawing objects relative to one another to generate the graphical representation of the utility network.
Additionally, a given 2D drawing object may be displayed with a label that presents information regarding the real-world component being represented by the 2D drawing object. Such attributes may be part of engineering and construction documentation generated from the 2D drawing. For example, a line representing a pipe may be displayed with a label that provides attributes such as the diameter, length, inner diameter etc., of the pipe.
Typically, the user of a CAD application will create many different views to represent the same utility network from different perspectives. For example, a plan view may provide a “top-down” perspective and a profile view may provide a cross-sectional perspective of the utility network. To modify the utility network represented by the 2D drawing objects, the designer or engineer may have to edit one or more of the 2D drawing objects within an individual view. For example, if a user changes the diameter of a 2D graphical object representing a pipe displayed in a profile view, the user may also have to determine what other changes have to be made to the 2D drawing objects in the profile view to account for this modification. Further, the user must also make similar modifications to other views, such as a plan view. The editing process is thus quite tedious and labor intensive.
Furthermore, the 2D graphics objects such as lines and curves only provide a crude representation of the network parts and thus the utility network and do not adequately describe or portray the actual real-world parts being used to construct the utility network. As stated, users often compose 2D graphical models to generate engineering and construction documentation. For example, a user may compose a plan view that includes labels or annotations that indicate the size, type, manufacturer, model number, etc. for a particular utility network component. In addition to the requirement that multiple views may have to be modified to reflect a desired change, a user may also have to update the labels or annotations provided with a given view. Because modifications to 2D drawing objects (and any attributes or annotation labels) must be replicated individually within each view, the process is both time consuming and error-prone.
Accordingly, the crude 2D drawing objects fail to reflect the real-world characteristics of utility network components. Moreover, because views are created independently from one another, any changes made for one view requires other views to be updated individually.
SUMMARY OF THE INVENTION
Embodiments of the invention provide a method, apparatus, and article of manufacture that allows for the efficient composition of three-dimensional models (3D models) of a utility network. In one embodiment, a 3D model may be composed from many virtual network part objects (or more simply, just “parts”). This allows a utility network to be modeled as a set of inter-connected network parts representing, for example, pipes, wires, conduit, manholes, catch basins, pumps, valves, transformers, etc., rather than as a set of 2D drawing objects. Network parts may be associated with a set of properties related to both an individual part and to other parts connected together throughout the topology of the utility network. Part objects in the 3D model may be aggregated to include surrounding part objects, allowing the aggregation to be managed as an interconnected group.
The parts available for a given 3D model are provided through a network part list, and part connectivity among network parts is established through part placement. Part placement is the process where a user specifies 3D coordinates to position a network part in the 3D model. In one embodiment, a user places a network part in an approximate location using drag-and-drop techniques, and the CAD application may be configured to calculate a final position based on the “drop” location and any rules specified for a particular network part or 3D model.
Depending on the application, network parts used to compose the 3D model may be developed specifically for a given project or may be selected from an external catalog and configured for a given project. For example, a project may specify a known set of pipe sizes and structures that have been approved for the project. Network parts corresponding to these real-world components may be made available to the user through the network part list. In addition, parts may also be grouped into families (e.g. 10″, 12″, and 14″ pipe available form a common supplier).
Part rules for layout and editing behavior may be defined, and the exact look and feel (e.g. part texturing and shading) required for construction documents may specified as parts are added into the model. Layout and editing jigs may be provided to guide a user in placing a particular part within a 3D model. For example, a 12″ pipe may be placed with a new catch basin structure, or the pipe may be connected to an existing structure in the model if user input occurs at or near the existing structure in the 3D model.
As parts are placed within the 3D model, automated resizing of structures already present in the 3D model occurs to match these structures with the newly added network parts. For example, a pipe length may be adjusted to maintain a connection with a catch basin structure. During part layout, part selection may be made from a predefined list of network parts, and layout jigs may be provided to guide user input for part placement and part connectivity. Regardless of the active view used to modify and add network parts, the underlying 3D model remains active throughout the editing process. For each part inserted into a utility network model, the CAD application may be configured to generate a graphical representation that is sized and shaped to approximate the real-world part and to connect it with other network parts in the model.
In addition, modifications made to a selected network part may be translated throughout the utility network, and to any view of the utility network generated from the 3D model. For example, catch basins and manholes typically connect to surrounding pipes and have intrinsic properties such as height, diameter, material, etc. and also include properties that reflect the connected pipes (e.g., each connected pipe has a size, inflow or outflow, direction etc.). When a user modifies the attributes or position of a network part within a utility network, interconnected parts may also move automatically, and the pipe end points may shift position to maintain connectivity and relative position. At the same time, data attributes corresponding to these parts may be updated to reflect modifications made to the network part. Further, one part may itself be provided as a composite of other parts, such as a catch basin composed from a barrel, collar, cap, and manhole cover.
The combined set of properties may be managed as a single property set which may be queried and displayed on the a graphical user interface (GUI) of the CAD application, exported as data for regarding one or more connected parts, or displayed on labels generated in construction documentation.
Additionally, a completed 3D model may be used to generate 2D construction and engineering documentation related to the model reflecting the attributes and properties of the parts included in the 3D model. Embodiments of the invention improve upon how parts are represented graphically, how parts are provided to users of a CAD application for composing the 3D model, and improve the reliability and speed of editing or revising 2D construction and engineering documentation. Thus, embodiments of the invention speed access to part editing and display of connected part properties and provide automatic updating of all views of the utility network as the utility model is changed (e.g., pipes added or removed, resized, moved to new orientation or depth. etc.). Editing of the model may be performed from any view thereof (e.g., a plan, a model or a profile view) and the results will automatically be reflected in other views of the utility network, without the user intervention required by current systems.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram illustrating a system for composing a 3D computer model of a utility network, according to one embodiment of the invention.
FIG. 2 is a block diagram illustrating data elements used to define a network part that may be added to 3D model of a utility network, according to one embodiment of the invention.
FIG. 3 illustrates an exemplary graphical representation of a network part.
FIG. 4 is a block diagram illustrating data elements used to define a 3D model of a utility network, according to one embodiment of the invention.
FIG. 5 illustrates a 3D model of a utility network, according to one embodiment of the invention.
FIG. 6 illustrates a profile view of a utility network, according to one embodiment of the invention.
FIG. 7 illustrates a method for composing a 3D model of a utility network, according to one embodiment of the invention.
FIG. 8 illustrates a method for modifying the attributes of a utility network, according to one embodiment of the invention.
FIG. 9 illustrates a method for generating engineering or construction documentation from a 3D model of a utility network, according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention provide a method, apparatus, and article of manufacture for creating a computer-generated three-dimensional model (3D model) of a utility network that is composed from many network part objects (or more simply, just “parts”). Each part inserted into a 3D model may correspond to a real-world component of a utility network. For example, embodiments of the invention may be used to model a utility network such as a gravity pipe system, etc using network parts such as pipes, manholes, catch basins and storm sewers. However, embodiments of the invention are not limited to modeling utility networks of any single type and may be extended to other utility networks. For example, embodiments of the invention described herein may be adapted to model utility networks such as telecommunications networks, pipeline networks, power grid networks etc.
In one embodiment, users of a CAD application may be provided with a catalog of network parts or part families that may be used to compose the 3D model. The CAD application may be configured to allow a user to dynamically size and resize the network parts within the 3D model. Typically, the network parts themselves, represent real-world constructs (e.g., pipes, catch basins, manholes, etc.). Further, many 2D graphical views may be generated using a 3D model, such as various, plan, profile, and section views.
When the properties for one part are modified, other parts in the 3D model may be automatically updated. Any part visible from a given view may be selected and modified. When a user modifies a part within one view, other views are also dynamically updated to reflect these modifications. Similarly, the attributes and annotations regarding a given part may be modified from a single view, and every view of the model that includes the part may also be updated without requiring any further actions by the user.
FIG. 1 is a functional block diagram illustrating an exemplary CAD environment 100 for generating a 3D computer model 120 of a utility network. In one embodiment, the components illustrated in environment 100 include computer software applications executing on existing computer systems, e.g., desktop computers, server computers, laptop computers, tablet computers, and the like. The software applications described herein, however, are not limited to any currently existing computing environment or programming language, and may be adapted to take advantage of new computing systems as they become available.
Additionally, the components illustrated in FIG. 1 may be executing on distributed systems communicating over computer networks including local area networks or large, wide area networks, such as the Internet. For example, a graphical user interface 110 may include a software program executing on a client computer system communicating with a CAD application 105 and a network parts catalog 130 residing on a networked server computer.
As shown, the CAD environment 100 includes, without limitation, CAD application program 105 , graphical user interface 110 , 3D model 120 , user input devices 145 , display device 115 , and network parts catalog 130 .
In one embodiment, the CAD application 105 is a computer program configured to allow a user interacting with GUI interface 110 to generate a 3D model 120 . Preferably, the Civil 3D® application program and associated utilities available from Autodesk®, Inc. may be used. CAD application 105 stores the all the data, attributes, properties, and geometry data regarding to the real world structure being modeled in 3D model 120 .
The graphical user interface 110 may provide GUI elements that allow a user to select, add, and modify the network parts (and part attributes) included in the 3D model 120 . As a user specifies the characteristics of the utility network being modeled, 3D display device 115 provides a visual representation of the 3D model 120 . The data for the 3D model 120 may be used as to generate the various views or graphical representations of the 3D model 120 as well as to generate 2D engineering and construction documentation for the 3D model 120 . Although distinct from one another, each view (e.g., profile, plan or a cross-section view) is generated from a common set of network parts data. Input devices 145 allow a user to interact with the 3D model 120 and GUI interface 110 . Typically, user input devices 145 include a mouse pointing device and a keyboard, and display device 115 is a CRT monitor or LCD display.
The network parts catalog 130 provides a master collection of parts available for use in composing a 3D model 120 of a utility network. Parts in the catalog may be fixed, single-size parts or part of a parametric part family. Each network part in catalog 130 provides an individual component that may be selected as an entity for inclusion in 3D model 120 . Importantly, parts may themselves be defined as a composite of multiple parts that may be managed as a single entity.
In one embodiment, the parts catalog 130 may include network parts representing the pipes, structures, and fittings of a gravity based utility network. A “pipe” is a network part serving to move fluids from one point to another. In one embodiment, the CAD application 105 models a pipe network part by sweeping the cross-sectional shape of the pipe along a base curve, which may be a line for a straight pipe, or a more complex curve. Examples of “pipe” network parts include: circular pipes, elliptical pipes, rectangular pipes, egg-shaped pipes, etc. “Pipe” network parts may be used to connect structures, and a “structure” is a network part serving a specific engineering function in the system. Examples of “structure” network parts include manholes, catch basins, headwalls, flared end sections, etc. “Fittings” and “junctions” are network parts serving to branch pipe flow or alter flow direction, examples include, elbow, Wye, tee, cross, etc. To model other utility networks, a different parts catalog may be provided.
In one embodiment, a 3D model 120 may include data representing one or more utility networks. In turn, each utility network may be constructed using a collection of network part elements. Further, in some cases a given network part element may itself comprise a composite of two or more network parts that may be manipulated by a user as a single entity. Each of these elements used to construct a 3D model of a utility network is discussed more fully below in FIGS. 2-4 .
FIG. 2 is a block diagram 200 illustrating data elements used to define a network part that may be added to 3D model of a utility network, according to one embodiment of the invention. Illustratively, network part 210 may include data elements such as network part size data 220 , part connection data 230 , part sub components 240 and part body 250 . Each network part 210 may be defined using some or all of these data elements ( 220 - 250 ). Further, each network part reflects properties of the real-world object corresponding to the part. Therefore, the 3D model 120 composed from the network parts has characteristics mirroring those of a real world utility network.
The part size data 220 may include a data record used to store all size parameters and location parameters of a network part 210 that has been added to a 3D model 120 . The part size data may be fixed for a given network part or may be parametric. For example, parametric data may include size values selected from a pre-defined list or selected from a given range. Alternatively, multiple parameters may be grouped in a table and be selected together as a row, or size values may be defined as a calculation dependent on other parameter values.
Once a network part 210 is integrated into a particular 3D model 120 , part connection data may be used to manage connections between the parts 210 and other parts in the 3D model 120 . For example, each network part 210 may have one or more connections to other parts in the 3D model. In one embodiment, a network part 210 may itself be composed of other network parts. Accordingly, subcomponent data 240 may provide a list of one or more other parts integrated as a single entity. Such a network part may be provided by the catalog 120 . Alternatively, the user interface 110 may allow users to group multiple network parts together, and subsequently manipulate the group as a single network part entity.
The part body 250 provides a 3D graphical image representing the part that may be used in the 3D model. The part body 250 may also include model data such as part-part interference, part volume, connection rules, etc. In one embodiment, the graphical representation may include data defining a bounding shape that provides an approximate 3D body representing the part as a cylinder, box, or spherical solid, or an indication of a routine used to generate the approximate 3D body from part size data 220 . The graphical representation provides an approximation of the real world appearance of a particular network part. Additionally, one individual part may itself be composed from other parts provided by the parts catalog 130 .
FIG. 3 shows a graphical representation of a catch basin 300 defined as a composite of other network parts, including a barrel section 310 , an eccentric barrel cap 320 , and a manhole cover 325 . Additionally, the barrel section 310 includes inlet/outlet ports 330 and 340 . Each of these components may itself be a network part that may be individually manipulated. Further, the catch basin 300 may be selected as a composite network part and inserted into a 3D model 120 . The coordinates in the 3D model where the catch basin 300 is inserted may be selected by the user creating the utility model. When placed at a particular location, the user may also select to connect the catch basin 300 with other network parts already present in the 3D model. For example, a user may specify an existing pipe structure be connected to inlet 330 . In doing so, the size and position of the existing pipe structure may be modified by the CAD application 105 to reflect the new connection.
FIG. 4 is a block diagram illustrating data elements used to define a 3D model 120 , according to one embodiment of the invention. The 3D model 120 includes one or more utility network systems 410 , each including the network parts of the particular utility network being modeled. In one embodiment, the individual network parts allow a user to compose a 3D model 120 of a utility network from individual parts, much like a real-world utility network. Regardless of the particular utility network, each network system 410 includes a collection of inter-connected parts. In addition, the 3D model 120 includes model geometry 450 , terrain model 460 , and network parts list 470 .
Network parts list 470 may indicate a collection of parts 3D that may be used to compose a particular utility network 410 . Depending on the real-world utility network being modeled, network parts list 470 may be used to limit the parts available for inclusion in a particular 3D model 120 . In addition, as the 3D model 120 provides a graphical representation of a corresponding to a real world utility network, the model geometry 450 and terrain model data 460 may define the geography present for a particular location. Typically, the geography represents the real-world location being modeled. Depending on the application, a 3D model may include one or more terrain models 470 and geometry data 460 that may each be used to represent sections of both existing ground surfaces (and sub-surfaces).
FIG. 5 illustrates a portion of a 3D model utility network composed from a collection of network parts 310 , according to one embodiment of the invention. In this example, the view 500 in FIG. 5 , illustrates a 3D view of a model 120 zoomed in to focus on a catch basin 400 and pipe 510 . Perspective indicator 520 indicates that the view 500 illustrates the 3D model 120 from a 3D perspective using the X and Y axes to represent a grid-based location of a part element in the 3D model and the Z axis to represent an elevation. Any of the catch basin elements may be selected and modified, or other parts may be selected and added to the 3D model. For example, a user may click on one more components of the catch basin 400 , or may select individual components from the list. Illustratively, barrel section 410 has been selected, as indicated by the dashed lines. The catch basin 300 also includes an outlet port 440 , an eccentric barrel cap 420 and a manhole cover 425 , corresponding to the same elements from Fig. 3 . The view 500 also displays part label annotation 530 for the catch basin 400 . The part label corresponds to the network part data for barrel section 410 . The annotation 530 displays parametric values 540 selected for this network part, along with instance data specifying the location 550 of the catch basin 400 in a particular 3D model. This data may be included in documentation generated for the 3D model. Further, by modifying any of these values, the user can alter the 3D model without having to manually edit the graphical representation provided for catch basin 400 , or having to edit the same network part in multiple views.
FIG. 6 illustrates a profile view 600 of a utility network composed from a collection of network parts, according to one embodiment of the invention. The profile view 600 may be generated directly from the network parts present in 3D model 120 . Thus, the 2D profile view 600 is generated from the same collection of network parts (e.g., structures 420 , fittings 430 and pipes 440 ) included in the 3D model 120 . Further, a 2D view created from the 3D model may be easily edited by changing the attributes associated with a network part, or by changing data values associated with an instance of the network part within the 3D model (e.g., data values specifying the location of the part using coordinates of the terrain model 460 ).
As changes are made to the model 120 , the profile view 600 may be updated, accordingly. As illustrated, the profile view 600 includes a data display area 610 . The data display area 610 provides a list of network parts available for in the 3D model. For example, utility networks 620 shows a list of one or more utility networks defined for the 3D model. The model display area 630 shows a profile view of the 3D model 120 . Perspective indicator 605 has changed to indicate a two dimensional perspective. Ground surface boundary 640 is based on the model geometry 250 and terrain model data 460 . Illustratively, profile view 600 includes four “structure” network parts 650 1-4 connected by three pipe network parts 660 1-3 . As shown, the network part 650 4 corresponds to the catch basin 300 illustrated in FIG. 3 and plan view 500 .
In one embodiment, the CAD application 105 may allows a user to select any of the network parts displayed in profile view 600 . In response, the CAD application may highlight the selected part and display any data values (e.g., part data 220 - 250 ). If a user elects to modify the part, the CAD application may be calculate changes throughout parts connected to the one being modified (e.g., resizing pipe lengths or repositioning pipe connections). Thus, if after modifying an attribute of catch basin 650 4 , the user selects to return to the plan view 500 , the CAD application may regenerate the plan view 500 and display a representation of the utility network that includes changes specified using the profile view 600 .
FIGS. 7-9 illustrate different actions a user interacting with CAD application 105 may perform to create display and modify a 3D model of a utility network. In these methods, it is assumed that the user is interacting with a CAD application 105 is configured according to an embodiment of the invention, as described above. Thus, the CAD application 105 may be configured to provide a collection of network parts that may be selected and integrated into a 3D model 120 ; the CAD application may allow a user to switch between multiple views, such as plan, profile, and perspective views; and as network parts are inserted, the CAD application 105 may be configured to update the 3D model 120 to reflect which parts are connected to one another. When switching from one view to another, the display of the 3D model 120 remains updated, and construction and engineering documentation may be generated from the data associated with the network parts in the 3D model.
First, FIG. 7 illustrates a method 700 for composing a 3D model of a utility network, according to one embodiment of the invention. The method begins at step 710 where a user selects a network part from a parts list. First, the user may select a part from a given part family (e.g., a family of similar pipes, or a family of catch basins). Each family provides a group of related network parts. Next, at step 720 , the user selects the particular network part family member. At step 730 , the user interface 110 may display the current (or default) set of attributes for the selected network part. In response, the user may accept these values or modify them as desired. Once the network part to be added to the 3D model is fully specified, at step 740 the CAD application 105 generates the appropriate size and instance data for a network part instance included in the 3D model. At step 750 , the CAD application 105 integrates the instance of the network parts into the 3D model. At step 760 , the instance of the network part is attached to others, and data values for the part being added, as well as other parts may be adjusted. The method 700 may be repeated for an arbitrary number of network parts allowing users to add as many parts as required to complete a particular 3D model 120 .
FIG. 8 illustrates a method for modifying the attributes of utility network parts, according to one embodiment of the invention. The method 800 begins at step 810 where the CAD application receives an indication that a user has selected a particular part, or group of parts, to modify. For example, from any view of the 3D model 120 (e.g., model view 500 or profile view 600 ), a user may select a given part by clicking on a graphical representation 350 of the part using a mouse cursor. In addition, the display area 630 may provide a list of all network parts included in a given 3D model, whether visible in the current view or not. Once selected, at step 820 , the CAD application may be configured to display the attributes, or annotation data for the selection. For example, a table of attribute/value pairs may be displayed. Once displayed, individual properties may be modified.
Alternatively, the graphical interface 110 may allow a user to add (or move) a network part by dragging and dropping an image of the network part from a catalog display into the currently displayed view of the 3D utility network. Doing so triggers the CAD application 105 to generate the appropriate network part size and position data 220 . After the user has selected a location within the current view to place the network part, the CAD application 105 integrates the part into the geometry of the overall utility network being modeled.
At step 830 , the user confirms the modifications for a given network part. In one embodiment, changes are not automatically updated until a user confirms a given action. For example, a user may have carefully positioned a group of parts and not wish the position to be continually disrupted by other changes, until confirming that a given change should be propagated throughout the 3D model of a utility network. If the user rejects the modifications, the 3D model may be revered to a prior state at step 840 , and the method 800 terminates. Otherwise, at step 850 if the user confirms the modifications, then the modified values for the network part selected at step 810 are saved. At step 860 , the CAD application evaluates any parts connected to the network part just modified to determine if the data for any connected part must also be modified.
FIG. 9 illustrates a method for generating engineering or construction documentation from a 3D model of a utility network, according to one embodiment of the invention. The method 900 begins at step 910 where a user interacting with CAD application 105 selects to open an existing 3D model or to create a new 3D model (e.g., according to the methods illustrated in FIGS. 7 and 8 ). Once completed, the user specifies a segment of the 3D model and a desired view to use in generating construction or engineering documentation for the model. At step 920 , the CAD application retrieves the network part data associated with the selected section and view. In addition, the user may specify that the attributes, labels and annotations should be generated with the requested documentation. For example, labels and part annotations may be included in the requested documentation. At step 930 , the documentation corresponding to the user selection is generated.
The disclosed CAD application and methods for composing a 3D model of a utility network allow users to construct a utility network from a collection of network parts. Further, the network parts are defined to include attributes that mirror the attributes of their real-world counterparts. Further, the described methods improve the reliability and speed of editing or revising a 3D model of a utility network. For example, modifications to one network part may trigger updates to occur to any connected parts. Users may edit the attributes of the utility network in a 3D model view and subsequently, when 2D construction or engineering documentation is generated, such changes are automatically reflected. Similarly, users may also edit attributes regarding network parts appearing in a 2D view such as a plan view or a profile view and the overall 3D model may be automatically updated without the user intervention required by current systems. | Embodiments of the invention provide a method, apparatus and article of manufacture for modeling a variety of three-dimensional (3D) utility networks constructed from individual network part elements. In one embodiment, users may construct a utility network by selecting and assembling a network of inter-connected parts, where each part is selected from a pipe and structure list. Connectivity among parts is established through part placement. Structure and connected pipe properties may be managed as a single property set. As parts are placed in the utility network, auto-sizing logic resizes existing structures to connected pipes. Pipes and structures are represented by part model data that defines a set of common behavior and properties. When a user modifies part model data or property sets or moves inter-connected parts, a logic component resizes and automatically updates any associated two-dimensional and three-dimensional views of the utility network. | 6 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to processes for preparing dibenzocycloheptene compounds and specifically to novel processes for the production of 5H-dibenzo[a,d]cycloheptene derivatives which are substituted at 5-position, more particularly N-methyl-5H-dibenzo (a,d)-cycloheptene-5-propanamine hydrochloride.
[0002] Protriptyline hydrochloride is a dibenzocycloheptatriene derivative with the chemical name N-methyl-5H-dibenzo (a,d)-cycloheptene-5-propanamine hydrochloride. Protriptyline hydrochloride is used as an antidepressant under the trade name VIVACTIL™ and is supplied as tablets in strengths of 5 and 10 mg.
[0003] U.S. Pat. No. 5,932,767 assigned to Merck & Co., Inc. discloses the preparation of protriptyline from 5-dihydrodibenzocycloheptatriene, by deprotonation, followed by reaction at low temperatures with 1,3-bromochloropropane to give the 5-(chloropropyl)-dibenzocycloheptatriene, which is reacted with methylamine in a displacement reaction to give the protriptyline product.
SUMMARY OF THE INVENTION
[0004] An object of the present invention is to provide a simple, cost-effective and reliable process for the preparation of protriptyline hydrochloride.
[0005] Another object of the invention is to provide a simple, cost-effective and reliable process for preparation of the intermediate 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2).
[0006] Still another object of the invention is to provide a simplified procedure for the isolation of 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) hereinbelow which is desired for generating a compound having formula (3) hereinbelow having a suitable leaving group such as mesylate, tosylate, besylate or acetyl. In one embodiment this achieved using methane sulfonyl chloride.
[0007] Yet another object of the invention is to provide a process whereby the compound of formula (3) which upon reaction with methyl amine gives rise to the compound 5-(N-methyl-aminopropyl) dibenzocycloheptatriene of formula (4). These and other aspects of the invention will be apparent to those skilled in the art.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0008] In the following description, for purposes of explanation, specific numbers, materials and configurations are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one having ordinary skill in the art that the invention may be practiced without these specific details. In some instances, well-known features may be omitted or simplified so as not to obscure the present invention. Furthermore, reference in the specification to phrases such as “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 of the invention. The appearances of phrases such as “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
[0009] In accordance with one embodiment the present invention relates to novel processes for the production of 5H-dibenzo[a,d]cycloheptene derivatives which are substituted at the 5-position. In one embodiment, N-methyl-5H-dibenzo (a,d)-cycloheptene-5-propanamine hydrochloride is prepared by reacting 5-dihydro dibenzocycloheptatriene with chloro propyl alcohol in the presence of an excess of n-butyl lithium solution. The resulting product is converted to a mesylate, tosylate, besylate or acetyl derivative, followed with a nucleophilic displacement reaction using methylamine in methanol, water or tetrahydrofuran. The resulting product is then converted to protryptilene hydrochloride.
[0010] Scheme
[0011] The following provides a process for the production of protriptyline hydrochloride of formula (5):
[0000]
[0012] Experimental Procedures
[0013] Thus, in accordance with an embodiment the present invention a first step involves condensation of the starting material of the formula (1) to 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2).
[0000]
[0014] In one example the process for this transformation involves inert reaction between excess equivalent of n-butyl lithium and chloropropyl alcohol with starting material of formula (1) at −15° C. to −20° C. in dry tetrahydrofuran. After 4.0 hours reaction, reaction mass was quenched with water. Upon distillation of organic layer gives crude 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2). Crude product upon high vacuum distillation gives pure 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) in 65-75% yield range.
[0015] The second step of this process involves formation of formula (3) from 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2).
[0000]
[0016] wherein R denotes a mesylate, tosylate, besylate or acetyl group.
[0017] In one example this reaction was carried out in inert conditions. 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) was dissolved in dry tetryhydrofuran and cooled down to 0° C.-5° C. Triethyl amine (1.5 eq.) was added followed by methane sulfonyl chloride (1.2 eq.) drop wise at 0° C.-5° C. After addition, the reaction mass temperature was raised to room temperature. The reaction mass was quenched with water and the organic layer was washed with brine solution. The solvent was distilled out under reduced pressure which yielded a light yellow color viscous compound, namely, the mesylate derivative of formula (3) in 90-95% yield.
[0018] The third step of the invention involves nucleophilic displacement of the mesylate group in formula (3) with methylamine solution in methanol which gives rise to the compound 5-(N-methyl-aminopropyl) dibenzocycloheptatriene of formula (4).
[0000]
[0019] In one example of this step the mesylate derivative of formula (3) and methylamine solution were mixed in methanol and refluxed for 2.0 hours. After 2.0 hours the solvent was distilled out under reduced pressure. The remaining residue was dissolved in water and pH was adjusted to 2.0 to 3.0 with concentrated HCL. One isopropyl ether washing was given to the aqueous solution. The pH was adjusted to 6.0 and given one isopropyl ether washing. pH was adjusted to 7.0 and given one more IPE wash. The aqueous layer was basified with ammonium hydroxide and extracted with dichloromethane. The organic layer was washed with water followed by brine solution and dried using sodium sulfate in the solution. The solution was filtered with sodium sulfate and washed with dichloromethane. To the filtrate charcoal was added and stirred for 1 hour at 25-30° C. The reaction mass was filtered through a celite bed and washed with dichloromethane.
[0020] The fourth step of the present process invention involves conversion of the 5-(N-methyl-aminopropyl) dibenzocycloheptatriene (4) to protriptyline hydrochloride (5) using ether HCl and dichloromethane.
[0021] In one example this step was carried out by distilling the dichloromethane from the 5-(N-methyl-aminopropyl) dibenzocycloheptatriene formula (4) residue under reduced pressure. Fresh dichloromethane was added to dissolve the residue. The solution was cooled to 5° C. to 1° C. After addition, dichloromethane was distilled out under vacuum. The residue was co-distilled twice with ethyl acetate. To the residue was added ethyl acetate and the reaction mass cooled to room temperature. The reaction mass was stirred for 5-6 hours at room temperature. The solid formed was filtered and washed with ethyl acetate and vacuum dried.
[0022] Purification of crude protriptyline hydrochloride was carried out by making a slurry by taking the above wet cake in 4 volumes of toluene and heated to 80° C. with stirring. At the same temperature the slurry was stirred for a half-hour. The reaction mass was cooled to room temperature and the solid filtered and washed with acetone. The wet cake was subjected to two acetone hot Teachings. This yielded a pure protriptyline hydrochloride with chemical name N-methyl-5H-dibenzo (a,d)-cycloheptene-5-propanamine hydrochloride of formula (5) in 20-30% yield range to afford 99.95% to 100.00% pure material by HPLC.
EXAMPLES
3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the Formula (2)
[0023] 200 gm of starting material of formula (1) was charged into a 10 L three-neck flask containing dried tetrahydrofuran, under nitrogen atmosphere. The reaction mass was cooled to −15° C. to −20° C. n-butyl lithium solution 4.0 eq. (1.6 M in hexane) was added drop wise. After addition, the reaction mass was stirred for 2.0 hours at −10° C. to −15° C. To the reaction mass was added 3-chloropropyl alcohol 1.05 eq. drop wise at −15 to −20° C. After addition, the reaction mass was stirred for 2.0 hours at −10° C. to −15° C. Completion of the reaction was checked by TLC. The reaction mass was quenched with water. The organic layer was washed with brine solution and dried with sodium sulfate. Solvent was removed under reduced pressure to afford crude light yellow color viscous liquid product 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) in 300.0 gm yield.
Purification of crude 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the Formula (2)
[0024] The crude product 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) was subjected to high vacuum fractional distillation. The first fraction was collected at vapor temperature 48° C.-55° C. The second fraction was collected at vapor temperature 120° C.-165° C. The product fraction was collected at vapor temperature 165° C.-195° C. to afford light green color to colorless product of 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) in 135-145 gm (50%) yield.
Mesylate Derivative of Formula (3)
[0025] 3-(5H-Dibenzo[a,d]cyclohepten-5-yl)-propan-1-ol of the formula (2) (100.0 gm) was charged into a 2.0 L single neck flask and dissolved in dried tetrahydrofuran under nitrogen atmosphere and Cooled to 0° C.-5° C. Triethyl amine (84.5 mL, 1.5 eq.) was added drop wise at 0° C.-5° C. followed by drop wise addition of methane sulfonyl chloride (37.3 mL, 1.2 eq.) at 0° C.-5° C. The reaction mass temperature was raised to room temperature. Completion of the reaction was checked by TLC. The reaction mass was quenched with water and a brine wash was given. The organic layer was dried over sodium sulfate. Solvent was removed under reduced pressure to afford light yellow color viscous product mesylate derivative compound of formula (3) (130 to 135 gm).
5-(N-methyl-aminopropyl)dibenzocycloheptatriene of Formula (4)
[0026] The mesylate derivative of formula (3) 100.0 gm was charged into a 2.0 L single neck flask. 582 ml (20 eq) of methylamine solution in methanol (30%) was added into the flask. The reaction mass was heated to reflux temperature (65°-70° C.) and stirred at reflux temperature for 2.0 hours. Completion of the reaction was checked by TLC. The solvent was removed under reduced pressure. The residue was dissolved in water at pH 3.0 and given an isopropyl ether wash. The isopropyl ether wash was repeated at pH 6.0 and again at pH 7.0. The aqueous layer was basified and extracted with dichloromethane. The organic layer was washed with water, followed by brine solution and dried over sodium sulfate to obtain 5-(N-methyl-aminopropyl) dibenzocycloheptatriene of formula (4).
Protriptyline Hydrochloride of Formula (5)
[0027] Charcoal (15 gm) was added to 5-(N-methyl-aminopropyl) dibenzocycloheptatriene of formula (4) and stirred for 1.0 hour at 25° C. to 30° C. The contents of the flask were filtered through a celite bed and washed with dichloromethane. The dichloromethane solution was distilled atmospherically 40° C. to 45° C. up to half of the volume. The reaction mass was cooled to 20° C.-25° C. and chilled to 5° C. to 10° C. 37.0 mL of ether HCl (15-20%) was added drop wise into the reaction mass at 5° C. to 110° C. After this addition the dichloromethane was distilled out completely under vacuum. To the reaction mass ethyl acetate (300 mL) was added and the reaction mass was cooled to 25° C. to 30° C. The reaction mass was further stirred for 5-6 hours at 25° C. to 30° C. The resulting solid was filtered and washed with ethyl acetate and vacuum dried yielding 40 gm of wet cake crude protriptyline hydrochloride of formula (5).
Purification of Protriptyline Hydrochloride (5)
[0028] Crude protriptyline hydrochloride (5) 40.0 gm was charged into a 500 ml single neck flask. 160 mL of toluene was added. The slurry was heated to 80° C. to 85° C. and stirred for 60 minutes. The reaction mass was cooled to room temperature and the solid was filtered off and washed with acetone. The product was dried at 70° C. under vacuum for 15-20 hours to afford white color solid (40.0 gm).
[0029] 40.0 gm of the above dried product was charged into a 500 ml single neck flask. 200 mL of acetone was added and the slurry was heated to reflux temperature and stirred for 60 minutes. The reaction mass was cooled to room temperature and the solid was filtered off and washed with acetone. The product was suck dried well to afford white color wet cake (35.0 gm).
[0030] 35.0 gm of the above prepared wet cake was charged into a 500 ml single neck flask. 200 mL of acetone was added and the slurry was heated to reflux temperature and stirred for 60 minutes. The reaction mass was cooled to room temperature and the solid was filtered off and washed with acetone. The product was suck dried well to afford white color wet cake (30.0 gm). The resulting wet cake was dried at 60° C. under vacuum for 20 hours. After drying the 22.0 gm of dried protriptyline hydrochloride was unloaded. The dried protryptilene was substantially pure, having a purity of greater than 99.9%.
[0031] While the preferred embodiments have been described and illustrated it will be understood that changes in details and obvious undisclosed variations might be made without departing from the spirit and principle of the invention and therefore the scope of the invention is not to be construed as limited to the preferred embodiment. | A process for preparation of protriptyline hydrochloride from 5-dihydrobenzocycloheptatriene of formula (1) by coupling with chloropropyl alcohol in the presence of excess n-butyl Lithium in tetrahydrofuran under inert atmosphere, followed by preparation of mesylate derivative of formula (3) and finally the nucleophilic displacement of the mesylate group by reacting methylamine solution in methanol to give protriptyline free base of the formula (4). Also the present process reveals the hydrochloride salt formation and purification of the same to give pure pharmaceutical grade protriptyline hydrochloride with impurities less than 0.1% w/w. | 2 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to pulse combustion devices, and more particularly to pulse combustion engines.
[0002] Diverse pulse combustion technologies exist. Pulse detonation engines (PDE's) represent areas of particular development. In a generalized PDE, fuel and oxidizer (e.g. oxygen-containing gas such as air) are admitted to an elongate combustion chamber at an upstream inlet end. The air may be introduced through an upstream inlet valve and the fuel injected downstream thereof to form a mixture. Alternatively, a fuel/air mixture may be introduced through the valve. Upon introduction of this charge, the valve is closed and an igniter is utilized to detonate the charge (either directly or through a deflagration to detonation transition process). A detonation wave propagates toward the outlet at supersonic speed causing substantial combustion of the fuel/air mixture before the mixture can be substantially driven from the outlet. The result of the combustion is to rapidly elevate pressure within the chamber before substantial gas can escape inertially through the outlet. The effect of this inertial confinement is to produce near constant volume combustion as distinguished, for example, from constant pressure combustion. Exemplary pulse combustion engines are shown in U.S. Pat. Nos. 5,353,588, 5,873,240, 5,901,550, and 6,003,301.
[0003] Additionally, pulse combustion devices have been proposed for use as combustors in hybrid turbine engines. For example, the device may replace a conventional turbine engine combustor. Such proposed hybrid engines are shown in U.S. Pat. No. 3,417,564 and U.S. Publication 20040123583 A1.
BRIEF SUMMARY OF THE INVENTION
[0004] One aspect of the invention involves a pulse combustion device having a circular array of combustion conduits. Each conduit includes a wall surface extending from an upstream inlet to a downstream outlet. At least one valve is positioned to admit at least a first gas component of a propellant to the combustion conduit inlets. The device includes an outlet end member. The array and outlet end member are rotatable in at least a first direction relative to each other. Means are provided at least partially in the outlet end member for providing a circumferentially varying effective nozzle geometry.
[0005] In one or more implementations, the means may provide a circumferentially varying effective throat area. The outlet end member may be essentially fixed and the array may rotate. Alternatively, the array may be essentially fixed and the outlet end member may rotate. The means may include a passageway through the outlet end member. The outlet end member may further include an igniter. The inlet valve may comprise an inlet end member non-rotating relative to the outlet end member.
[0006] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a schematic side view of a gas turbine engine.
[0008] FIG. 2 is a sectional view of a combustor of the engine of FIG. 1 , taken along line 2 - 2 .
[0009] FIG. 3 is a sectional view of a combustor of the engine of FIG. 1 , taken along line 3 - 3 .
[0010] FIG. 4 is a longitudinal sectional view of a conduit array and nozzle of the combustor of FIG. 2 , taken along line 4 - 4 .
[0011] FIG. 5 is a longitudinal sectional view of a conduit array and nozzle of the combustor of FIG. 2 , taken along line 5 - 5 .
[0012] FIG. 6 is a partially schematic unwrapped longitudinal circumferential sectional view of the combustor of the engine of FIG. 1 .
[0013] FIG. 7 is rear view of an alternative nozzle.
[0014] Like reference numbers and designations in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0015] FIG. 1 shows a gas turbine engine 20 having a central longitudinal axis 500 . From upstream to downstream, the exemplary engine 20 includes a fan section 22 , at least one compressor section 24 , a pulse combustion combustor section 26 , and a turbine section 28 . The exemplary combustor 26 includes a circumferential array of longitudinally-extending conduits 30 ( FIG. 2 ) mounted within an engine case 32 for rotation about the axis 500 (e.g., supported or formed on a carousel structure 34 which may be on one of the compressor/turbine spools or a separate free spool).
[0016] The exemplary combustor array includes eighteen combustor conduits 30 (shown for illustration as straight passages oriented longitudinally and having a transverse cross-section of an annular sector). Alternative cross-sections including circular sections are possible, as are non-longitudinal orientations and non-straight configurations. The direction of rotation is labeled as 506 . The exemplary passageways are formed between inner and outer walls 36 and 38 spanned by radial walls 40 .
[0017] FIG. 6 shows further details of the exemplary combustor 26 during steady-state operation. Positions of the conduits at an exemplary point in the cycle are respectively designated as 30 A- 30 R. Each exemplary conduit 30 has an upstream inlet 42 and a downstream outlet 43 . For ease of reference, the conduits will be identified by the reference numerals associated with the illustrated positions. Fixed inlet (upstream) and outlet (downstream) end members 44 and 45 are positioned respectively upstream and downstream of the conduit array and have respective open areas 46 and 47 for admitting gas to the conduits and passing gas from the conduits. As is discussed in further detail below, member 45 serves as a nozzle structure and its open area 47 serves as a nozzle aperture.
[0018] At the illustrated instance in time, a last bit of a purge flow 50 of combustion products is exiting the outlet 43 of the conduit 30 A at a first end 51 of the open area 47 . A slug of a buffer gas 52 is in a downstream end portion of the conduit 30 A following right behind the purge flow 50 . A propellant charge 54 follows behind the buffer slug 52 , being delivered by a propellant fill flow 56 through the inlet 42 . An exemplary propellant flow includes a gaseous oxidizer (e.g., air) and a fuel (e.g., a gaseous or liquid hydrocarbon). In the exemplary turbine engine embodiment, the air may be delivered from the compressor 24 and the fuel may be introduced by fuel injectors (not shown).
[0019] At the illustrated point in time, the next conduit 30 B has just had its outlet closed by passing in front of an upstream face 58 along a blocking portion 60 of the downstream member/nozzle 45 . At the point of closure/occlusion, some or all of the buffer slug 52 may have exited the conduit outlet. The buffer slug 52 serves to prevent premature ignition of the charge 54 due to contact with the combustion gases. The closure of the outlet port causes a compression wave 62 to be sent in a forward/upstream direction 510 through the charge 54 leaving a compressed portion 63 of said charge in its wake.
[0020] This compression process continues through the position approximately shown for conduit 30 C. At some point (e.g., as shown for the conduit 30 D) the conduit outlet becomes exposed to the operative end 64 of an ignition source 66 (e.g., a spark ignitor in the member 45 ). The ignitor 66 ignites the compressed charge 63 causing detonation and sending a detonation wave 68 forward/upstream after the compression wave 62 (e.g., as shown for conduits 30 D, 30 E, and 30 F). The combustion products 70 are left in the wake of the detonating wave.
[0021] A surface 80 of a main portion of the combustor upstream member 44 is positioned to block the conduit inlets during a main portion of the combustion process. In the exemplary implementation, the surface 80 (a downstream face) is positioned to block the inlets 42 to prevent upstream expulsion of the charge 54 as the compression wave 62 approaches. The surface 80 is also positioned to prevent upstream discharge of combustion products during a high pressure interval thereafter. An exemplary circumferential extent of the surface 80 is between 40° and 160° (more narrowly, 90° and 120°).
[0022] In the exemplary combustor, there is a brief interval shown for the conduits 30 D, 30 E, and 30 F wherein both its inlet and outlet are blocked after the outlet been exposed to the ignitor. Alternative configurations may lack this interval. Shortly thereafter (e.g., as shown for the conduit 30 G) the conduit outlet clears the surface 58 at a second end 82 of the open area 47 and is thus opened. A blow down flow 84 of high pressure combustion gases then exits the conduit outlet. This blow down interval may continue (e.g., for the conduits shown as 30 G, 30 H, 30 I, 30 J, and 30 K).
[0023] After the blow down interval, there may be a buffer filling interval wherein an inlet buffer flow 90 generates the buffer slug 52 upstream of the combustion gases 70 . The exemplary flow 90 may be of unfueled air. In the exemplary combustor, this flow 90 is isolated from the flow 56 by a narrow segment 92 of the upstream member 44 (thereby defining a port through which the flow 90 passes). Alternative configurations could lack such a segment 92 and rely on injector positioning to keep the flow 90 relatively unfueled. Thereafter, through several further stages (e.g., for conduits 30 M, 30 N, 300 , 30 P, 30 Q, 30 R, and finally returning to 30 A, 30 B, and 30 C) the conduit may be recharged with propellant.
[0024] Further details of the downstream member 45 can be seen in FIGS. 3-5 . In the exemplary somewhat schematic illustration, the downstream member has a downstream face 100 generally radially extending. From the upstream face 58 to the downstream face 100 , the open area 47 defines a convergent-divergent nozzle ( FIG. 4 ) characterized by a convergent (flow contraction) portion 102 , a throat portion 104 , and a divergent (flow expansion) portion 106 . The exemplary convergent portion 102 is characterized by inboard and outboard surface portions 107 and 108 of a circumferentially elongate upstream channel. Viewed in central longitudinal section, the exemplary portions 107 and 108 are straight and downstream convergent toward each other. Similarly, the exemplary divergent portion 106 is characterized by inboard and outboard surface portions 110 and 112 of a circumferentially elongate downstream channel. Viewed in central longitudinal section, the exemplary portions 110 and 112 are straight and downstream divergent away from each other. Sectionally convex throat transitions join the surface portion 107 to the surface portion 110 and the surface portion 108 to the surface portion 112 . Other nozzle shapes (e.g., curved or otherwise contoured surface portions) are possible.
[0025] According to the present invention, the effective nozzle properties may vary circumferentially. In the exemplary embodiment, the effective throat area may be varied by varying the throat radial span ART. The effective exit area may be varied by varying the exit radial span ΔR E . The effective exit angle may be varied by varying longitudinal/radial angle θ E between the surface portions 110 and 112 . There may be similar control of the properties of the convergent portion 102 . Other parameters may be varied. In the exemplary nozzle, the radial span ART generally decreases in the direction of rotation 506 (e.g., from near the second end 82 to near the first end 47 ). The change may be stepwise or smoothly continuous. The change occurs over a greater circumferential span than the technical incidental and transient change from a conduit passing from a blocked area to a nozzle area that remains constant for the rest of the discharge cycle. The change may take place over a major portion of the cycle (e.g., at least 180° of a single cycle per revolution configuration). More broadly, the change may take place over an area between a third of a cycle and a full cycle. FIG. 7 shows a full cycle change in a nozzle 200 effectively eliminating the blocking of the conduit outlets. A divider wall 202 in the nozzle divergent section 204 helps block any backflow of high pressure exhaust products into the adjacent tube purging at a lower pressure.
[0026] In steady-state operation, the rotation may be driven by aerodynamic factors (e.g., from a slight tangential orientation of the conduits). At start-up, engine spool rotation may be commenced by conventional drive (e.g., pneumatic, electric, or starter cartridge). Operation of the exemplary combustor may tend to be self-timing. However, additional timing control may be provided. For example, means may be provided to change the relative phases of the downstream and upstream members 44 and 45 (e.g., by shifting their orientational phase about the axis 500 ). Alternatively, means may be provided for varying the attributes of either of these members individually. For example, there may be multiple open areas in the downstream member 45 or a single passageway may have multiple outlets or inlets which may be selectively opened or closed individually or in combinations. Similarly, the circumferential extent of blocking provided by the upstream member 82 might be made adjustable as might be the circumferential extents and positions of the respective fueled and unfueled flows 56 and 90 .
[0027] In alternative embodiments, the conduit array may be fixed and at least the downstream member may be rotating. An upstream member rotating synchronously with the downstream member will provide a similar operation as discussed above for FIG. 6 . However, the valving interaction of the upstream member with the conduits could easily be replaced with discrete valves at the inlet ends of each conduit. Such discrete valves would provide greater flexibility in timing control of the combustion process.
[0028] One or more embodiments of the present invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. For example, even with the basic construction illustrated, many parameters may be utilized to influence performance. Accordingly, other embodiments are within the scope of the following claims. | A pulse combustion device has a number of combustors with upstream bodies and downstream nozzles. Coupling conduits provide communication between the combustors. For each given combustor this includes a first communication between a first location upstream of the nozzle thereof and a first location along the nozzle of another. There is second communication between a second location upstream of the nozzle and a second communication between a second location upstream of the nozzle of a second other combustor and a second nozzle location along the nozzle of the given combustor. | 5 |
This is a continuation of application Ser. No. 08/904,137, filed Jul. 31, 1997.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an IC card having a writable memory and more particularly to an IC card for writing a program in this memory by keeping security and a method thereof.
2. Description of the Prior Art
An IC card is excellent in security and finds wide applications. Generally, an IC card has a built-in memory for writing and storing a program as well as various information which can be erased electrically and is used to write various information after a user owns it. For example, the invention disclosed in Japanese Laid-Open Patent Application 6-309558 stores customer information in an IC card and provides quick services. In Japanese Laid-Open Patent Application 6-309384, a use that inspection results and dosing data of a patient in a medical institution are stored in an IC card is described. Furthermore, recently, study has been given to use of an IC card in an electronic money system and an IC card is used to write money information.
As mentioned above, the use method of writing information in an IC card is generally carried out. To keep security, the use method of changing and adding to an internal program stored already and writing a new program is limited.
To improve or change the function of an IC card, there is a case that changing of a program is necessary. Furthermore, to keep security, a case that changing of the cryption method is necessary also may be caused. However, to make it possible to modify an already stored program leads to information opening to public of the microprocessor chip of the IC card and the program thereof and it is not suitable for the use of this IC card for which high security is evaluated.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide an IC card for changing or adding to an internal program with the high security of an IC card kept and writing a new program and a method thereof.
To accomplish this object, the present invention is a program writable IC card comprising a microprocessor and a memory for storing a program write control program having at least one of the decryption function and the function for converting a program code and a program for the aforementioned microprocessor, wherein when the program for the microprocessor is given from the outside, the IC card performs at least one of the decryption process and the process of converting a program code according to the program write control program and stores the program in the memory.
More concretely, according to the present invention which is a program writable IC card comprising a microprocessor and a memory storing a program for the microprocessor, one characteristic is a constitution that the IC card includes a write control program having the decryption function and/or the program code conversion function in a program built in the IC card and a memory for program writing and the other characteristic is a constitution that the IC card includes a write control microprocessor for executing the write control program having the decryption function and/or the program code conversion function in addition to the microprocessor for IC card, a means for switching the two microprocessors, and a memory for program writing.
Another characteristic of the present invention is a constitution that the IC card having a microprocessor whose technical information such as a specification is not opened to public includes a microprocessor whose technical information such as a catalog and a specification is opened to public, a memory for program writing for storing a program for the microprocessor, and a means for switching the two microprocessors.
These constitutions make it possible to change or add to an internal program by keeping the security necessary for the IC card and to write a new program.
The foregoing and other objects, advantages, manner of operation and novel features of the present invention will be understood from the following detailed description when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing a first embodiment of the program writable IC card of the present invention.
FIG. 2 is a block diagram showing a second embodiment of the program writable IC card of the present invention.
FIG. 3 is a block diagram showing a third embodiment of the program writable IC card of the present invention.
FIG. 4 is a block diagram showing a fourth embodiment of the program writable IC card of the present invention.
FIG. 5 is a block diagram showing a fifth embodiment of the program writable IC card of the present invention.
FIG. 6 is a block diagram showing a sixth embodiment of the program writable IC card of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a block diagram showing a first embodiment of the writable IC card of the present invention. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 3 B a write control program having decryption function, 4 a memory for writing, and L 1 a data bus.
The microprocessor for IC card 1 , the connector 2 , and the IC card function program 3 A are components for realizing the original function of the IC card. An external instruction is given to the microprocessor 1 via the connector 2 and the IC card performs an operation according to this instruction. A write command for instructing writing is incorporated in the IC card function program 3 A beforehand and the IC card function program 3 A activates the write control program 3 B by an external write instruction. The write control program 3 B is provided with the decryption function beforehand and when the write control program 3 B is activated, communication with the IC card requires a crypted command and data, a cryption key, and others. If a program, command, and data to be written later are not crypted correctly, they are rejected by the write control program 3 B and the program and data cannot be written into the memory for writing 4 . If a program to be written later is crypted, even if it is opened to public, a problem of loss of security will not arise and there is no need to manage the program writing process strictly. Therefore, in addition to keeping of security for a program in the IC card, security can be kept also for a program to be written later.
FIG. 2 is a block diagram showing a second embodiment of the writable IC card of the present invention. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 3 C a write control program having program code conversion function, 4 a memory for writing, and L 1 a data bus.
The microprocessor for IC card 1 , the connector 2 , and the IC card function program 3 A are components for realizing the original function of the IC card and the operations thereof are the same as those of the aforementioned first embodiment. A write command for instructing writing is incorporated in the IC card function program 3 A beforehand and the IC card function program 3 A activates the write control program 3 C by an external write instruction. This write control program 3 C has a function for converting a program code and a program to be written later is processed by this write control program 3 C, converted in a different format from that of a code inputted from the connector 2 , and then written into the memory for writing 4 . This program to be written later is created in a location where the security thereof is managed and the program code thereof is converted beforehand according to a rule which is reverse to the program code conversion rule in the write control program 3 C. By doing this, in the same way as with the first embodiment, in addition to keeping of security for a program in the IC card, security can be kept also for a program to be written later.
If the function of a prior art for converting a program code for microprocessor to a program code for microprocessor in an IC card which is not open to public is provided as a program code conversion function of the write control program 3 C, there is no need to open the information on the microprocessor 1 in the IC card to public for a program developer. Namely, from an advantage that a program code to be given from the outside may be a known code and there is no need to open an instruction code of a program in the IC card to the outside, the security of the IC card can be kept and furthermore the program development efficiency can be improved. In this case, from a viewpoint of keeping of security, adding of a function for eliminating fetching of information on the IC card function program 3 A by a program to be written later is effective.
If the write control program 3 C has both the two functions explained in the first and second embodiments, that is, the decryption function and the program code conversion function, it is more effective in the respect of security keeping of the IC card.
FIG. 3 is a block diagram showing a third embodiment of the writable IC card of the present invention. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 4 a memory for writing, 5 a microprocessor for writing, 6 a program ROM ( 2 ), 6 A a write control program having decryption function, 7 a switch, L 1 a data bus, L 2 a switching signal ( 1 ), and L 3 a switching signal ( 2 ). The switch 7 is a means for selectively switching the microprocessors 1 and 5 connected to the connector 2 and switches them by the switching signals L 2 and L 3 . When the switch 7 selects the microprocessor 1 , the microprocessor 1 , the connector 2 , and the program ROM ( 1 ) 3 realize the original IC card function.
A write command for instructing writing is incorporated in the IC card function program 3 A beforehand, and the switching signal ( 1 ) L 2 is outputted from the IC card for microprocessor 1 by a write instruction from the outside, and the switch 7 is switched to the microprocessor for writing 5 . The write control program 6 A is provided with the decryption function. The write control program 6 A executes the decryption function by the microprocessor for writing 5 . Communication with the IC card after the switch 7 is switched to the microprocessor for writing 5 requires a crypted program, command, and data, a cryption key, and others. If a program, command, and data to be written later are not crypted correctly, they are rejected by the write control program 6 A and the program and data cannot be written into the memory for writing 4 . Therefore, in addition to keeping of security for a program in the IC card, security can be kept also for a program to be written later. When the IC card is structured like this, even if it can be switched to the write mode by an incorrect operation, if the process ends normally and the switch 7 cannot be returned to the microprocessor for IC card 1 by the switching signal L 3 , the use as an ordinary IC card can be made impossible forever and the security can be kept. This is an advantage which is not found in the first and second embodiments. Even in a constitution that one microprocessor is used, if it is used incorrectly, by adding a circuit receiving no external reset signal, the same effect can be obtained. Since the two microprocessors 1 and 5 are independent of each other, a microprocessor in a quite different format can be used and a constitution with higher security can be obtained.
FIG. 4 is a block diagram showing a fourth embodiment of the writable IC card of the present invention. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 4 a memory for writing, 5 a microprocessor for writing, 6 a program ROM ( 2 ), 6 B a write control program having program code conversion function, 7 a switch, L 1 a data bus, L 2 a switching signal ( 1 ), and L 3 a switching signal ( 2 ). The functional operation of this embodiment as an IC card and the switching operation for the two microprocessors are the same as those of the third embodiment mentioned above. This embodiment has both the functions of the second and third embodiments mentioned above.
If the write control program 6 B is provided with both of the two functions explained in the third and fourth embodiments, that is, the decryption function and the program code conversion function, it is more effective in the respect of keeping of security of the IC card.
FIG. 5 is a block diagram showing a fifth embodiment of the writable IC card of the present invention. This embodiment shows a program writable IC card for keeping the internal security of the IC card by perfectly opening a program to be written later to the user side. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 3 D a program for write control, 4 a memory for writing, 7 a switch, 8 a microprocessor whose information is opened to public, L 1 a data bus, L 2 a switching signal ( 1 ), L 3 a switching signal ( 2 ), and L 4 a chip select signal. A program to be written into the memory for writing 4 is structured so as to be executed only by the microprocessor whose information is opened to public 8 . The chip select signal L 4 for the program ROM ( 1 ) 3 storing the IC card function program 3 A is structured so as to be controlled only by the microprocessor for IC card 1 . Therefore, it is impossible to access the program ROM ( 1 ) 3 by a program to be written later and the security of the IC card function can be kept.
The program writing operation for the memory for writing 4 is started when the microprocessor for IC card 1 activates the program for write control 3 D by an external write instruction. The program for write control 3 D performs a process of writing an external program and data into the memory for writing 4 . The program in this case is created for the microprocessor whose information is already opened to public 8 and the security of the IC card function is kept inside the IC card, so that there is no need to protect a program to be written later.
This embodiment is a one which is suited to a use for making openly handling a program to be written later and keeping the security as an IC card compatible with each other.
FIG. 6 is a block diagram showing a sixth embodiment of the writable IC card of the present invention. Numeral 1 indicates a microprocessor for IC card, 2 a connector with an external device, 3 a program ROM ( 1 ), 3 A a program for realizing the IC card function, 4 a memory for writing, 7 a switch, 8 a microprocessor whose information is opened to public, 6 a program ROM ( 2 ), 6 C a write control program for the microprocessor 8 , L 1 a data bus, L 2 a switching signal ( 1 ), L 3 a switching signal ( 2 ), and L 4 a chip select signal. The respect of keeping the security of the IC card function by the chip select signal L 4 is the same as that of the fifth embodiment.
According to this embodiment, the program ROM ( 2 ) 6 storing the write control program 6 C for the microprocessor whose information is opened to public 8 is independent of the program ROM ( 1 ) 3 storing the IC card function program 3 A, so that keeping of the security of the IC card function can be enhanced more.
When a program is to be written later, the microprocessor for IC card 1 passes the control process to the microprocessor whose information is opened to public 8 by the switching signal L 2 . The microprocessor whose information is opened to public 8 performs all the write control process according to the write control program 6 C and returns the control process to the microprocessor for IC card 1 by the switching signal L 3 when the write process ends.
According to the fifth and sixth embodiments, the development efficiency can be improved by use of a microprocessor whose information is opened to public under a catalog specification or operation specification. However, by combining the function for controlling writing like the other embodiments, the security for a program to be written later can be kept.
The memory for writing program 4 has no independent constitution and can serve as a memory for program of a microprocessor if it is writable.
In each aforementioned embodiment, a memory which can write only once can be used for the aforementioned memory for writing.
Effects of the Invention
As mentioned above, according to the present invention, an IC card which keeps the security of the IC card function high and can write a program later can be obtained. | An IC card and a method thereof for adding or changing a program for a memory for writing without adversely affecting the function of the IC card and by keeping the security of a program to be written later by restricting writing by a write control program having a decryption function or a program code conversion function. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
This Non-provisional application claims priority under 35 U.S.C. §119(a) on patent application No(s). 098119635 filed in Taiwan, Republic of China on Jun. 12, 2009, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of Invention
The invention relates to an image processing method and an image processing system and, more particularly, to an image processing method and an image processing system performed by a looking up table (chrominance-luminance lookup table, luminance lookup table).
2. Related Art
With the progress of digital image display techniques, electronic display devices with high definition, high stableness, and multi-functions are widely used in people's daily life. Digital electronic devices such as a liquid crystal display (LCD) screen, a plasma display and a projector become to be main media in people's life for getting information or communicating with each other.
The key factor which affects the display quality includes a luminance contraction and a color saturation of an image. Generally, the contraction means the luminance difference between a bright area and a dark area in the image, and enhancing contraction properly may make a user feel agreeable. The color saturation is determined by the chrominance of various kinds of colors.
The conventional image contraction and color enhancement are performed in the RGB color space format. However, the current formats of the images in most images or the video streams do not use the RGB color space, they use the YCbCr color space format which separates the luminance and the chrominance to store the information or transmit information. That is, conventionally, the images or video streams with YCbCr image format may need to be converted to the RGB image format first, and then they are performed to enhance the contraction or the saturation. Even after the image is processed, the RGB image format needs to be reconverted to the YCbCr image format for adapted to the display system. Therefore, additional color space conversion is a load to the system, and the video stream cannot be processed instantly.
In another aspect, in the image contraction and saturation enhancement to the YCbCr image format images, since the YCbCr image format has a luminance component (Y) and two color components (Cb and Cr), the image processor may establish a luminance lookup table (LUT) to adjust the luminance component (Y), and it also may establish one or more chrominance luminance lookup table to adjust the chrominance components (Cb and Cr) according to the requirement in enhancing chrominance. However, in each image processing flow path, each component (Y, Cb or Cr) in the image information are adjusted according to the luminance lookup table or the chrominance LUT, and that means the components need to be calculated for three times. Therefore, the troublesome calculation is a heavy load to the system without independent image processor.
SUMMARY OF THE INVENTION
The invention discloses an image processing method adapted to processing image information, and the image information with multiple process pixels.
According to an embodiment of the invention, the image processing method includes the following steps: a) setting a group of parameters; b) establishing a luminance lookup table according to the group of parameters; c) establishing a chrominance-luminance lookup table according to the parameters and the luminance lookup table; d) retrieving the image information; e) determining a format of the image information; f) generating an adjusted chrominance and a first adjusted luminance corresponding to one of the process pixels using the chrominance-luminance lookup table if the format of the image is a first format (for example, the YCbCr is 4:2:2); and g) generating an adjusted chrominance, a first adjusted luminance and a second adjusted luminance corresponding to one of the process pixels using the chrominance-luminance lookup table and the luminance lookup table if the format of the image is a second format (for example, the YCbCr is 4:2:0).
The invention also discloses an image processing system including a memory module, a calculating module and a processing module. The calculating module and the processing module are electrically connected to the memory module, respectively.
According to an embodiment of the invention, the memory module stores image information, and the image information with multiple process pixels. The calculating module establishes a luminance lookup table according to a group of parameters, and then the calculating module establishes a chrominance-luminance lookup table according to the parameters and the luminance lookup table, and stores the luminance lookup table and the chrominance-luminance lookup table in the memory module.
The processing module retrieves the image information from the memory module and determines the format of the image information. If the format of the image is a first format, the processing module uses the chrominance-luminance lookup table stored in the memory module to generate an adjusted chrominance and a first adjusted luminance corresponding to one of the process pixels. If the format of the image is a second format, the processing module uses the chrominance-luminance lookup table and the luminance lookup table stored in the memory module to generate an adjusted chrominance, a first adjusted luminance and a second adjusted luminance corresponding to one of the process pixels.
That is, in the image processing method and the image processing system of the invention, by establishing the luminance-chrominance LUT, the luminance and the chrominance of the image can be adjusted only via a single calculation procedure. Therefore, the image processing time is shorted, and the flow path is simplified.
These and other features, aspects and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart diagram showing the image processing method in an embodiment of the invention; and
FIG. 2 is a functional block diagram showing an image processing system which can perform the image processing method in the invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a flow chart diagram showing the image processing method in an embodiment of the invention. FIG. 2 is a functional diagram showing the image processing system 1 which can perform the image processing method in an embodiment of the invention. The image processing method and the image processing system are adapted to processing image information (such as an image, a multi-media movie or a video stream). The image information has a format of the image. As shown in FIG. 2 , in the embodiment, the image processing system 1 includes a memory module 10 , a calculating module 12 , a processing module 14 and an input module 16 . The calculating module 12 and the processing module 14 are electrically connected to the memory module 10 , respectively. The input module 16 is electrically connected to the calculating module 12 . The memory module 10 stores the image information including multiple process pixels.
In the embodiment, the image processing method and the image processing system 1 may process images having different format of the images. In practical usage, the common format of the images may be divided into YCbCr 4:4:4 (it means that the YCbCr format of the color space is used and the sampling ratio is 4:4:4, which is completely sampled), YCbCr 4:2:2 (it means that the YCbCr format of the color space is used and the sampling ratio 4:2:2, which is partially sampled), YCbCr 4:2:0 (it means that the YCbCr format of the color space is used and the sampling ratio 4:2:0 or 4:1:1, which is partially sampled) and other types.
Taking the common YCbCr 4:2:2 format of the image as an example, it includes YUY2, UYVY, and YUV2 formats and so on. The common YCbCr 4:2:0 format of the image includes YV2, NV12 formats and the I420 format adapted to the digital video disk (DVD).
In the image information, the minimum unit image is pixel, and in the YCbCr 4:4:4 format of the image (completely sampled), each pixel has three complete components (Y, Cb and Cr). To satisfy the compression or image processing requirement, in the YCbCr 4:2:2 or the YCbCr 4:2:0 format of the image, the adjacent multiple pixels are defined as a macro pixel and the macro pixel is defined according to different formats. For example, it may be two adjacent pixels or 2*2 adjacent pixel areas.
Generally, in the YCbCr 4:2:2 format, a macro pixel may be composed of the Y component (Y 1 ) of the first pixel, the Cb component (Cb 1 ) of the first pixel, the Y component (Y 2 ) of the second pixel and the Cr component (Cr 2 ) of the second pixel. Namely in each macro pixel of the YCbCr 4:2:2, the luminance and the chrominance are 1:1 (two luminances and two chrominances). In practical usage, to facilitate the processing, in the YCbCr 4:2:2 format, a macro pixel [Y 1 , Cb 1 , Y 2 , and Cr 2 ] is usually divided to two process pixels a processing pixel [Y 1 , Cb 1 ] and another process pixel [Y 2 , Cr 2 ]. In the embodiment, the processing module takes a process pixel as a basic unit to process and adjust the image.
In another aspect, in the YCbCr 4:2:0, a macro pixel may be composed of four different Y components (Y 1 , Y 2 , Y 3 and Y 4 ), a Cb component, and a Cr component (therefore, the sampling ratio of the YCbCr 4:2:0 format also may be called 4:1:1). That is, in each macro pixel of the YCbCr 4:2:0, the luminance and the chrominance is 2:1 (four luminances and two chrominances). In practical usage, to facilitate the processing, in the YCbCr 4:2:0 format, a macro pixel [Y 1 , Y 2 , Y 3 , Y 4 , Cb, and Cr] is usually divided into two processing pixels. In the embodiment, the two processing pixels are a process pixel [Y 1 , Y 2 , and Cb] and another process pixel [Y 3 , Y 4 , and Cr].
As shown in FIG. 1 and FIG. 2 , step S 100 is firstly performed to set a group of parameters. In the embodiment, the parameter may be generated automatically by a calculating module 12 , or it may be inputted by the user via an input module 16 and transmitted to the calculating module 12 , which is not limited thereto. In the embodiment, the parameters may be (St, Sa), and Stε[0,1], Sa≧0, and the parameters may be set according to the practical requirements, and it also may be adjusted according to the quality of the image processing result.
Then, step S 102 is performed. The calculating module 12 generates a luminance lookup table according to the parameters. In the embodiment, the calculating module 12 may store the luminance lookup table in the memory module 10 . In the embodiment, the luminance of the image information of the invention is stored in an 8 bits mode, and the luminance is divided to 256 classes (the luminance is distributed in 0˜255). In the embodiment, the luminance lookup table is generated according to the formula herein below:
Y out( x )=Bound[ f y ( St,f ( x )) x−b y ( St,f ( x ))] min max , wherein x is an integer between 0 and 255,
f y (St,f(x))=St×f(x)+(1−St) b y (St,f(x))=16×St×(f(x)−1), wherein f(x) is a non-liner function for generating a gain value corresponding to the input signal. For example, f(x)=[255(x/255) r +1]/(x+1), r>0. The equation f(x) may be adjusted according to practical usage. The Bound function is defined as: B=Bound[A] min max . When the min≦A≦max, B=A; when A≦min, B=min; when max≦A, B=A. wherein 0≦min<max, and in the embodiment, the max value may be 255 or 235, and the min value may be 0 or 16.
In the embodiment, the format of the luminance lookup table may be shown herein below:
TABLE 1
Input luminance
Output luminance
0
Yout[0]
1
Yout[1]
.
.
.
.
.
.
255
Yout[255]
Then, step S 104 is performed. The calculating module 12 may establish a chrominance-luminance lookup table according to the parameters and the luminance lookup table. In the embodiment, the calculating module 12 also may store the luminance lookup table in the memory module 10 . The chrominance-luminance lookup table is generated according to the parameters and the luminance lookup table. In another aspect, the luminance of the image information in the invention also may be stored in the 8 bits mode, and the luminance is divided into 256 classes (the chrominance Cb and Cr are distributed between 0 and 255). In the embodiment, the luminance lookup table is generated according to the following formula:
CY out( x,y )=Bound[ f C ( St,Sa,f ( x )) y−b C ( St,Sa,f ( x ))] min max ×256 +Y out( x )
Wherein x is an integer between 0 and 255, and y is an integer between 0 and 255.
f C (St,Sa,f(x))=Sa×St×f(x)+(1−St)b C (St,Sa,f(x))=128×St×(Sa×f(x)−1),
and f(x) is a non-liner function for generating a gain value corresponding to the input signal.
In the embodiment, the chrominance-luminance lookup table format may be shown in table 2 as follows:
TABLE 2
Input
Output
chrominance-luminance(C, Y)
chrominance-luminance
0, 0
CYout[0, 0]
0, 1
CYout[0, 1]
.
.
.
.
.
.
255, 255
CYout[255, 255]
That is, for example, when a luminance and a chrominance need to be looked up via the chrominance-luminance lookup table in the invention, a corresponding group of luminance and chrominance are found in a single search process.
Then, step S 106 is performed to retrieve the image information from the memory module 10 using the processing module 14 . Afterwards, step S 107 is performed to determine the format of the image information using the processing module 14 .
In the embodiment, when the format of the image information is determined to be the first format, in the image processing method, step S 108 is performed, and the first format herein is the YCbCr 4:2:2, which is the YCbCr color space, and the YCbCr sampling ratio is 4:2:2. The image information of the first format with multiple pixels (such as 1024*768 pixels), and two adjacent pixels correspond to a macro pixel.
To facilitate the processing, each macro pixel may be composed by two process pixels, and each process pixel includes a chrominance and a first luminance. In step S 108 , the processing module 14 looks up the chrominance-luminance lookup table stored in the memory module 10 according to the chrominance and the first luminance of one of the process pixels. Then, step S 110 is performed, and the processing module 14 obtains the adjusted chrominance and the first adjusted luminance corresponding to the chrominance and the first luminance from the chrominance-luminance lookup table, and then the chrominance and the luminance corresponding to a process pixel are adjusted.
Then, step S 112 is performed. The processing module 14 determines whether each process pixel of the image information is adjusted. If not, step S 108 to step S 110 are performed repeatedly to adjust all the process pixels in the image information.
In the image processing method of the prior art, the luminance is adjusted by looking up the luminance lookup table, and the chrominance is adjusted by looking up the chrominance LUT. In the image processing method of the invention, via the chrominance-luminance lookup table, the luminance and the chrominance may be adjusted in a single flow path, and thus the image processing speed is improved.
On the other hand, when the format of the image information is determined to be the second format, step S 114 of the image processing method in the invention is performed. The second format herein may be YCbCr 4:2:0, which is the YCbCr color space, and the YCbCr sampling ratio is 4:2:0 or 4:1:1. The image information with the second format with multiple pixels, and the four adjacent pixels of the second format correspond to a macro pixel.
To facilitate the processing, each macro pixel is formed by two process pixels, and each process pixel in the image information of the second format includes a chrominance, a first luminance and a second luminance. Step S 114 is performed, and the processing module 14 looks up the chrominance-luminance lookup table stored in the memory module 10 according to the chrominance and the first luminance of one of the process pixels. Then, step S 116 is performed, and the processing module obtains the adjusted chrominance corresponding to the chrominance and the first adjusted luminance corresponding to the first luminance from the chrominance-luminance lookup table. Then, step S 118 is performed, and the processing module 14 looks for the luminance lookup table according to the second adjusted luminance of one of the process pixels, thereby adjusting the chrominance and luminance of the process pixel. Afterwards, in step S 120 , the processing module 14 obtains the second adjusted luminance in the luminance lookup table according to the second luminance. Consequently, the luminance and chrominance adjustment are performed.
Then, step S 122 is performed. The processing module 14 determines whether each process pixel of the image information is adjusted. If not, step S 114 to step S 120 are repeatedly performed to adjust the process pixels of the image information.
Comparing with the prior art in which the three components of the color space are separately looked for, in the image processing method of the invention, a group of adjusted luminance and chrominance are obtained in only one flow path via the chrominance-luminance lookup table. When the ratio of the luminance and the chrominance in each process pixel is not 1:1, the luminance lookup table is also looked up to generate the second adjusted luminance. Therefore, it corresponds to multiple format of the images, and different LUTs may be fully used to improve the processing speed.
Then, in the image processing method and the image processing system 1 , step S 124 is further performed to reset the parameters (St, Sa). When the image processing system 1 determines that the adjusted image information does not satisfy the requirement, or the user updates the parameter by himself or herself via the input module 16 , the parameter (St, Sa) may be reset. Therefore, in the image processing method and the image processing system 1 , step S 102 to S 122 may be reperformed. According to the set parameters, the calculating module 12 reestablishes the luminance lookup table and the chrominance-luminance lookup table. Then, the processing module 14 may adjust the image information according to the reestablished luminance lookup table and the reestablished chrominance-luminance lookup table.
To sum up, in the image processing method and the image processing system, a chrominance-luminance lookup table is established to adjust a luminance and a chrominance in a single flow path. As a result, the processing flow path is simplified, and processing time is saved.
Although the present invention has been described in considerable detail with reference to certain preferred embodiments thereof, the disclosure is not for limiting the scope of the invention. Persons having ordinary skill in the art may make various modifications and changes without departing from the scope. Therefore, the scope of the appended claims should not be limited to the description of the preferred embodiments described above. | An image processing method and an image processing system adapted to processing image information with multiple process pixels are disclosed. The image processing method includes steps of: setting a group of parameters; establishing a luminance lookup table; establishing a chrominance-luminance lookup table; retrieving the image information; determining a format of the image information; and if the format of the image is a first format, utilizing the chrominance-luminance lookup table to generate an adjusted chrominance and a first adjusted luminance corresponding to one of the process pixels; if the format of the image is a second format, utilizing the chrominance-luminance lookup table and the luminance lookup table to generate an adjusted chrominance, a first adjusted luminance, and a second adjusted luminance corresponding to one of the process pixels. | 7 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates generally to apparatus for forming concrete or other flowable paving material into a paved surface and, more particularly, to such a paving apparatus of the self propelled type for continuous slip-form paving of roadways, sidewalks and like concrete pavement surfaces.
[0002] Self-propelled construction vehicles and other construction equipment of diverse types are well known. One type of such construction equipment are so-called slip-form paving machines essentially adapted to continuously form concrete or another flowable paving material along the ground or other base surface, for example, to form a roadway. Diverse forms of such machines have been described in prior patents, representative examples of which may be found in U.S. Pat. Nos. 3,175,478; 3,264,958; 3,637,026; 3,771,892; 3,970,405; 4,197,032; 4,360,293; 4,925,340; 4,948,292; 5,044,820 and 5,590,977.
[0003] Conventionally, it is commonplace for paving equipment of this type to support the machine frame on a plurality of drivable transport assemblies, such as so-called crawler track assemblies, adapted to facilitate steerable driving of the paving machine over substantially any ground surface along which a roadway or like surface is to be paved. The frame of the machine is equipped with various devices and mechanisms to perform various functions of the paving operation, including typically an auger or other suitable mechanism for distributing the paving material laterally across the front of the machine, followed by a vertically disposed plate or like structural member, commonly referred to as a strike-off plate, positioned with a lower edge thereof at a desired elevation with respect to the ground surface to be paved to control the amount of paving material passing thereunder and thereby to initially form the material generally as a slab of the desired thickness, and then followed by a substantially horizontally disposed undersurface, commonly referred to as a screed, for purposes of leveling and finishing the concrete material.
[0004] In basic operation, a continuous supply of concrete or other suitable paving material is deposited in front of the paving machine between its transport assemblies as the machine is driven over the intended path of the pavement surface, with the auger mechanism initially distributing the paving material laterally, after which the lower edge of the plate “strikes off” a rough slab form of a desired thickness of the concrete material which then is more precisely spread, leveled and finished by vibration devices followed by the screed.
[0005] Once such a paving machine is under operation, it is a relatively simple matter to maintain ongoing operation on a substantially continuous basis, absent any malfunctions in the machinery itself, merely by maintaining a sufficient supply of concrete in front of the advancing machine. However, the initial start-up of a paving operation, including beginning operation at the start of each work day or otherwise after a period of sufficiently extended inactivity in the paving operation by which the concrete of a previously paved section of roadway has solidified and begun to cure, requires special efforts and can be much more problematic.
[0006] Specifically, the initial start-up of a slip-form paving operation, especially when continuing the paving of a previously formed section of pavement, requires that a sufficient starting supply of concrete be deposited not only in front of the auger mechanism and the strike-off plate but also therebehind beneath the screed fully up to the previously formed section of pavement, so as to ensure that there will be no interruption in the continuity nor the quality of the pavement slab. Generally, the only reliable way of accomplishing start-up of a slip-form paving machine under such circumstances is to position the machine immediately above the previously formed section of pavement and then to have workers manually shovel and preliminarily level a sufficient quantity of new wet concrete beneath and behind the auger mechanism, the strike-off plate and the screed, in addition to depositing a supply of concrete in front of the auger mechanism, whereupon operation of the machine can begin. This process is not only labor-intensive, time-consuming, expensive and inefficient, it is also difficult to ensure that the starting portion of the new section of pavement is of comparable quality and uniformity to that of the previously-formed section.
SUMMARY OF THE INVENTION
[0007] It is accordingly an object of the present invention to provide an improved slip-form paving apparatus which will address and overcome the disadvantages of the known paving apparatus as discussed above. More particularly, it is an object of the present invention to provide a slip-form paving apparatus which will better facilitate the deposition of a supply of concrete beneath the apparatus for starting up a new paving operation.
[0008] Briefly summarized, the present invention is basically applicable to any slip-form paving apparatus having a frame supported on a steerable self-propelled transport arrangement with a pavement forming assembly or like means disposed on the frame at a forward side thereof. In accordance with the present invention, the pavement forming assembly is movable with respect to the frame between an operative position disposed relative to a ground surface to be paved for distributing and forming a paving material on the ground surface generally into a desired form of pavement and an inoperative position disposed at a greater elevation relative to the ground surface than in the operative position for permitting access beneath the frame during an initial start-up of the apparatus so as to enable a starting quantity of the paving material to be readily deposited thereat.
[0009] In a preferred embodiment, the pavement forming assembly comprises a spreading mechanism or like means for distributing paving material across the forward side of the frame, e.g., an auger mechanism, a plow-type spreader, or the like, and a strike-off member or like means for generally leveling the pavement material on the ground surface. The spreading mechanism and the strike-off member, such as a strike-off plate, are integrally mounted pivotably to the frame for pivoting movement between the inoperative and operative positions. Thus, with the pavement forming assembly pivoted or otherwise moved into its inoperative position, workers have ready access to deposit and preliminarily work a starting supply of concrete or other paving material beneath the paving apparatus behind the normal operative disposition of the spreading mechanism and the strike-off member, after which the pavement forming assembly may be pivotably moved into its operative position for beginning the paving operation.
[0010] Other details, features and advantages of the present invention will be described and understood from a detailed description of a preferred embodiment of the invention set forth below with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [0011]FIG. 1 is a front perspective view of a slip-form paving apparatus equipped with a retractable pavement forming assembly in accordance with the present invention, illustrating the pavement forming assembly in operative disposition; and
[0012] [0012]FIG. 2 is another front perspective view of the slip-form paving apparatus of FIG. 1, illustrating the pavement forming assembly in retracted disposition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0013] Referring now to the accompanying drawings and initially to FIG. 1, a self-propelled slip-form paving apparatus in accordance with the present invention is indicated in its totality at 10 . The paving apparatus 10 basically comprises a structural framework 12 supported substantially horizontally on four front and rear steerable transport assemblies 14 , 16 , each preferably comprising a so-called crawler assembly of the endless track type, disposed at the four corners of the structural framework 12 in laterally and longitudinally spaced relation to provide stable suspension of, and steering control for, the framework 12 . An internal combustion engine (not shown) or other suitable self-contained power generator, preferably in conjunction with a hydraulic pump (also not shown), is mounted to the structural framework 12 to provide drive power to and steering control of the transport assemblies 14 , 16 , and to otherwise supply operational power to the various systems of the paving apparatus.
[0014] The embodiment of the paving apparatus 10 depicted in the accompanying drawings is particularly adapted for use in road construction for the continuous slip-form paving of a slab-type concrete roadway, the lateral width of the apparatus 10 between the front and rear transport assemblies 14 , 16 being sufficient for the formation simultaneously of two road lanes side-by-side one another. However, as those persons skilled in the art will understand, the essential features and inventive concepts forming the present invention are equally well-adapted to substantially any other form of self-propelled slip-form paving apparatus.
[0015] The paving apparatus 10 is equipped with a screw-type auger assembly 18 transversely spanning the framework 12 at the forward leading side thereof, comprised of two aligned auger sections 18 A, 18 B each of which is selectively driveable in opposite rotational directions independently of the other auger section, for laterally distributing a supply of concrete, or another suitable flowable paving material, deposited in front of the apparatus across the ground structure over which the roadway is to be paved. However, as those persons skilled in the art will recognize, other types of mechanisms for spreading the paving material may also be utilized instead of the auger assembly, e.g., a plow-type spreader or the like. Immediately rearwardly of the auger assembly 18 , a vertically disposed plate 20 , commonly referred to as a strike-off plate, is supported by the framework 12 with a lower edge 20 A of the plate 20 extending laterally across substantially the full width of the apparatus 10 at an elevation essentially corresponding to the desired elevation to which the roadway slab is to be paved, to act as a metering gate controlling the level of concrete material passing underneath the strike-off plate 20 .
[0016] A series of vibratory devices, only partially visible at 22 in FIG. 1 but more fully shown in FIG. 2, are mounted to the framework 12 at regular spacings across the transverse width of the paving apparatus 10 immediately behind the strike-off plate 20 to further assist in the leveling and settlement of the distributed concrete material by imposing a rigorous vibratory action on the concrete material passing under the strike-off plate 20 . A finish screed 24 is disposed rearwardly of the vibratory devices 22 and is preferably in the form of a substantially horizontal plate extending transversely across the width of the paving apparatus 10 and rearwardly from the vibratory devices 22 .
[0017] Thus, the basic operation of the paving apparatus 10 will be understood. As the paving apparatus 10 is self-propelled via the front and rear crawler assemblies 14 , 16 on the ground surface over which the roadway slab is to be formed, a suitable supply of concrete is maintained continuously in front of the auger assembly 18 . The operator of the paving apparatus 10 actuates and deactuates one or both of the sections 18 A, 18 B of the auger assembly 18 in either direction as necessary to distribute the concrete material with general uniformity laterally across the forward side of the paving apparatus. As the paving apparatus 10 advances, the vertically-disposed plate 20 strikes off a limited amount of the concrete material and partially compacts it to a uniform density, following which the vibratory devices 22 serve to expel any air bubbles from the concrete material and to further settle and smooth the upward surface of the concrete material. As the paving apparatus 10 continues to advance forwardly, the screed 24 is then drawn over the vibrated depth of the concrete material, performing a final compacting thereof and smoothing of its upper surface.
[0018] To the extent thus far described, the basic structure and operation of the paving apparatus 10 is essentially conventional. As already described above, it will be recognized that the operative disposition of the auger assembly 18 and the strike-off plate 20 substantially closes off access to the underside of the paving apparatus 10 and makes difficult the delivery, manually or otherwise, of a suitable quantity of concrete or other paving material underneath the apparatus for start-up purposes.
[0019] Accordingly, the present invention deviates from the structure and operation of conventional paving apparatus by mounting the strike-off plate 20 pivotably to the forward side of the framework 12 for selective retraction of the strike-off plate upwardly away from its normal operative disposition. Specifically, a laterally-extending support member 26 is supported from an elevated forwardly-facing portion 12 A of the framework 12 by two crank arms 28 affixed rigidly to the support member 26 at a spacing therealong and, in turn, pivotably affixed to correspondingly spaced support brackets 30 on the frame member 12 A. The strike-off plate 20 is rigidly affixed to the support member 26 for depending relation therefrom in its operative disposition via a pair of bracket arms 32 . Pivoting movement of the support member 26 , the crank arms 28 , the bracket arms 32 , and the strike-off plate 20 about the pivot axis P is controlled via extension and retraction of a linear actuator 34 , preferably in the form of an hydraulic piston-and-cylinder assembly 34 the cylinder body of which is mounted at an elevated disposition on the framework 12 via an upstanding mounting bracket 36 , with the piston extending downwardly to a point of affixation to one of the bracket arms 32 .
[0020] Additionally, in accordance with the present invention, the auger assembly 18 is affixed integrally with the strike-off plate 20 via a pair of support arms 38 extending forwardly in spaced facing relation to one another from the opposite lateral ends of the strike-off plate 22 , and an intermediate support bearing 40 disposed midway therebetween. Each support arm 38 carries an hydraulic motor 42 from which a respective one of the auger sections 18 A, 18 B extends in alignment with the other auger section to the intermediate support bearing 40 to which each of the auger sections 18 A, 18 B is rotationally mounted.
[0021] The operation of the present invention may thus be understood. As a result of the mechanical arrangement described above, the auger assembly 18 , the strike-off plate 20 , the bracket arms 32 , the support member 26 , and the crank arms 28 are rigidly affixed with respect to one another for pivoting movement as a unit relative to the pivot axis P defined by the two brackets 30 . With the piston-and-cylinder assembly 34 fully extended, the auger assembly and the strike-off plate unit 20 is pivoted downwardly in its normal operational disposition wherein the auger assembly 18 and the strike-off plate 20 face forwardly from the paving apparatus 10 in relatively close adjacency to the ground surface on which the paving apparatus 10 is supported, so as to operate in the normal manner already described above to distribute, compact and preliminarily level concrete material deposited in front of the paving apparatus 10 as it advances, as illustrated in FIG. 1. However, upon full retraction of the piston-and-cylinder assembly 34 , the unit of the auger assembly 18 and the strike-off plate 20 is pivoted approximately 90 degrees upwardly and then rearwardly to dispose the auger assembly 18 and the strike-off plate 20 at a substantial elevated spacing from the ground surface and thereby exposing the vibratory devices 22 and the screed 24 to ready access by workers, as illustrated in FIG. 2.
[0022] Thus, with the auger assembly 18 and the strike-off plate 20 in the inoperative disposition of FIG. 2, the ability of workers to quickly and easily deposit a start-up supply of concrete, or other paving material, beneath and forward of the screed 24 behind the normal operating disposition of the auger assembly 18 and the strike-off plate 20 is greatly facilitated and simplified. Preparation of the paving apparatus 10 for beginning a new paving operation, whether at a new paving location or continuing from the terminal point of an ongoing paving operation can be accomplished with less labor and in a shorter period of time and, hence, more efficiently and less expensively than with conventional paving apparatus. Once the appropriate start-up supply of concrete has been deposited beneath the paving apparatus 10 , the auger assembly 18 and the strike-off plate 20 are pivoted downwardly as a unit into their normal operative disposition via extension of the piston-and-cylinder assembly 34 to begin the paving operation. An additional benefit of the present invention is that the overall width of the paving apparatus is reduced with the auger assembly 18 and the strike-off plate 20 pivoted upwardly into the inoperative position, which achieves a narrower configuration to better facilitate over-the-road transport of the apparatus.
[0023] It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof. | In a slip-form paving apparatus, a forwardly disposed pavement forming assembly, such as an auger assembly and a strike-off plate, are pivotably mounted to the apparatus frame for movement between an operative disposition disposed adjacent a ground surface for distributing and forming paving material thereon generally into a desired form of pavement and an inoperative position more elevated from the ground surface for permitting access beneath the apparatus for depositing a starting quantity of the paving material during an initial start-up of the apparatus. | 4 |
This application is a continuation in part of U.S. patent application Ser. No. 08/022,365, filed Feb. 25, 1993, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method of manufacturing and using a brazing composition for use in various aluminum brazing applications.
2. Description of the Related Art
The brazing process typically involves joining aluminum or metal components together by disposing a brazing composition such as an aluminum or metal alloy and flux adjacent to or between the faying surfaces, i.e., the surfaces to be joined. The brazing filler alloy and flux and the faying surfaces are then heated to the brazing temperature, typically above the melting temperature of the braze alloy but below the melting temperature of the components to be joined. The brazing composition then melts, flows into the joint by capillary action and forms a fillet and seal that bonds the faying surfaces. Usually, the brazing alloy has a melting point that is about 30° C. to 40° C. lower than that of the faying surfaces. An example of a suitable aluminum brazing alloy is an aluminum-silicon (Al--Si) eutectic composition, which typically has a melting point at about 577° C.
It is often necessary to apply a flux composition to the faying surfaces prior to brazing. The application of flux to the surfaces to be brazed helps to remove any oxides ordinarily present on the exposed metal surfaces, helps to promote the flow of the molten brazing alloy during brazing, and inhibits further oxide formation on the surfaces. Thus, the flux material must be capable of removing metal oxides at preselected brazing temperatures while remaining substantially inert with respect to the brazing alloy. Since fluxes are usually reactive, e.g., capable of removing oxides, the flux should be transformed to its molten state at or near the melting temperature of the brazing alloy.
Chloride fluxes have been used in the past to braze aluminum assemblies. However, chloride fluxes are known to be hygroscopic and corrosive and to leave a hygroscopic, corrosive residue on the external surfaces of the faying assemblies. The chloride fluxed assemblies must be brazed soon after applying the flux to prevent corrosion of the aluminum and deterioration of the flux After brazing, this flux residue must be removed to enhance the assembly's anti-corrosion properties. The removal of the residue is difficult and expensive since the assemblies require extensive post brazing washing and treatment to obtain the required corrosion resistance. Moreover, disposal of the post brazing washing compound presents a problem since it contains contaminants from the chloride fluxing compound.
Non-corrosive, non-hygroscopic flux materials have recently been developed and used. Such fluxes are formed from a mixture of potassium fluoro aluminate complexes (typically kaI 4 and K 3 IF 6 ) and are sold by Solvay Performance Chemicals under the trademark NOCOLOK.
Various techniques are used to apply flux to the joint area and to the external portion of the faying surfaces. Usually, the flux is applied to the surfaces to be brazed and the surfaces are heated to allow the flux to melt, flow and coat the metal surfaces. The application of flux by such techniques is costly and time consuming as the flux must be removed from areas where it is not desired and because flux application and brazing must be performed in separate steps. Where non-corrosive fluxes, such as potassium fluoro aluminate complexes, are applied by such techniques it is particularly difficult to remove excess flux because these fluxes leave a residue that is substantially insoluble in water.
There exists some welding wire compositions that combine a flux with a welding filler alloy. U.S. Pat. No. 4,800,131 discloses a cored wire filler metal comprising an outer metal sheath that encloses a wire core, and a method of manufacturing such an assembly. This patent further discloses that the core wire can utilize an iron-wire core having a packed ferrous powder filler as a center. The center may also include other components such as admixtures of nickel, chromium and zinc. All examples, disclosures and teachings of 4,800,131 relate to welding of ferrous alloys.
U.S. Pat. No. 4,831,701 discloses a non-corrosive flux particulate coated with zinc or a zinc alloy, such as an aluminum zinc alloy. The coating is predisposed on the flux particulate by vacuum vapor deposition or ion plating. The coated flux particles can then be applied to a faying surface by spray coating. Although somewhat useful, such a composition does not provide for the ability to apply the flux particulate to precise locations without any associated flow of molten flux and brazing alloy that adheres to the faying surfaces in places where flux is not desired. This composition does not provide for the braze filler metal necessary to join the faying surfaces.
The use of non-corrosive fluxes such as NOCOLOK solve many of the problems associated with brazing aluminum. However, attempts at using such fluxes so that it can be applied to precise locations in the proper proportions have failed due to the inability of producing a flux cored product in anything other than very short lengths. Short lengths, while workable, having no commercial value since only long lengths of a flux cored product can be made into the variety of sizes needed to meet industrial needs.
Despite known brazing compositions and methods, there still exists a need for a fluxed cored brazing composition suitable for brazing aluminum that can be produced in continuous lengths from at least 500 feet to more than 10,000 feet long; is easily applied to various faying surfaces, is simple to handle, minimizes flux usage and flow and precisely controls the amount of filler metal and flux at each joint.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a method of preparing a flux-cored brazing composition that is easily utilized and able to conform to the contours of most faying surfaces.
It is still another object of the invention to provide a method of preparing a flux-cored brazing composition that is easily formed to a desired shape, such as ring, disc or ribbon.
Still another object of the invention is to provide a method of preparing a flux-cored brazing composition having a non-corrosive, non-hygroscopic flux disposed within a brazing alloy sheath.
Still another objective is to provide a method of preparing a flux-cored brazing composition that eliminates the use of organic materials to bind the flux to the braze filler metal alloy.
Yet another object of the invention is to provide a method of preparing a flux-cored brazing composition that mounts easily to surfaces to be brazed and leaves no excess flux by minimizing the amount of run-off experienced.
Finally, it is an objection of the invention to provide a method of preparing a flux-cored brazing composition that can be made in lengths ranging from 500 feet to more than 10,000 feet of continuous lengths. Other general and more specific objects of this invention will be apparent from the description and drawings which follow.
These and other objects are attained by the invention which provides, in one aspect, a brazing composition having an outer sheath or shell composed of an aluminum-silicon (Al--Si) alloy that encases a core of solid non-corrosive flux. The brazing alloy typically has a melting temperature in the range of 577°-613° C. The flux material typically is an eutectic mixture of K 3 IF 6 and KAI 4 that has a melting range between approximately 562° C. and 577° C. The flux material employed preferably is non-hygroscopic and non-corrosive. Because the flux and brazing alloy melt at approximately the same temperature range, there is little or no uncontrolled flow of flux to undesired areas of the surfaces to be brazed.
The flux-cored composition is produced by carefully feeding the finely powdered flux via a volumetric feeder to a strip of aluminum filler material that has been formed to provide a channel, then rolling the strip to form an elongate sheath having a length of at least five hundred feet long.
The flux core of the brazing component may also be a fluoride and/or chloride salt-containing corrosive flux that is disposed within a non-hygroscopic organic vehicle, such as acrylic, polybutene or a wax Such a composition has properties somewhat similar to a non-corrosive, non-hygroscopic flux as the vehicle prevents absorption of water vapor from the atmosphere and corrosion of the Al--Si sheath by the flux Such a composition also prevents deterioration of flux activity, thus increasing the shelf life of the product. Another advantage of such a composition is that it utilizes a premeasured volume of corrosive component and use of the flux is kept to a minimum. Although the vehicle helps such a flux composition achieve properties similar to a non-corrosive, non-hygroscopic flux the non-corrosive, non-hygroscopic flux has inherently greater environmental stability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a partially formed metal alloy strip.
FIG. 2A is a cross-sectional view taken along line 2A--2A of FIG. 1 of a rolled Al--Si strip formed into a substantial channel arrangement and filled with the finely powdered flux;
FIG. 2B is a cross-sectional view taken along line 2B--2B of FIG. 1 depicting a circular arrangement and of the flux core.
FIG. 3 depicts a braze ring of the flux cored brazing composition according to a preferred embodiment of the invention; and
FIG. 4 is a cross-sectional view taken along line 4--4 of FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates the progressive forming of the flux cored brazing composition 10 according to the present invention. The composite comprises a strip 12 of a brazing metal, such as a metal alloy, that is formed into channel 15 about its longitudinal axis. As illustrated, the channel is filled with powdered flux material 14. This extremely fine powder is extremely difficult to handle and especially difficult to introduce into channel 15 in precisely controlled and evenly distributed amounts. The inventor has found this is possible when a volumetric feeder having an auger feeder is utilized. Preferred is the type of volumetric feeder principally used for handling pharmaceutical materials such as made by Acrison, Inc. of Moonachie, N.J. This model features inter-auger action which is the rotation of double concentric augers operating at dissimilar speeds, thereby achieving the filling of channel 15 with powdered flux 14 at uniform density through the length of strip 12. Attempts to fill strip 12 with flux 14 without the use of such equipment is not possible and prevents the preparation of the flux-cored product in continuous lengths of more than 500 feet to 10,000 feet long.
Once filled with flux 14, channel shape 15 is rolled to form a cylinder 16, comprising a sheath of metal alloy strip encircling solid flux material 14. Preferably, the cylinder 16 is formed by an overlapping of lips 18 & 20 of strip 12.
FIG. 2A depicts a cross-sectional view of the formed channel 15 in which a braze alloy sheath 12 is a repository for a solid flux material 14.
FIG. 2B depicts a cross sectional view of cylinder 16 in which a brazing alloy sheath 12 encompasses a core of a solid flux material 14. The flux core 14, as shown in FIG. 2B, can be of firmly packed solid flux particulate mixture that effectively resembles a solid mixture. Alternatively, the flux core can be less dense and more loosely packed than the solid mixture of FIG. 2B.
Cylinders 16 can be formed into a variety of shapes to provide ease of brazing. FIGS. 3 and 4 illustrate a flux cored brazing composition in which cylinder 16 is formed into a braze ring 24 of a circular toroidal shape. As noted above, once the flux-cored brazing material is produced into extremely long lengths, it is economically feasible to reduce that length to various sizes as dictated by industry needs.
As illustrated, the circular flux cored component 24 includes a solid flux core 28 surrounded by a sheet of metal alloy 30. This and similarly shaped flux cored compositions facilitate ease of brazing as the composition can be formed to a number of desired shapes and sizes and easily positioned over a joint or surface to be brazed. The application of heat to the brazing composition causes essentially simultaneous flux application and brazing of the surface as the melting point of the flux and alloy are essentially the same. Thus, a single, manageable composition forming a unitary structure comprising the brazing alloy and flux is easily applied to the surfaces to be brazed. Moreover, each component of the unit has substantially the same melting temperature range.
The metal alloy strip 12 preferably comprises a suitable brazing alloy such as a eutectic mixture of aluminum-silicon. A preferred aluminum-silicon alloy preferably has an aluminum content between 87 and 93% by weight and, most preferably about 88% by weight, and a silicon content between 7 and 13% by weight and, most preferably 12% by weight. Strip 12 can be formed to any desirable thickness as will be appreciated by one having ordinary skill in the art. In a preferred embodiment strip 12 has a thickness between about 0.003 and 0.032 inch, and more preferably between about 0.008 and 0.012 inch, for ease of rolling and subsequent shaping.
Preferably, the aluminum-silicon alloy useful with the invention melts in the range of 577° to 613° C., and most preferably in the range of about 577° to 582°. Generally, the melting range will be about 577° C. to 613° C. where the silicon content of the alloy is 7.5%, about 577° C. to 599° C. where the silicon content of the alloy is 10%, and about 577° C. to 582° C. where the silicon content of the alloy is 12%.
The present invention preferably employs a solid, non-hygroscopic, non-corrosive flux material that is placed into the metal alloy channel 15 via the volumetric feeder discussed above. The flux preferably comprises, in powdered form, a mixture of potassium fluoro aluminate complexes, preferably, potassium tetrafluoroaluminate (KAI 4 ) and potassium hexafluoroaluminate (K 3 IF 6 ). Suitable fluxes for use as a flux core once the metal alloy strip 12 is formed into a sheath encasing the flux, can be obtained from Solvay Performance Chemicals Aluminum Corp. under the tradename NOCOLOK.
In one embodiment, it is desirable to incorporate a powdered metal alloy within the potassium fluoro aluminate flux in order to reduce the flux content of the brazing composite. The flux can thus be diluted with a powdered metal alloy, such as a silicon-aluminum alloy having silicon and aluminum contents similar to what is present in the brazing alloy sheath. The powdered metal alloy can be added to the flux at an amount of about 40 to 10% by weight of the flux.
The eutectic aluminum-silicon alloys useful in forming the flux cored brazing composition usually melt at about 577° C. Eutectic mixtures of potassium fluoroaluminates, and specifically combinations of KAI 4 and K 3 IF 6 , have a melting temperature in the range of about 562° C. and 577° C., a temperature slightly below the melting point of the brazing alloy. The melting points of both the flux and the brazing alloy are below that of the fraying surfaces. Other non-corrosive flux compositions may be employed provided they are suitable for brazing aluminum, even if the liquidus point thereof is somewhat above, rather than below, the melting point of the brazing alloy, provided the flux becomes reactive below the melting temperatures of the faying surfaces.
In one aspect of the invention, a non-corrosive flux is combined with an Al--Si eutectic alloy in a form that is easy to handle and simple to apply to various surfaces to be brazed. Accordingly, a narrow, elongate sheet or strip of a metal alloy composition 12, preferably Al--Si is formed or bowed about its longitudinal axis to form a channel shaped receptacle for the flux After the flux is deposited, the channel is formed into a cylindrical elongated sheath of metal alloy enclosing the flux. In a preferred embodiment, the ratio of flux to metal alloy by volume is in the range of about 60:40 to 10:90, and preferably, is about 30:70.
The cylindrical, elongate sheath of flux-cored brazing composition can subsequently be formed to a desired shape, such as a circle or oval. The composition can then be placed between or adjacent to the faying surfaces. The entire unitary structure and the faying surfaces are then heated to a suitable brazing temperature sufficient to melt the flux and the glazing alloy and thus join the faying surfaces. The components are then cooled to solidify the brazing alloy to secure the bond between the faying surfaces.
The metal alloy strip 12 may be formed or bowed into any desired shape and size. For example, the strip 12 may be rolled about its longitudinal axis in a substantially circular manner. Once rolled, the preformed sheet may be shaped, twisted or molded into various shapes, usually adopting a configuration complementary to the various angles and sizes of the surfaces to be brazed. As illustrated in FIGS. 3 and 4, the sheath can be formed into braze rings having a circular cross-section, and further having a diameter between 0.032 and 0.125 inches.
In another embodiment, a corrosive and hygroscopic flux particulate may be intimately combined with a moisture repelling vehicle composition, such as polybutene, a wax or acrylic. The flux and vehicle are then ball milled (for about 10 to 30 minutes) with a wetting agent and solvent to make the mixture non-hygroscopic and to keep captive any residual moisture inherent to a corrosive flux. The vehicle also serves to protect the brazing alloy sheath from the corrosive properties of the flux.
Such a formulation generally includes about 2-20% by weight vehicle, about 50-60% by weight flux and the balance solvent. The vehicle, as noted above can be an acrylic, a polybutene or a wax Suitable waxes include long chain fatty acids such as oleic and stearic acid. Suitable solvents are those compatible with the vehicle materials and can include mineral spirits, napthas, and straight chain or aromatic hydrocarbons.
The invention further contemplates a flux cored Al--Si elongate sheath having various cross-sectional shape and size dimensions. The elongate sheath can then be formed into a variety of shapes depending upon the faying surface contours and dimensions. Thus, the braze rings can be manufactured to meet whenever processing demands the user may have.
While there have been described what are at present considered to be the preferred embodiments of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention and it is, therefore, aimed to cover all such changes and modifications as fall within the true spirit and scope of the invention. | A method of producing a flux-cored brazing composition for brazing aluminum that can be produced in lengths ranging from 500 to 10,000 feet long. The flux, preferably a finely powdered potassium fluoroaluminate complex, is deposited in an extremely small channel of aluminum filler material using a volumetric feeder to ensure an even distribution of flux to metal alloy. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESERCH OR DEVELOPMENT
Not Applicable
REFERENCE TO A MICROFICHE APPENDIX
Not Applicable
BACKGROUND OF THE INVENTION
The proposed concept is related to conversion of liquid and gaseous hydrocarbon and alcohol fuels to product gas containing hydrogen, carbon monoxide, and traces of hydrocarbons that is useable in fuel cells. In particular, it relates to the unique capability of internal combustion engines (ICEs) operated with fuel in excess of the stoichiometric quantity to carry out this fuel conversion process.
The background of the invention includes processes and systems for supplying fuel to fuel cells, the use of internal combustion engines as chemical reactors, and power plants combining these elements.
Fuel cells are electrochemical systems that generate electrical current by chemically reacting a fuel gas and an oxidant gas on the surface of electrodes. Conventionally, the oxidant gas is oxygen or air, and the fuel gas is hydrogen or a mixture of hydrogen, carbon monoxide, and traces of hydrocarbons. The fuel gas may also contain non-fuel gases including nitrogen, water vapor and carbon dioxide. The specific fuel gas composition requirements depend on the type of fuel cell. Low temperature fuel cells, exemplified by proton exchange membrane (PEM) cells and alkaline fuel cells (AFC), can only utilize hydrogen as fuel, and contain precious metal catalysts that are poisoned by carbon monoxide. High temperature fuel cells, exemplified by solid oxide fuel cells (SOFC) and molten carbonate fuel cells (MCFC), do not contain precious metal catalysts, and utilize hydrogen, carbon monoxide, and traces of hydrocarbons as fuel. Most fuel cell types are adversely affected by sulfur compounds.
Pure hydrogen is the ideal fuel for all fuel cell types, but it is not widely available. Further, storage and transportation involves large, heavy and costly means such as compressed gas bottles. Practical fuel cell generators must therefore utilize commonly available and easily transported fuels including natural gas, liquefied petroleum gas (LPG), methanol, ethanol, gasoline and diesel fuel, and logistic fuel. These hydrocarbons and alcohols must be reformed to fuel gas suitable for the particular fuel cell application. In addition, these fuels often contain sulfur that must be removed. Conventional processes for desulfurizing and reforming liquid and gaseous fuels are well known in the art, and will only be summarized.
Fuel reforming is based on the endothermic reaction of hydrocarbon or alcohol fuel with steam and/or CO 2 , to form CO and H 2 . This can be done in two ways. The first is steam reforming. Steam reformers use high temperature catalyst filled tubes heated by burners fueled by fuel cell exhaust fuel and air streams. Steam is supplied by a waste heat boiler. Heat transferred across the tube wall drives the endothermic reaction. Such systems provide the highest hydrogen yield, but tend to be large, complex, and slow to start up and respond to load changes. Further, they require sulfur removal from the feedstock to avoid catalyst poisoning. The second is partial oxidation (POX) reforming. POX reformers and catalytic autothermal reformers eliminate high temperature heat exchangers by reacting a rich mixture of fuel and air to provide the reforming heat within the gas stream. Steam is added to the hot hydrogen and carbon monoxide to cool the stream and increase hydrogen yield. Non-catalytic POX reformers operate at temperatures around 1000° C. for gasoline and up to 1400° C. for heavy hydrocarbons, necessitating special heat-resistant materials. Autothermal reformers use a catalyst to operate at temperatures under 1000° C., and may be less costly. These systems are smaller, simpler and faster responding than steam reformers, and are preferred for applications such as vehicle propulsion. Even so, there is a delay before power is available in a cold start and the feedstock must be low in sulfur.
Generally heavier liquid hydrocarbons such as diesel fuel are the most difficult to reform, and have the greatest tendency to form soot rather than the desired product gas. Further, they are more likely to contain large amounts of sulfur. “Logistic” fuel is an extreme case. It is a low-grade, high sulfur diesel fuel that may be the only fuel available to the military in the field. While reciprocating and turbine ICEs operate directly on logistic fuel, fuel cell power plants require extensive fuel processing capability, resulting in additional size and weight.
The method of sulfur removal depends on both the reforming system and the type of fuel. If the reforming reaction uses a catalyst, then the sulfur is typically removed from the feedstock prior to reforming. Hydrodesulfurization is the classic means used for liquid hydrocarbons. Hydrogen separated from the product gas stream is reacted with the fuel over the catalyst to convert the sulfur compounds to hydrogen sulfide. The hydrogen sulfide is then removed by passing the stream through a zinc oxide bed. Activated charcoal filtration is sufficient to remove sulfur from natural gas before reforming. Non-catalytic POX reformers tolerate sulfur in the fuel, and convert it to hydrogen sulfide that can be removed from the product gas with a zinc oxide bed.
Since low temperature fuel cells can only utilize hydrogen and do not tolerate over 50 ppm CO, shift conversion and selective oxidation stages must be added to increase hydrogen and decrease CO levels. The situation is simpler for high temperature fuel cells. At 600° C. to 1000° C., CO and moderate quantities of hydrocarbons are reformed at the nickel anode surface using the steam, CO 2 and heat from the power generation reaction. The reforming process only needs to break down the heavy hydrocarbons into a mix of gasses that the SOFC can utilize directly or reform internally without soot formation. High-temperature fuel cell systems can therefore use the product gas from steam, autothermal and POX reformers directly.
Startup characteristics are often important in fuel cell power plants operating on hydrocarbon and alcohol. A certain amount of time is needed to start a reformer to generate hydrogen, and high temperature fuel cells require time to heat to operating temperature regardless of the availability of fuel. This delay necessitates an interim power source such as a battery or ICE for applications that require immediate response, such as vehicle propulsion or emergency power.
ICEs include turbine, reciprocating piston or other machines that compress air, heat the air by reacting fuel with the oxygen in the air, and expand the heated air to produce work. The theoretical amount of fuel required to consume the oxygen in the air is termed the stoichiometric quantity. Typically, the amount of fuel added is less than the stoichiometric quantity (a lean mixture), since this makes the most efficient and economical use of the fuel. Fuel in excess of the available oxygen (a rich mixture) is discharged in the exhaust and produces no useful work. The composition of excess hydrocarbon fuel, however, is changed by the combustion process. Rich mixture exhaust contains hydrogen, carbon monoxide, and small amounts of hydrocarbons in addition to nitrogen and water vapor. Oxides of nitrogen (NOX), typical pollutants produced by lean mixtures, are suppressed by the reducing environment created by the rich mixture. In addition, sulfur compounds are converted to hydrogen sulfide. The overall result of rich ICE operation with hydrocarbon fuel is shaft work and almost complete conversion of the excess fuel into product gas containing hydrogen and CO. One of the specific problems with a rich running ICE is the production of soot. The theoretical rich soot formation limit for fuel with a stoichiometric ratio of 14.65 is 5.5, but in a real piston ICE soot formation occurs at higher ratios.
Use of an air/fuel mixture richer than stoichiometric in an ICE is a known technique to produce combustible gas. U.S. Pat. No. 4,041,910 by Houseman, assigned to NASA, describes a multicylinder engine in which the exhaust from two rich-running cylinders is used to fuel six lean-running cylinders. This avoids the oxide of nitrogen formation peak near stoichiometric operation, while providing complete fuel combustion. Houseman states that soot-free operation as low as 6.5 can achieved by adding water or steam, recycling the water-containing exhaust from the lean-running cylinders, or vaporizing and thoroughly mixing the fuel with heated air. U.S. Pat. No. 5,339,634 by Gale et. al., assigned to Southwest Research Institute, shows a similar system. In Gale et. al. a shift conversion catalyst is used to increase the hydrogen content of the rich-running cylinder exhaust. This exhaust is then mixed with additional fuel and air and fed to the lean-running cylinders where the hydrogen extends the lean limit. Neither of these patents contemplates using the rich exhaust as fuel for fuel cells.
U.S. Pat. No. 6,276,473 B1 by Zur Megede shows fuel cells and ICEs combined in an integrated vehicle power plant. It does not, however, utilize the ICE as a fuel processor for the fuel cell. Instead, it uses it as a means of providing immediate vehicle motion, as a heat source to warm the fuel cell to operating temperature, and as a supplemental power source after warm-up. The ICE and fuel cell both use a common hydrogen fuel source.
BRIEF SUMMARY OF THE INVENTION
The present invention is a means for generating power from hydrocarbon and alcohol fuels in a power plant that integrates an ICE and a fuel cell. The ICE is operated with a rich hydrocarbon or alcohol fuel mixture to produce shaft power and an exhaust stream containing a mixture of gasses including hydrogen, carbon monoxide, and traces of hydrocarbons. The fuel cell then electrochemically oxidizes this product gas at the anode to produce electric power, while reducing oxygen at the cathode. The depleted fuel cell product gas and air exhaust streams may be handled in several ways. The prior art approach is to mix and combust the streams in an afterburner to produce process heat and eliminate exhaust pollutants. This invention includes additional productive uses for the depleted product gas stream. In one, a portion of the depleted product gas stream is recycled and combined with the ICE inlet fuel-air mixture to supply water vapor for soot suppression. In another, the depleted product gas stream is mixed with air to form a lean mixture that is burned in a separate ICE to produce shaft power and serve as an afterburner. The separate ICE may also be a section of the same machine used to process fuel. An example is to use one or more dedicated cylinders in a multi-cylinder reciprocating ICE that also includes fuel processing cylinders as an afterburner.
The present invention has a number of objectives. First, it employs the high peak temperatures in the ICE cycle to decompose the hydrocarbons and alcohols and hydrogenate sulfur compounds without catalysts. In particular, difficult feedstock such as “logistic” fuel may be processed. At the same time, oxide of nitrogen formation is strongly suppressed through the reducing effect of excess fuel. Reciprocating ICEs are particularly effective in achieving high peak combustion temperatures (on the order of 2000° C.) while maintaining the engine components at relatively low temperatures compatible with ordinary materials. Second, thermodynamic advantages are gained. The gas expansion work produces shaft power and reduces the gas temperature so that the exhaust temperature is on the order of 700° C. Like electric power, shaft power is thermodynamically the highest grade of energy, and contributes to the overall system efficiency. Third, system operation is enhanced. ICEs start in seconds and, while the system warms up, produces immediate shaft power that may be used for a number of purposes including vehicle propulsion and emergency electric power generation. The hot exhaust serves to heat the balance of the fuel processing system and start the electrochemical power generation process. The ICE may be controlled such that startup operation is near stoichiometric to maximize shaft power output and minimize fuel waste and exhaust pollution while the system is heated, and then shifted to rich operation. In general, the ICE facilitates system control. Rotational speed, throttle position and fuel-air ratio may be varied over a wide range to control the composition and flow rate of product gas. Fourth, the invention utilizes mature, low cost ICE technology that is supported by a ubiquitous manufacturing, service and fuel supply infrastructure. This facilitates earlier widespread fuel cell application with the attendant environmental and energy conservation benefits.
In summary, rich-running ICEs are more that simple replacements for conventional reformers in fuel cell systems. The integration of ICEs and fuel cells of the present invention is a novel and synergistic combination that forms a power plant with the energy efficiency and environmental advantages of fuel cells together with the fast response and fuel flexibility of ICEs.
Upon examination of the following detailed description the novel features of the present invention will become apparent to those of ordinary skill in the art or can be learned by practice of the present invention. It should be understood that the detailed description of the invention and the specific examples presented, while indicating certain embodiments of the present invention, are provided for illustration purposes only. Various changes and modifications within the spirit and scope of the invention will become apparent to those of ordinary skill in the art upon examination of the following detailed description of the invention and claims that follow.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The appended claims set forth those novel features that characterize the invention. However, the invention itself, as well as further objects and advantages thereof, will best be understood by reference to the following detailed description of preferred embodiments taken in conjunction with the accompanying drawings, where like reference characters identify like elements throughout the various figures, in which:
FIG. 1 is an illustration of a reciprocating ICE serving as a fuel processor for high temperature fuel cells;
FIG. 2 is a graph reproduced from E. M. Goodger, Petroleum and Performance in Internal Combustion Engineering , Butterworth Scientific Publications, London, 1953 that shows the exhaust composition of reciprocating engine exhaust as a function of air/fuel ratio;
FIG. 3 is a graph reproduced from Fritz A. F. Schmidt, The Internal Combustion Engine , Chapman and Hall, London, 1965 that shows the rich and lean combustion limits of pentane, carbon monoxide and hydrogen as a function of mixture temperature;
FIG. 4 illustrates a power plant embodying the invention using high-temperature fuel cells and an afterburner to consume depleted product gas;
FIG. 5 illustrates a power plant embodying the invention using low-temperature fuel cells and an afterburner to consume depleted product gas;
FIG. 6 illustrates a power plant embodying the invention using high-temperature fuel cells and an ICE for utilizing depleted product gas.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to energy conversion systems that combine ICE and fuel cell elements to convert hydrocarbon and alcohol fuels to electric power and shaft power. The present invention is described with respect to a reciprocating four-stroke Otto cycle IEC. However, it will be obvious to those skilled in the art that the following detailed description is similarly applicable to many types of ICEs that may be operated with excess fuel including rotary, Brayton cycle turbine, and two-stroke reciprocating machines.
FIG. 1 illustrates the basic invention. A four-stroke engine 1 is combined with a high temperature fuel cell stack 2 . The engine is of generally conventional design, and may be single-cylinder as shown or multi-cylinder. The piston 3 is reciprocated in the cylinder 4 by the connecting rod and crank assembly 5 . The fuel injector 17 adds hydrocarbon or alcohol fuel to the incoming air in the inlet passage 7 forming a rich, homogeneous air/fuel mixture. The inlet valve 8 and the exhaust valve 9 are opened and closed in a timed relationship with the motion of the piston 3 such that air/fuel mixture is drawn in through the inlet passage 7 , compressed, ignited, expanded to produce shaft power, and pushed out into the exhaust passage 10 as product gas. The combustible constituents of the product gas include hydrogen, carbon monoxide, and small amounts of hydrocarbons. A duct 11 delivers the product gas to the fuel cell anode passages 12 , where its combustible constituents are electrochemically oxidized. Air is passed through the cathode passages 13 where its oxygen is electrochemically reduced. The product gas oxidation and oxygen reduction combine to generate electric power that is collected at terminals 14 connected to the cell anodes and cathodes. It should be noted that production of net ICE shaft power is not essential. Operation at idle with no net shaft power output, or operation in which shaft power is supplied to the engine is within the scope of the invention.
FIG. 2 shows the dry exhaust gas composition of a four-stroke reciprocating spark ignition ICE operating on liquid hydrocarbon fuel at air/fuel ratios both richer and leaner than stoichiometric. At a rich air/fuel ration of 10:1, for example, the exhaust gas fuel components are about 6.5% hydrogen, 12% carbon monoxide, and a faction of a percent methane. Non-fuel gases include about 7% carbon dioxide and 74% nitrogen. The previous quantities are on a dry basis: wet exhaust gas contains about 15% by volume of water vapor. Oxide of nitrogen content is very low because of the strongly reducing environment in rich, homogeneous combustion. Very rich operation is desirable for several reasons. First, it shifts the energy conversion from the ICE to the fuel cell, which is in many cases more efficient. Second, it increases the fuel concentration in the product gas stream, reducing the flow volume and the size of the flow passages. Finally, it decreases oxide of nitrogen formation. Historically, rich ICE operation has been used with piston engines primarily for cold starting and to generate peak power for motor vehicle acceleration or aircraft takeoff. Normal operation is slightly leaner than stoiciometric for efficiency and low exhaust emissions. The smoke limit, the point at which some excess fuel is converted to soot rather than hydrocarbon monoxide, forms the practical limit to rich operation. In theory, soot formation occurs below an air/fuel ratio of 5.5 for fuel with a stoichiometric ratio of 14.65, but in real ICEs soot formation occurs at higher ratios. According to Houseman, (U.S. Pat. No. 4,041,910) soot-free operation as low as 6.5 can be achieved by a combination of means including addition of water, steam or recycled exhaust to the air/fuel mixture, and vaporizing and thoroughly mixing the fuel with heated air. The data in FIG. 3 supports Houseman's conclusions. The rich combustion limits for several different fuels are two or more times the stoichiometric fuel quantity, and the limits increase with temperature.
A power plant is defined as a system that contains all the elements required to convert fuel and air into electric or mechanical power, and complete power plants using the present invention may require elements in addition to the ICE and fuel cell. Three power plant system variations are shown schematically in FIG. 4 -FIG.6 below. All include sulfur removal, but it should be understood that availability of low-sulfur fuel or use of fuel cells that are sulfur tolerant could eliminate this need. In addition to the major components shown, a number of components including a supervisory control system, sensors, valves, pumps, blowers, thermal insulation, electric power conditioning and control systems, and enclosures may be required to implement the invention and adapt it to particular applications. These are not part of the present invention, and are omitted from the descriptions for clarity.
FIG. 4 shows a power plant system containing high temperature fuel cells. ICE inlet air enters duct 15 , and is heated to 250° C. to 350° C. in heat exchanger 16 to assure fuel vaporization. Fuel is added through injector 17 and mixed with the heated air in chamber 18 . Optionally, depleted anode product gas from duct 19 is added to the inlet mixture to increase the water vapor content and suppress soot formation. The inlet mixture is then drawn into the ICE 1 and combusted to produce shaft power and product gas. The shaft power is delivered to a load 20 that may be an electric generator, power plant auxiliaries, vehicle propulsion, or other application. The product gas temperature is about 700° C. as it leaves the ICE, and is cooled to 350° in heat exchanger 21 before passing through zinc oxide bed 22 for hydrogen sulfide removal. Cooling is necessary since higher temperatures will damage the zinc oxide. The desulfurized product gas is reheated in heat exchanger 23 to 500° C. to 800° C. before entering the anode passages of the fuel cells 2 through duct 24 . Fuel cell inlet air enters duct 25 , and is heated to 500° C. to 800° C. in heat exchanger 26 before entering the cathode passages of the fuel cells 2 through duct 27 . A portion, typically 60% to 90%, of the fuel value of the product gas is electrochemically oxidized in the anode passages by the air passing through the cathode passages. Typically 30% of 80% of the oxygen is electrochemically reduced and removed from the air stream. The depleted air stream then enters the afterburner 28 through duct 29 .The product gas exhaust stream is optionally divided into two portions at junction 30 . One portion enters the afterburner 28 where it is mixed with the depleted air stream and combusted. The afterburner exhaust stream, which is largely free of unburned fuel constituents, is cooled in heat exchanger 31 and released to the atmosphere through exhaust duct 32 . The other portion of the product gas exhaust stream leaving junction 30 flows through duct 19 and is mixed with the ICE inlet mixture. The thermal management system 33 consists of multiple heat transfer paths that move heat from heat exchangers 21 and 31 that cool gas streams to heat exchangers 16 , 23 , and 26 that heat gas streams.
FIG. 5 shows a power plant system containing low temperature fuel cells. As in the high temperature system, ICE inlet air enters duct 15 , and is heated to 250° C. to 350° C. in heat exchanger 16 . Fuel is added through injector 17 and mixed in chamber 18 with the heated air. Optionally, afterburner exhaust from duct 19 . is added to the inlet mixture to increase the water vapor content and suppress soot formation. The inlet mixture is then drawn into the ICE 1 and combusted to produce product gas, and shaft power is delivered to load 20 . The product gas is cooled to 350° in heat exchanger 21 and passed through zinc oxide bed 22 for hydrogen sulfide removal. Additional process steps are required to condition the product gas for the low-temperature fuel cells. The high temperature shift converter 34 uses an iron oxide and chromium oxide catalyst to convert a portion of the carbon monoxide to hydrogen and carbon dioxide through a reaction with water vapor in the gas stream. The reaction is exothermic, and the conversion decreases with increasing temperature. For this reason, shift conversion is done in stages with cooling in-between. Heat exchanger 35 is used to cool the gas stream to 200° C. to 250° C. before it enters the low temperature shift converter 36 where a copper oxide and zinc oxide catalyst converts additional carbon monoxide to hydrogen. Heat exchanger 37 cools the stream to 150° C. to 200° C. It is then mixed with a small amount of air entering through duct 38 , and carbon monoxide is selectively oxidized by the platinum catalyst 39 . The product gas stream is cooled in heat exchanger 40 to a temperature compatible with the low temperature fuel cells before it enters the anode passages of the fuel cells 2 through duct 24 . Fuel cell inlet air enters duct 25 and flows into the cathode passages of the fuel cells 2 through duct 26 . A portion, typically 60% to 90%, of the product gas is electrochemically oxidized in the anode passages by the air passing through the cathode passages. Typically 30% of 80% of the oxygen is electrochemically reduced and removed from the air stream. The depleted air and product gas streams enter the afterburner 28 through ducts 29 , and 41 where they mix and combust. The afterburner exhaust stream, which contains carbon dioxide and water vapor and is largely free of unburned fuel constituents, is cooled in heat exchanger 31 and released to the atmosphere through exhaust duct 32 . A portion of the afterburner exhaust stream is optionally diverted at junction 42 into duct 19 to be mixed with the ICE inlet mixture. The thermal management system 33 consists of multiple heat transfer paths that move heat from heat exchangers 21 , 35 , 37 , 40 and 31 that cool gas streams to heat exchanger 16 that heats the inlet air stream.
FIG. 6 shows a power plant system containing high temperature fuel cells that uses a second ICE engine to combust the depleted product gas and extract additional work. The system flow up to the fuel cell exit in this example is similar to the high temperature fuel cell example of FIG. 4 . ICE inlet air enters duct 15 , and is heated to 250° C. to 350° C. in heat exchanger 16 , fuel is added through injector 17 and mixed in chamber 18 with the heated air. Optionally, system exhaust from duct 19 is added to the inlet mixture to increase the water vapor content and suppress soot formation. The inlet mixture is then drawn into the first ICE 1 and combusted to produce product gas, and shaft power is delivered to a load 20 . The product gas is cooled to 350° in heat exchanger 21 and passed through zinc oxide bed 22 for hydrogen sulfide removal. The desulfurized product gas is reheated in heat exchanger 23 to 500° C. to 800° C. before entering the anode passages of the fuel cells 2 through duct 24 . Fuel cell inlet air enters duct 25 , and is heated to 500° C. to 800° C. in heat exchanger 26 before entering the cathode passages of the fuel cells 2 through duct 27 . A portion, typically 60% to 90%, of the product gas fuel value is electro-chemically oxidized in the anode passages by the air passing through the cathode passages. Typically 30% of 80% of the oxygen is electrochemically reduced and removed from the air stream. The depleted product gas stream is optionally divided into two portions at junction 30 . Air is added to one portion of the depleted product gas through duct 43 to form a lean air/fuel mixture that enters the second ICE 44 . Lean-burning ICE 44 supplies shaft power to load 45 and acts as an afterburner to consume the remaining fuel in the product gas stream. Exhaust from the second ICE is cooled in heat exchanger 46 and released to the atmosphere through exhaust duct 47 . The depleted cathode air stream passes through duct 29 and heat exchanger 48 and is released to the atmosphere through exhaust duct 49 . The other portion of the product gas exhaust stream leaving junction 30 flows through duct 19 and is mixed with the inlet mixture of ICE 1 . The thermal management system 33 consists of multiple heat transfer paths that move heat from heat exchangers 21 , 46 , and 48 that cool gas streams to heat exchangers 16 , 23 , and 26 that heat fluid streams. The ICEs 1 and 44 may be separate machines as shown or dedicated fluid paths through a single machine. An example is a multicylinder reciprocating engine in which one group of cylinders comprises ICE 1 and another group comprises ICE 44 .
There are no definite upper or lower limits to the output of power plants incorporating the present invention, and output of less than 100 watts to tens of megawatts is contemplated.
The foregoing embodiments of the present invention have been presented for the purposes of illustration and description. These descriptions and embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in the light of the above disclosure. The embodiments were chosen and described in order to best explain the principle of the invention and its practical applications to thereby enable others skilled in the art to best utilize the invention in its various embodiment and with various modifications as are suited to the particular use contemplated. It intended that the invention be defined by the following claims. The term “air” is used in the claims to designate any gas that contains significant amounts of free oxygen, “system fuel” is used to designate any liquid or gaseous hydrocarbon or alcohol before conversion, and “product gas” is used to designate the reformed fuel gas stream. | The present invention uses an internal combustion engine operated at an air/fuel ratio richer than stoichiometric as a partial oxidation reformer in fuel cell power generation systems. Commonly available liquid or gaseous hydrocarbon or alcohol fuels, including “logistic” fuel in military applications, are converted to a product gas mixture containing hydrogen, carbon monoxide, and traces of light hydrocarbons. The product gas may be used directly or with minimum processing by high temperature fuel cells, or processed further for use in low temperature fuel cells. Advantages include high efficiency, adaptability to a variety of fuels, and quick system startup with immediate shaft power availability. | 2 |
This application is a continuation of application Ser. No. 09/373,336, filed Aug. 12, 1999, now abandoned, and claims priority to provisional application No. 60/096,869, filed Aug. 17, 1998.
BACKGROUND OF THE INVENTION
The present invention relates generally to an oxidation and corrosion resistant coating. More particularly, the present invention relates to a coating composition that is produced by a process for co-depositing transition metals on metallic components. This coating is particularly useful in protecting nickel and cobalt and iron-based superalloys from heat corrosion and oxidation attack, especially during high temperature operation. Such coating includes aluminum and silicon and the coated substrate may comprise precious metal, nickel, cobalt or MCrALY. Such coated substrates are particularly useful in gas turbine and jet engine hot zones.
BRIEF DESCRIPTION OF THE PRIOR ART
There are numerous applications in which metal components are exposed to elevated temperatures for prolonged periods of time. In such applications, it is important that the metal components retain their solid strength and mechanical properties after repeated exposures to high temperatures. High temperature operation is often found in turbomachinery blading members such as turbine blades, vanes, nozzles etc. used in aerospace and land-based machinery wherein the temperature of the component, or portion of the component, may rise to well above 1500° F. (815° C.). For example, modern gas turbine engines, commonly known as “jet engines,” frequently operate in high temperature environments in excess of 2000° F.
Components manufactured from what has become known in the art as “superalloy materials” are recognized as generally providing for a higher degree of shape retention, and significantly more strength retention, at a wider variety of temperatures than non-alloy materials. Superalloys include metals containing high nickel, high cobalt and high nickel-cobalt-base. While often exhibiting more desirable mechanical properties at high temperatures, superalloys frequently suffer, as many other metals and alloys, from oxidation, sulfidation and corrosion degradation reactions (as for example when such component is exposed to salt spray and sulfur compounds), all of which are accelerated at high temperatures. While the efficiency of a gas turbine engine generally increases with increasing nominal operating temperature, the ability of turbine blades and vanes made from superalloys to operate at increasingly great temperatures is limited by the ability of the turbine blades and vanes to withstand the heat, oxidation and corrosion effects of the impinging hot gas stream.
Superalloy components are frequently coated with materials that are less prone to such degradation reactions or which form an adherent oxide scale which protects the superalloy material from such reactions. Such degradation-resistant coatings often incorporate elements such as aluminum, silicon, chromium, and platinum group metals, and may comprise composite alloys such as MCrAlY, where M is selected from the group consisting of iron, nickel, cobalt, and various mixtures thereof. A thermal barrier coating, such as a ceramic, may also be bonded to a degradation-resistant coating to further insulate the component from the high temperature, as such ceramic materials often do not directly adhere to the oxidized superalloys themselves. Degradation-resistant coatings and thermal barrier coatings can markedly extend the service life of gas turbine engine blades, vanes, and the like.
Degradation-resistant coatings are often chosen to provide high resistance to oxidation or hot corrosion, with little regard to the mechanical properties of the coating. Degradation-resistant coatings are typically applied in a thickness of 0.001-0.010 inches. Components may be coated differentially depending on whether one or more areas of the component is subjected to more or less degradative environments. Preferably, the degradation-resistant coatings should not crack when subjected to mechanically or thermally-induced strain. If the degradation-resistant coating is designed to form a protective oxide scale on the component, such scale preferably should not be dissolvable in liquids which may come in contact with the coated component.
A wide variety of techniques and processes are known for applying a degradation-resistant coating or layer to the surface of metal articles. Such techniques include diffusion coating, physical vapor deposition, plasma spray, and slurry coating.
Diffusion Coating
In diffusion coating, elements such as Al, Cr, Si, and/or Ti are reacted with halogenated activator at elevated temperatures to form gaseous species of Al, Cr, Si, and/or Ti which condense on the substrate and form a coating. Pack cementation is one of the most commonly employed diffusion coating techniques wherein the parts to be coated are placed in surface contact with the coating source material.
An early example of aluminum-silicon co-deposition by pack cementation is set forth in U.S. Pat. No. 3,779,719 to Clark et al. The Clark et al. reference discloses that mixtures of aluminum, silicon and chromium heated at about 1750° F. for 8 to 12 hours to a maximum coating temperature of 1900° F. produce, by diffusion of such materials into the substrate, corrosion resistant coatings and that performance is enhanced when the silicon content is at least 5% by weight and the Si/Cr weight ratio is within the range of 0.6 to 1.4. A silicon pack cementation process is also described in U.S. Pat. No. 4,369,233 to van Schaik, wherein a silicon containing coating is produced by overcoating surfaces previously treated with active metal species, such as Y or Ti. Preferably, the active metal is said to be ion plated, diffused in a vacuum, and mechanically treated prior to application of the silicon. The van Schaik reference suggests that a protective coating of ternary silicides, such as Ti 6 Ni 16 Si 7 and Ni 49 Ti 14 Si 37 , is formed. Likewise, U.S. Pat. No. 5,492,727 to Rapp et al. describes a pack cementation process wherein chromium and silicon are co-deposited onto ferrous substrates utilizing a dual activator system in a two-step heating cycle.
Physical Vapor Deposition
In physical vapor deposition techniques (“PVD”), metallic components which are to be incorporated into a coating are applied by means of vaporization. Numerous physical vapor deposition techniques have been described in the literature and include above-the-pack (“ATP”), chemical vapor deposition (“CVD”), and electron beam physical vapor deposition (“EB-PVD”). ATP processes are accomplished in a manner similar to pack cementation, however, the substrate is held out-of-contact with the metal containing and activator containing source materials, and a coating forms by physical vapor deposition and diffusion of metal onto and into the substrate. The metal source may be present in powdered form or as metallic chunks. CVD, a specialized form of vapor coating, is usually accomplished using a starting gas. The gas can either be the source of the deposited metals or can be the reactant used to generate the metallic vapor done by passing it over or through a bed of metallic source. CVD processing typically requires more stringent processing controls and cleaner source materials. EB-PVD functions by creating a molten pool of metal from which material evaporates and then deposits on the substrate in a line-of-sight path. ATP, CVD, and EB-PVD processes typically result in coatings that are smoother, cleaner and cosmetically improved compared to parts coated by pack cementation. Numerous examples of ATP, CVD, and EB-PVD and other types of physical vapor deposition processes can be found in the art. The list of reactant sources, materials and substrates used in such processes is long and varied.
U.S. Pat. No. 3,486,927 to Gauje (SNECMA Corp.) discloses a method for vapor depositing aluminum to make a coating that protects metal articles subject to high temperature. At the Third International Conference on Chemical Vapor Deposition (Salt Lake City, Utah 1972), Felix and Beutler demonstrated coated nickel superalloys by CVD methods in a stream of silicon tetrachloride and hydrogen at 980° C. to 1080° C. Resultant coatings were said to be upwards of 10 mils thick with upwards of 25% silicon. Increased corrosion protection was claimed for such coating.
U.S. Pat. No. 4,371,570 to Goebel et al. discloses an overlay coating for superalloys, the outer layer of which is silicon enriched, wherein the surface layer is produced by diffusing silicon via, among other methods, physical vapor deposition (see col. 4, lines 27-60). The Goebel et al. patent describes physical vapor deposition wherein the article to be coated is held over a molten pool of silicon in a vacuum chamber and the surface of the substrate is preferably heated at 1750° F. as the silicon vapors condense on the substrate. Further heat treatment to 1850° F. is said to promote further diffusion of the silicon into the overlay coating. The Goebel et al. reference discloses increased corrosion protection when a composite coating formed by siliconizing over MCrAlY-type coatings is performed, and in particular when the outer layer coating is rich in silicon.
Likewise, U.S. Pat. No. 5,217,757 to Milaniak et al. discloses a powder mixture for applying gas phase aluminide coatings to nickel or cobalt based superalloys. The Milaniak et al. reference describes a powder mixture consisting essentially of about 5-20 weight percent ammonium bifluoride as an activator (or halides (preferably fluorides) of alkali or alkaline earth metals), 10-30 weight percent chromium as buffer and a balance of Co 2 Al 5 . The Milaniak et al. reference states that elimination of aluminum oxide as a powder constituent dramatically improves the quality of the aluminide coating.
Moreover, U.S. Pat. No. 5,492,726 to Rose et al. discloses a process for applying a protective coating to nickel and/or cobalt-based superalloys involving applying a thin layer of a platinum-group metal onto the surface of a superalloy, heating the superalloy in the presence of a silicon vapor to diffuse the resulting platinum-group metal silicide into the superalloy surface, diffusion coating the silicided superalloy with vapors of a diffusion powder composition containing sources of aluminum, and heating the superalloy to form a ductile protective coating. Such coating is said to comprise an outer zone of an aluminide of said platinum-group metal and an inner stabilizing zone of silicided platinum-group metal comprising from 3 to 20% by weight silicon.
U.S. Pat. No. 4,034,142 teaches application of Al, Cr, Si and Y to the surface of superalloys by sputtering, a physical vapor deposition technique, or by an EB-PVD method. The Si, at 0.5 to 7.0 weight percent, is present in elemental form as a solid solution in both the gamma and beta phases of the nickel aluminide coating. U.S. Pat. No. 4,933,239 to Olson et al., discussed below with respect to plasma spray techniques, also discloses that its overlay coating can be applied by EB-PVD.
Many different apparatuses utilizing physical vapor phase deposition methodologies are described in the art, the design often varying with respect to the particular industry in which such technology is employed, e.g., aerospace vs. semiconductor industries. For example, several patented equipment designs and processes are described in U.S. Pat. Nos. 5,462,013, 5,407,704, and 5,264,245 to Howmet Corporation, wherein it is disclosed, among other things, that varying temperature locally to match local metal halide reactivity enhances the uniformity of aluminide coatings.
Plasma Spray
Another coating method frequently employed to form degradation-resistant coatings is the so-called “plasma spray” method. Plasma sprays incorporate mixtures of powders that are made molten and sprayed onto substrates at very high velocity and temperature. Plasma spray coatings typically have good corrosion resistance due to high Cr content and fairly good oxidation resistance due to the presence of Al and Y or Hf. Such coatings typically have a matrix of MCrAlYX(Hf). Examples of plasma spray techniques include vapor plasma spray (“VPS”), high velocity oxygen fuel spray (“HVOF”), low pressure plasma spray (“LPPS”), and air plasma spray (“APS”).
U.S. Pat. No. 4,615,864 to Dardi et al. teaches that a plasma spray coating containing 5 to 15% wt % aluminum, up to 12 wt % silicon, and various other active metals, such as Hf or Y, improves resistance to sulfidation and oxidation reactions. The Dardi et al. reference also contemplates ion plating and physical vapor deposition methods for the application of various coatings.
U.S. Pat. No. 4,933,239 to Olson et al. discloses an improved coating that is produced in a two-step process which may employ plasma spray techniques encompassing over-aluminizing a thin, nominally 0.0015″, metallic overlay coating containing Si, Y and Hf. The Olson et. al. reference describes a duplex microstructure comprising about 20-35 weight percent aluminum enriched with about 0.1-5.0 weight percent yttrium, about 0.1-7.0 weight percent silicon and about 0.1-2.0 weight percent hafnium.
U.S. Pat. Nos. 5,401,307 and 5,582,635 to Czech and Schmiz describe plasma sprayed and PVD deposited MCRAlY coatings containing 1-2% silicon that have improved corrosion resistance and ductile-to-brittle transition temperature below 500° C.
Slurry Coating
Slurry coating may also be used to form degradation-resistant coatings. Slurry coatings are typically applied by dip or paint spray application techniques. The slurry may be applied in single or multiple steps, before firing to form the coating. Typical slurry coatings are heated to between 1600° F. and 2000° F. U.S. Pat. No. 3,741,791 to Maxwell et al. discloses a paint slurry coating for superalloys containing MCrAlYSi. Silicon content in the described Maxwell et al. slurry is disclosed to be in the range of 10% -16%. The Maxwell et al. reference further discloses applying the slurry to substrate material heated to 2100° F.-2225° .F to cause the slurry to become molten on the substrate surface thereby dissolving some of the substrate while the material diffuses into the substrate material.
U.S. Pat. No. 4,310,574 to Deadmore et al. describes a method for aluminum and silicon application that requires spraying a lacquer slurry comprising cellulose nitrate containing high purity silicon powder and subsequently pack-aluminizing the silicon slurry sprayed superalloy substrate. A sublayer of high purity silicon in an aluminide structure characterizes the resultant coating.
U.S. Pat. No. 4,500,364 to Krutenat describes a slurry method for the application of aluminum and silicon to iron-based materials. This slurry method is similar to that described in U.S. Pat. No. 4,310,574 above, where eutectic compositions of aluminum and silicon in binder systems are sprayed onto superalloy surfaces and thermally diffused. The slurries become molten in processing and produce coatings that have high levels of silicon in the outer layers. Silicides and elemental silicon are disclosed to be present.
U.S. Pat. No. 5,547,770 to Meelu et al. may be said to present an advancement in slurry Al—Si coatings. Such coating is multi-layered and silicon-enriched and is produced by multiple and sequential slurry-spray-and-diffuse cycles. This coating limits the silicon content of the coating directly adjacent to the surface to a maximum of 10% and also forms multiple bands of chromium-silicon spaced inside the aluminide coating. Diffusion of nickel and chromium from the base metal into the coating zone are disclosed to improve coating performance. Such coating is disclosed as reducing silicon-induced surface brittleness, associated with prior art coatings, while increasing the corrosion resistance through the presence of an equally spaced sublayer of chromium silicide bands. Diffuse distribution of the silicide phases has been reported to enhance coating performance. See Berry et al., International Gas Turbine and Aeroengine Congress and Exposition, Jun. 5-8, 1995. A coating based on the Meelu et al. disclosure is produced commercially and known in the industry under the trade name SERMALOY™ 1515.
The presently available coating deposition techniques suffer from a number of disadvantages. For example, pack cementation, plasma spray, and slurry deposition methods are less than desirable when parts of relatively complex design, having internal passages and the like, are to be coated. Such techniques may clog or obstruct small internal passages, mandating a thorough cleaning of the part prior to shipment. On the other hand, physical vapor deposition techniques (such as ATP, CVD and EB-PVD), while avoiding such clogging problems and in general permitting more uniformity in thickness and composition, as currently employed, often require multi-step processes to produce many types of multiplex coatings.
Among the degradation-resistant coatings available today, it is recognized in the art that degradation-resistant coatings comprising Al—Si offer significant advantages, such as increased ductility and corrosion protection. Al—Si degradation resistant coatings typically contain more than 0.5 weight percent Si and may contain numerous other elements and compounds thereof. U.S. Pat. No. 5,057,196 to Creech et al. describes a two-step process for producing a Pt-Si-Al coating on superalloys. The critical processing steps involve the electrophoretic co-deposition of platinum and silicon material, diffusion heat treatment, electrophoretic deposition of aluminum-containing material, and heat treatment.
U.S. Pat. No. 5,492,726 to Rose et al. describes a multi-step method for producing a platinum group silicon-modified aluminide to nickel and/or cobalt-based superalloys. This method involves applying a thin layer of a platinum-group metal on the superalloy, heating the superalloy over a thermal cycle in the presence of a silicon vapor phase to diffuse the resulting platinum-group metal silicide into the superalloy surface, diffusion coating the silicided superalloy with vapors of a diffusion powder composition containing sources of aluminum and heating the superalloy to form a ductile protective coating.
Much work has been undertaken with respect to the co-deposition of oxide forming species in order to reduce the time and expense involved with multi-step coating processes. However, with respect to the co-deposition of silicon and aluminum, successful co-deposition has only been effectuated by means of pack cementation, EB-PVD, plasma spray, and slurry coating techniques. Attempts to use the arguably more advantageous ATP or CVD techniques have been unsuccessful or uneconomical. In a work authored by R. Bianco and R. Rapp entitled “Pack Cementation Aluminide Coatings on Superalloys: Codeposition of Cr and Reactive Elements”, Apr. 1993 (4), pages 1181-1190, the authors argue that while it is theoretically possible to co-deposit aluminum and silicon at high temperatures, using physical vapor deposition in levels of Si greater than 1 wt. % would be extremely difficult. These authors cite at least two major obstacles which need to be overcome in the co-deposition of silicon and aluminum by physical vapor deposition: (1) the formation of silicon carbide at the coating surface due to the high carbon content of many superalloys which inhibits the co-deposition and (2) the great difference between aluminum halide partial pressures and silicon halide partial pressures. Bianco and Rapp were unable to co-deposit such elements by conventional ATP means. Many others in the art do not believe that co-deposition using ATP techniques is possible.
Given the advantages associated with ATP techniques discussed above, the superior degradation-resistant coating formed with Al—Si, and the economic and time saving advantages of co-deposition, it would be highly advantageous to be able to employ ATP techniques to co-deposit Al and Si on superalloys and superalloys overcoated with MCrAlY coatings and precious metal materials. Furthermore, it would be advantageous to be able to co-deposit Al and Si using a relatively inexpensive methodology.
BRIEF SUMMARY OF THE INVENTION
In accordance with one embodiment of the present invention a degradation-resistant coating comprising Al and Si is formed by the process of: (a) furnishing a nickel, cobalt or iron-based superalloy substrate; (b) furnishing one or more powder mixtures containing from about 1 to about 10 percent Al and from about 1-20 percent Si; (c) heating the one or more powder mixture(s) at a temperature between about 1500° F. to about 2200° F.; (d) supporting the heated superalloy substrate out of contact with the heated powder mixture(s) at a distance such that vapor from said powder mixture(s) can contact with the superalloy substrate; (d) depositing an Al—Si containing coating on the superalloy substrate from about 1 to about 12 hours; (e) heating the superalloy substrate to form a protective layer containing aluminum and silicon at the surface of the substrate.
The present invention relates to a simplified process for applying a protective coating containing aluminum and silicon onto metallic bodies or components by means of vapor deposition.
More particularly, the present invention relates to a process whereby aluminum and silicon may be co-deposited onto metallic superalloys utilizing ATP techniques.
Further, the present invention relates to an improved aluminum and silicon degradation-resistant coating formed by co-depositing aluminum and silicon by means of ATP techniques.
And yet further, the present invention relates to a vapor phase process, and a coating made utilizing such process, wherein aluminum and silicon are co-deposited in vapor phase in a temperature range of approximately about 1600° F.-2100° F. for more than approximately two hours to produce a coating thickness ranging from approximately 0.001″ to approximately 0.005″. And finally, the present invention relates to a co-deposited vapor Al—Si coating containing at least 6 wt. % Si and no more than 32 wt. % Al with the preferable ratio of SLIM in the range of 0.1-0.5, and more preferably the ratio being between 0.2-0.4.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a graph interrelating average coat thickness to the weight composition of coat elements in a CMSX-4 nickel-based substrate coated with Al—Si by the process of the present invention.
FIG. 2 is a graph interrelating average coat thickness to the weight composition of coat elements in a IN713 nickel-based substrate coated with Al—Si by the process of the present invention.
FIG. 3 is a graph interrelating average coat thickness to the weight composition of coat elements in a MAR-M-002 nickel-based substrate coated with Al—Si by the process of the present invention.
FIG. 4 is a graph interrelating average coat thickness to the weight composition of coat elements in a CM188LC nickel-based substrate coated with Al—Si by the process of the present invention.
FIG. 5 is a graph interrelating average coat thickness to the weight composition of coat elements in a CM188LC nickel-based substrate coated with Al—Si by the process of the present invention.
FIG. 6 is a graph interrelating average coat thickness to the weight composition of coat elements in a GX-4 cobalt-based substrate coated with Al—Si by the process of the present invention.
FIG. 7 is an energy dispersive spectroscopy plot for an exemplary CMSX-4 substrate coated with Al—Si by the process of the present invention.
FIG. 8 is an energy dispersive spectrascopy plot for an exemplary IN713 substrate coated with Al—Si by the process of the present invention.
FIG. 9 is on energy dispersive spectroscopy plot for an exemplary MAR-M-002 substrate coated with Al—Si by the process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
According to this invention, it has been found that aluminum and silicon can be caused to co-deposit on alloy metal substrates, in particular, those selected from the group of iron, nickel, cobalt, palladium, platinum, rhodium and chromium, through a vapor phase deposition process in which the aluminum and silicon are carried from one or more powdered mixtures to the surfaces of the substrate. The coating process of the present invention may be carried out at any of the conventional temperatures at which physical vapor deposition techniques such as ATP, CVD and EB-PVD are performed, but more preferably 1500° to 2100° F.
While the substrate to which the coating of the present invention may be applied is not limited by composition, the substrate may incorporate a quantity of, or contain a significant weight percent of, a metal such as nickel, cobalt, palladium, platinum and rhodium. Preferably, the substrate on which the coating is placed contains cobalt or nickel.
In general, the aluminum and silicon sources may be present in powdered or chunk form. The aluminum and silicon sources may be kept separated in two powder mixtures, or may be combined into one master mix. However, it has been found that for the same powder chemistries, that a combined mix may result in a Si content in the coating which is slightly lower than when the powders are kept separate. The powdered silicon source may also be replaced with an external source of silicon that is accomplished using hydrogen or argon as a carrier gas for gaseous silicon tetrachloride. The advantages of combined or separate mixes or external silicon supplies have not been fully investigated, but are not considered to be limitations to the process.
Preferably, the silicon to aluminum ratio is approximately 0.1-0.5, even more preferably between 0.2-0.4.
Preferably, two separate powder mixtures are prepared, one containing the source of aluminum for the coating, the other containing the source of silicon for the coating. Most preferably, the first powder mixture providing the source of aluminum may comprise by weight 1-10 percent AlF 3 , 1-5 percent 200-mesh aluminum, and the balance 100-mesh aluminum oxide. Preferably, the second powder mixture providing the source of the silicon may comprise by weight 0.5-4 percent NH 4 Cl, 1-20 percent 325-mesh silicon, and balance 100-mesh aluminum oxide.
The substrate and aluminum and silicon source materials are placed together in a retort and heated. Preferably, the sources of aluminum and silicon are separate mixtures each placed in a separate container in the retort. The substrate should be placed at a distance from the source materials such that vapor containing aluminum and silicon from the heated source materials impinges upon the surface thereof. Preferably, the substrate is supported at least 3 cm from the source materials with positioning being above or beside the source mix.
The powder mixture(s) are preferably heated at a temperature of 1700° F.-2100° F., more preferably at a temperature of 1800° F.-2000° F. and yet more preferably between a temperature of 1850° F.-1975° F. The substrate should preferably be heated in the same retort as the powdered mixtures, and thus heated to the same temperature range as the powder mixtures. Preferably the temperature of the retort is ramped up over time until the desired temperature of the coating is reached.
The substrate and source are exposed to a thermal cycle wherein aluminum and silicon start to deposit at about 1400° F. At higher temperatures, the rate of metallic gas production is accelerated and coating deposition is accelerated as the metallic vapors impinge on the substrate. Uniform dispersion of silicon in the nickel or cobalt aluminum matrix is achieved at 1600° F. or higher. Temperature holds at 1600° F., 1700° F., and even 1800° F. may be used, but are not necessary to the final microstructure and in some cases may be detrimental if final heating is 1850° F. or higher. For example, the retort may be heated to 1975° F. in 2-6 hours or more preferably in 3-4 hours, without holds at any lower temperature. The substrate shall remain in the coating vapors for 1-15 hours, more preferably 2-12 hours, and more preferably 4-8 hours. The duration at temperature is temperature, substrate, atmosphere and coating thickness dependent.
Preferably, heating is accomplished in a retort purged with either argon or hydrogen. The retort may either have forced gas flow impinging on the substrate surface or may be a sealed retort with no forced gas flow directly on the substrates and source. For example, the retort may be heated to in excess of 1300° F. in argon, and then switched to hydrogen flow and continued heating to 1850° F. or higher in 2-6 hours with optional holds at intermediate temperatures before reaching maximum coating temperature and holding for the required time of 1-15 hours. The substrate should preferably remain in the vapor phase preferably from 1-15 hours, more preferably 2-7 hours, and yet more preferably 3-6 hours.
The Al—Si degradation-resistant coating made by the process described above typically comprises at least three distinct aluminide zones. The coating is predominantly grown by outward diffusion of nickel and cobalt. As an example, the following can be said of a 75 micron thick coating. The outer most zone approximately 10-15 microns thick should be nearly free of chromium and refractory metal phases and low in chromium and refractory elements when compared to substrate base metal levels. The outer zone is a solid solution that usually contains only nickel, cobalt, aluminum, silicon, and chromium unless the substrate has been precoated with a platinum group metal. Nickel suicides and other suicides may be present but are note required for good performance. The next inner zone contains silicide phases of at least chromium. The third, inner most zone is the diffusion zone that usually contains the highest levels of silicon. The average weight percent of Al is preferably 18-32, more preferably 22-30, and yet more preferably 24-28. The weight percent of Si is preferably 1-20, more preferably 3-15 percent, and yet more preferably 6-9. The Si/Al ratio is preferably 0.1-0.5, more preferably 0.2-.04, and yet more preferably 0.22-0.32. The ratio of Si/Cr is not critical in coating of this invention. Coating thickness is preferably between 0.001″-0.006″, more preferably 0.0015″-0.0045″, and yet more preferably between 0.002″-0.004″.
In general, if a bare nickel-based substrate is to be coated, a particularly advantageous Al—Si corrosion resistant coating of the present invention comprises 4-65 weight percent Ni, 18-32 weight percent Al, and 1-12 weight percent Si, more preferably 45-60 weight percent Ni, 20-30 weight percent Al, and 3-10 percent Si, and yet more preferably 48-55 weight percent Ni, 25-30 weight percent Al, and 5-10 weight percent Si.
If a cobalt-based substrate is to be coated, a particularly advantageous Al—Si degradation-resistant coating of the present invention may comprise 10-35 weight percent Al, 3-25 weight percent Si, and the remainder primarily Co and Ni, more preferably 20-30 weight percent Al, 5-15 weight percent Si, and the remainder primarily Ni and Co, and yet more preferably 22-28 weight percent Al, 6-15 weight percent Si, and the remainder primarily Co and Ni.
If the substrate is prepared with a precious metal coating such as platinum, the minimum content should be 15 weight percent with 18-32 weight percent Al and 1-12 weight percent Si, more preferably, 18-28 weight percent Al and 1-10 percent Si, and yet more preferably 18-26 weight percent Al and 1-6 weight percent Si.
Such Al—Si degradation resistant coatings have been discovered to provide superior protection against sulfidation attack at 800° C. and 850° C. and show acceptable oxidation resistance in standard testing at 1121° C. as compared to currently available Al—Si and chromide degradation resistant coatings. Performance is enhanced by at least a factor of 2 and by as much as a factor of 12. Sulfidation resistance is far superior to simple aluminides and platinum aluminides with improvement factors of at least 4 and as much as 25 times or more for both. In thermal-mechanical testing, the coating of this invention outperforms the best slurry AlSi coating by a measure of at least 4 times and is nearly equivalent to single phase CVD PtAl coating, the most ductile of the advanced aluminide coatings.
Although the invention is not limited by any hypothesis regarding the cause of such superior effect, it is hypothesized that the more uniform deposition of Si in nickel and cobalt aluminides resulting from vapor deposition (as opposed to other coating methods), as well as an outwardly grown coating with dispersed silicon, and greater control on maximum Al content as noted on electron microscopy, may account for the enhanced protection provided by the coatings formed using the present invention.
The above method differs from the literature in several ways. Firstly no prior art reference cites any method of co-deposition of Al and Si by vapor, nor does any reference indicate that such deposition technique has been successfully employed with Al and Si (although there are references that mention that it might be possible). Secondly, the literature cites examples using powder mixes usually containing high levels of Al and Si and sometimes Cr. Most often these mixtures are not made from elemental forms, but from costly alloy forms of Al, Si, and/or Cr. With the reduction in metal content and simplification of powder form, the method of the present invention has an inherently lower cost while affording the advantage of applying a variety of coating compositions that have not yet been available. The Si/Al ratio is preferably 0.1-0.5, more preferably 0.2-.04, and yet more preferably 0.22-0.32. The ratio of Si/Cr is not critical in coating of this invention.
The present invention is believed to provide an important advance in the art of degradation-resistant coatings, and in particular in the art of coating superalloy materials with Al and Si. The present invention provides an oxidation-resistant and corrosion-resistant coating system for protection of superalloy materials, in particular when such materials are to be incorporated into gas turbine components, and a process for preparing such protected components. The chemistry of the coating is modified from that of prior coatings to increase the adherence of the protective oxide scale and to increase the strength and diffusional stability of the coating while maintaining adequate resistance to corrosion by salts and sulfur and oxidation by high temperature exposure. The coating process described in the present invention not only permits co-deposition of Al and Si in an economical and time-saving manner, but also results in a Al—Si degradation-resistant coating which is superior to similar coatings deposited by processes presently employed in the art. For example, the process for coating of the instant invention may be optimized to provide increased performance and operating life of a gas turbine.
Other advantages of the invention will be apparent from the following more detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. The following examples are meant to be illustrative rather than limiting.
EXAMPLES
The following commercially available alloys are used: MAR-M-002, CMSX-4, IN 713, CM186LC, and GX-4.
Example 1
A mixture comprising by weight, 10 percent AlF 3 , 5 percent 200-mesh aluminum, 5 percent 325-mesh silicon, 1 percent NH 4 Cl, and a balance of 100-mesh aluminum oxide is prepared. The mixture is pans on the bottom of a retort grid system and placed in a 30 inch diameter, pre-conditioned retort. A 1′ square piece of CMSX-4 (prepared for coating by TIG welding a wire on one end, degreasing in solvent, grit blasting with #220 grit aluminum oxide, and blowing clean with air) is suspended over the mixture at a distance of 1 centimeter at room temperature. The retort is purged with N 2 for forty-five minutes at 375 cubic feet per hour (CFH). The retort is then purged with argon at 375 CFH for 1 hour. The retort is placed in a furnace and the temperature is ramped up in equal gradients to 1400° F. over a 2.5 hour period. The temperature is subsequently ramped up to 1600° F. over a 1 hour period of time, to 1965° F. over a 3 hour period, and is held at 1975° F. (+25° F./−10° F.) for 2.5 hours. At 1350° F. the retort is purged with H 2 at 375 CFH and the H 2 flow maintained at 375 CFH for the remainder of the coating cycle. The coated substrate is then cooled in H 2 at 375 CFH until the chamber temperature reached 400° F., wherein the cooling gas is changed to argon (for 1 hour at a minimum CFH of 375). A smooth silvery-white-gray coating of 0.002″ to 0.003″ in thickness is formed on the CMSX-substrate. Electron-microscopic analysis of the coating evidences three distinct aluminide structures in the coating.
Example 2
Two powder mixtures are prepared. The first powder mixture, the source of aluminum, consists of, by weight, 5 percent AlF 3 , 2 percent 200-mesh aluminum, and balance 100-mesh aluminum oxide. The second powder, the source of the silicon, consists of, by weight, 0.5 percent NH 4 Cl, 10% 325-mesh silicon, and balance 100-mesh aluminum oxide. The powders are placed in separate containers in the same coating vessel at a ratio of approximately 6 parts aluminum mix to 1 part silicon mix. Nickel-base superalloy substrates, IN738, MAR-M-002 and CMSX-4 are cut into 1″ square tabs. Specimens for coating were prepared for coating by TIG welding a wire on one end, degreasing in solvent, grit blasting with #220 grit aluminum oxide, and blowing clean with air. The parts are suspended above the powders a minimum of one centimeter at room temperature. The coating vessel containing the powder and parts is placed in a coating retort and then with N 2 for forty-five minutes at 375 CFH. The retort is then purged with argon at 375 CFH for 1 hour. The retort is placed in a furnace and the temperature ramped up in equal gradients to 1400° F. over a 2.5 hour period. The temperature is subsequently ramped up to 1600° F. over a 1 hour period of time, to 1965° F. over a 3 hour period, and held at 1975° F. (+25° F./−10° F.) for 2.5 hours. At 1350° F. the retort is purged with H 2 at 375 CFH and the H 2 flow maintained at 375 CFH for the remainder of the coating cycle. The coated substrate is then cooled in H 2 at 375 CFH until the chamber temperature reached 400° F., wherein the cooling gas is changed to argon (for 1 hour at a minimum CFH of 375).
A smooth, silvery-white-gray coating is formed on all substrates tested. Depending on the coating zone, and the distance of the substrate from the source, the aluminum content ranges between 15-40 weight percent and the silicon content ranges between 1-20 weight percent, depending on location in the coating. The coating thickness ranges from 0.002-0.006″.
Plots of energy dispersive spectroscopy (EDS) for exemplary CMSX-4 substrate (See Tables IX and X, and FIG. 7 ), IN713 substrate (See Tables XI and XII, and FIG. 8) and MAR-M-002 substrate (See Tables XIII and XIV, and FIG. 9) are shown in the respective accompanying figures.
Example 3
The method of example 2 is repeated using as a substrate CM186LC single crystal pins of approximately 0.3″ diameter×4″ long. The coating formed is seen to be smooth, silvery-white-gray in appearance. Depending on the coating zone, and the distance at which the substrate is held from the source, the aluminum content of the coatings ranges between 15-35 weight percent and the silicon content ranges between 5-8 weight percent, depending on location in the coating. The coating thickness ranges from 0.002-0.003″.
Varying the Si content in the source powder over the ratio range yields varying composition profiles as shown in the difference between FIGS. 4 and 5, FIG. 4 representing the lower end of the range and FIG. 5 representing the higher end.
Example 4
The method of example 2 is repeated using a cobalt-based substrate GX-4. The substrate is cut into a 1″ square and treated as the substrate samples described in example 2. The coating formed is seen to be smooth, silvery-white-gray in appearance. Depending on the coating zone, and the distance at which the substrate was held from the source, the aluminum content of the coatings ranges from 1-20 weight percent and the silicon content ranges between 2-25 weight percent, depending on location in the coating. The coating thickness ranges from 0.002-0.003″.
A graph interrelating average coat thickness to the weight composition of coat elements of exemplary GX-4 substrates coated in the above manner are presented in FIG. 6 .
Additional data comparing various Al—Si coatings are attached.
Although the instant invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and the appended claims.
TABLE I
CMSX-4 Al—Si as-coated
DEPTH
% ELEMENT
MICRONS
AI
Cr
Ni
Co
Si
5
34.03
0.98
53.87
7.12
3.85
10
31.21
2.5
51.44
6.53
7.49
15
30.47
2.76
54.76
6.59
5.45
20
32.09
1.28
55.61
7.57
3.48
25
32.07
0.66
56.59
9.04
1.46
30
27.18
15.97
45.32
7.69
3.64
35
28.67
2.83
57.45
9.18
0.96
TABLE II
IN713 Al—Si as-coated
DEPTH
% ELEMENT
MICRONS
AI
Cr
Ni
Co
Si
5
33.55
2.11
60.98
0.01
3.02
10
28.66
7.66
54.59
0.45
7.98
15
31.34
3.54
61.17
0.18
3.5
20
30.77
3.71
60.97
0.47
4.1
25
32.98
0.93
65.37
0.35
0.4
30
17.15
26.96
45.5
0.39
8.79
35
25.47
4.56
68.81
0.27
0.01
TABLE III
MAR-M-002 Al—Si as-coated
DEPTH
% ELEMENT
MICRONS
AI
Cr
Ni
Co
Si
5
31.81
1.01
55.56
6.86
4.38
10
25.04
10.07
44.43
5.6
13.54
15
31.2
2.15
53.81
6.98
5.5
20
32.73
0.64
56.25
7.57
2.74
25
31.89
0.7
56.64
8.11
2.24
30
30.94
4.48
52.1
10.52
1.99
35
27.01
5.18
57.31
9.01
0.57
TABLE IV
CM188LC PINS Al—Si as-coated (Low Silicon Ratio)
DEPTH
% ELEMENT
MICRONS
NI
AL
CR
SI
CO
W
TA
TI
5
44.2
31.6
4.1
7.5
6.1
3.8
2.3
0.4
15
48.2
29.6
3
6.9
6.4
4.8
1.3
0
25
46.2
28.6
3
7.5
6.7
6
1.8
0.2
35
47.5
29.4
3.1
6.3
6.8
5.2
1.7
0.1
45
48.5
30.4
2.8
5.1
6.8
4.7
1.5
0.3
55
46.8
24.2
4.8
4.4
8.6
8
2.9
0.3
65
45.5
14.8
7.9
6.3
8.8
10.8
4.8
1.2
TABLE V
CM188LC PINS Al—Si as-coated (High Silicon Ratio)
DEPTH
% ELEMENT
MICRONS
NI
AL
CR
SI
CO
W
TA
TI
5
56.6
30.5
0.4
6
5.6
0.94
0
0
15
51.33
26.9
4.1
8.48
5.6
2.5
0.9
0.3
25
51.9
26
2.6
7.1
6.9
3.2
2.19
0.1
35
53.6
27.6
1.47
4.9
8.6
2.3
1.54
0
45
56.9
24.6
2.9
3.3
8
2.6
1.5
0.3
55
46.29
14.9
5.8
8.9
8.9
10.6
3.8
0.9
65
45.29
13.3
7.1
8.3
8.8
12.7
4
0.7
75
45.5
15.1
7.8
6
9.6
11.4
3.7
1
TABLE VI
GX-4 Al—Si as coated
DEPTH
% ELEMENT
MICRONS
AI
Si
Co
NI
Cr
Mo
Fe
5
17
20
35
11
14
1.2
1.8
10
25
15
40
11
7
0.9
1.8
15
20
15
37
10.5
13
2.6
1.7
20
18
17
31
8
22
2.9
1.5
25
22
14
40
10
11
1.5
1.5
30
20
15
37
9
16
2.2
1.2
35
24
10
47
9
9
0.3
1.1
40
20
9
37
9
24
1.7
0.8
45
8
13
18
5
50
5.2
0.7
50
6
9
31
8
30
14
1.2
55
2
7.4
38
5
40
5.9
2.2
60
2
5.4
46
7.8
31
5.5
2.4
65
2
4.2
46
8.5
32
4.6
2.7
70
1.6
3.1
47
9.7
32
4.1
2.4
TABLE VII
COMPARISON OF COATED & DIFUSED
Microns
t-Costs
I-Costs
t-Diffuse
I-Diffused
5
30.4
31.8
34.9
27.5
10
35.1
30.8
37.0
27.6
15
36.9
28.4
36.5
28.2
20
37.8
28.5
32.5
28.0
25
35.4
29.1
28.5
28.5
30
17.1
32.6
14.8
30.8
35
13.8
32.4
11.8
31.4
40
8.4
33.5
7.5
32.5
45
6.7
32.8
5.7
31.4
50
2.9
32.3
2.2
31.1
55
3.6
24.0
1.5
29.7
60
0.0
19.1
0.0
25.4
65
2.1
18.4
0.0
20.8
70
0.0
17.9
0.0
16.9
75
0.0
11.8
0.0
16.2
80
0.0
9.1
0.0
14.7
85
0.0
9.1
0.0
16.0
90
0.0
8.9
0.0
13.7
95
0.0
7.6
0.0
9.4
TABLE VIII
fPDSM Report
Input Pattern:
35C AI-SI COATING
10
d
I
d
I
d
I
d
I
d
I
2.8682
14
2.4130
4
2.2482
3
2.0263
100
1.4320
20
2.5519
2
2.3358
4
2.1028
9
1.6534
7
1.2812
3
Identified Phases:
JCPDS#
SI
ML/X
At % Identity . . .
2-1261
55
4/1
76 Aluminum Nickel = AlNi
Ierr: 50, 500
derr: 2.0 Bground: 2
dmax/min: 2.884/1.277
32-0700
7
3/*
6 Nickel Silicide = Ni3Si
Ierr: 50, 500
derr: 2.0 Bground: 2
dmax/min: 2.884/1.277
Summary Report:
Full
Resid
2-1261:
76%
32-0700:
6%
d
I
I
d
I
d
I
2.8682
14
None
2.87
30
2.5519
2
None
2.542
3
2.4130
4
4
2.3358
4
4
<2.273
3>
2.2482
3
3
<2.138
6>
2.1028
9
9
2.0263
100
18
2.02
76
2.024
6
<1.971
6>
<1.759
5>
1.6534
7
None
1.655
15
<1.567
3>
<1.545
2>
<1.459
3>
1.4320
20
None
1.434
15
<1.285
8>
<1.403
2>
<1.365
3>
<1.316
5>
1.2812
3
None
1.283
3
* = Obscured
< . . . > = Missing
[ . . . ] = Previously Removed
TABLE IX
Omni Instruments Auto-xRay Analysis Report
Omni Instruments
Data file: 35d.d1
Comment: 35D AL-SI COATING
Wavelength: 1.54178 Angstroms
Center
Height
Area
D
30.83687
504
6936
2.89954
35.18838
200
271
2.55031
37.94006
136
370
2.37143
40.27991
208
−207
2.23891
40.84195
252
965
2.21079
44.38614
4052
53870
2.04086
55.24129
589
3518
1.66278
64.70628
730
8968
1.44055
73.49693
201
283
1.28846
TABLE X
fPDSM Report
Input Pattern:
35C AL-SI COATING
9
d
I
d
I
d
I
d
I
d
I
2.8885
12
2.3714
3
2.2108
6
1.6628
15
1.2885
5
2.5503
5
2.2389
5
2.0409
100
1.4405
18
Identified Phases:
JCPDS#
SI
ML/X
At % Identity . . .
20-0019C
59
4/0
95 *Aluminum Nickel = AlNi
Ierr: 50, 500
derr: 2.0 Bground: 3
dmax/min: 2.916/1.285
Summary Report:
Full
Resid
20-0019:
95%
d
I
I
d
I
2.8995
12
None
2.89
26
2.5503
5
5
2.3714
3
3
2.2389
5
5
2.2108
6
6
2.0409
100
None
2.04
95
1.6628
15
10
1.667
5*
1.4405
18
None
1.444
12
1.2885
5
None
1.291
5
* = Obscured
< . . . > = Missing
[ . . . ] = Previously Removed
TABLE XI
Omni Instruments Auto-xRay Analysis Report
Omni Instruments
Data file: 37c.d1
Comment: 37C AL-SI COATING
Wavelength: 1.54178 Angstroms
Center
Height
Area
D
31.31942
464
4205
2.85596
39.06890
152
481
2.30547
43.58455
349
585
2.07651
44.80302
6342
58174
2.02283
55.62892
279
1522
1.65211
65.12015
743
6753
1.43239
73.87484
179
694
1.28280
TABLE X
fPDSM Report
Input Pattern:
37C AL-SI COATING
7
d
I
d
I
d
I
d
I
d
I
2.8560
7
2.0765
6
1.6521
4
1.2828
3
2.3055
2
2.0228
100
1.4324
12
Identified Phases:
JCPDS#
SI
ML/X
At % Identity . . .
12-1261
60
5/0
66 Aluminum Nickel = AlNi
Ierr: 50, 500
derr: 2.0 Bground: 2
dmax/min: 2.872/1.279
Summary Report:
Full
Resid
2-1261:
66%
d
I
I
d
I
2.8560
7
None
2.87
26
2.3055
2
2
2.0765
6
6
2.0228
100
34
2.02
66
1.6521
4
None
1.655
13
1.4324
12
None
1.434
13
1.2828
3
None
1.285
7
* = Obscured
< . . . > = Missing
[ . . . ] = Previously Removed
TABLE XIII
Omni Instruments Auto-xRay Analysis Report
Omni Instruments
Data file: 37d.d1
Comment: 37D AL-SI COATING
Wavelength: 1.54178 Angstroms
Center
Height
Area
D
31.52626
258
1497
2.83769
35.56687
132
449
2.52403
36.23339
122
223
2.47912
40.81715
183
422
2.21068
42.11810
131
107
2.14535
43.45442
345
−278
2.08243
44.92110
3685
45967
2.01779
47.42839
156
257
1.91680
55.83552
202
754
1.64648
65.48686
493
4841
1.42526
72.41316
117
107
1.30505
74.28386
149
−11
1.27675
TABLE XIV
fPDSM Report
Input Pattern:
37D SI-AL COATING
10
d
I
d
I
d
I
d
I
d
I
2.8377
7
2.5273
4
2.0824
9
1.9168
4
1.4253
13
2.6983
3
2.2107
5
2.0178
100
1.6465
5
1.2799
4
Identified Phases:
JCPDS#
SI
ML/X
At % Identity . . .
14-0429D
6
3/4
4 Nickel Silicide = Ni3Si2
Ierr: 50, 500
derr: 2.0 Bground: 3
dmax/min: 2.853/1.276
32-06990
<0
2/6
12 Nickel Silicide = Ni3Si
Ierr: 50, 500
derr: 2.0 Bground: 3
dmax/min: 2.853/1.276
Summary Report:
Full
Resid
14-0429:
4%
32-00699:
12%
d
I
I
d
I
d
I
2.8377
7
7
2.6983
3
None
2.700
2
2.5273
4
4
<2.446
7>
2.2107
5
5
<2.122
5>
2.0824
9
None
<2.038
4>
2.075
5
2.0178
100
84
2.011
4*
2.011
12*
<1.975
4>
<1.964
9>
1.9168
4
None
1.920
0
[1.915
9]
″
″
1.910
3
<1.747
3>
<1.741
13>
1.6465
5
5
1.564
5>
1.4253
13
8
1.429
5
<1.376
5>
1.2799
4
4
* = Obscured
< . . . > = Missing
[ . . . ] = Previously Removed | The present invention relates generally to an oxidation and corrosion resistant coating composition produced by a vapor phase co-deposition of transition metals on metallic components. In particular, this coating includes aluminum and silicon and the coated substrate may comprise precious metal, nickel, cobalt or MCrALY. Such coatings are particularly useful in protecting nickel and cobalt and iron-based superalloys from heat corrosion and oxidation attack, especially during high temperature operation, e.g., gas turbine and jet engine hot zones. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a US National Stage of International Application No. PCT/CN2010/070513, filed 4 Feb. 2010, designating the United States, and claiming priority to Chinese Patent Application No. 200910077471.1 filed 12 Feb. 2009. The contents of the foregoing applications are hereby incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
The present invention relates to the field of mobile communications and particularly to a method and device for positioning a terminal in a long term evolution system.
BACKGROUND OF THE INVENTION
It is highly required in a Long Term Evolution (LTE) system to position a terminal. At present, there are the following several general methods for positioning a terminal.
In a first method based upon positioning with a Global Position System (GPS), a GPS device is installed in a terminal to thereby acquire and report to the system the current position of the terminal.
In a second method based upon positioning with a system cell, a rough position of a terminal can be acquired by referring to a station address of a current serving cell of the terminal because the station addresses of serving cells are typically known during deployment of a communication system.
In a third method based upon positioning with Observed Time Difference of Arrival (OTDOA), a terminal measures concurrently transmission time differences of more than three nearby cells and multiplies the transmission time differences by transmission velocity (the velocity of light c) to derive distance differences and hereby plane curve equations of the position of the terminal, and the position of the terminal can be derived from an intersection of curves corresponding to the plane curve equations of the cells.
Among the foregoing three methods, the first method with relatively high precision of positioning has to rely upon the expensive GPS device, and this method is costly to implement and relies upon the required capability of the terminal to receive a GPS signal; the second method has too low precision of positioning, especially in a macro cell with a large coverage area of a base station; and the third method with relatively high complexity of measurement requires concurrent measurement and reporting by the terminal of the transmission time differences of three nearby cells, which may result in significant signaling overhead, furthermore, the terminal centered in a cell may measure a surrounding cell with a considerable error due to an interference and a signal strength.
SUMMARY OF THE INVENTION
In view of this, the invention provides a method and device for positioning a terminal in an LTE system to offer the advantages of a low cost, high precision and low complexity.
A method for positioning a terminal in an LTE system includes:
A. calculating, from a synchronization timing advance of the terminal and a signal reception delay of a serving base station of the terminal, a transmission delay of the terminal to the base station; and
B. determining, from the calculated transmission delay, a distance of the terminal from the base station and determining, from the distance and an angle of arrival of a signal of the terminal, a position of the terminal relative to the base station.
A device for positioning a terminal in an LTE system includes a first information acquisition unit, a transmission delay calculation unit, a distance calculation unit and a position determination unit, wherein:
the first information acquisition unit is configured to acquire a synchronization timing advance of the terminal, a signal reception delay of a serving base station of the terminal and an angle of arrival of a signal of the terminal;
the transmission delay calculation unit is configured to calculate, from the synchronization timing advance of the terminal and the signal reception delay, a transmission delay of the terminal to the base station;
the distance calculation unit is configured to determine, from the transmission delay calculated by the transmission delay calculation unit, a distance of the terminal from the base station; and
the position determination unit is configured to determine, from the distance determined by the distance calculation unit and the angle of arrival of the signal of the terminal acquired by the first information acquisition unit, a position of the terminal relative to the base station.
As can be apparent from the foregoing technical solutions, in the method and device according to the invention, the transmission delay of the terminal to its serving base station is calculated from the synchronization timing advance of the terminal and the signal reception delay of the serving base station of the terminal, the distance of the terminal from the base station is determined from the transmission delay, and the position of the terminal relative to the base station is determined from the distance and the angle of arrival of the signal of the terminal. The device according to the invention can position the terminal in a simple algorithm at a greatly lowered cost as compared with a GPS device, and since all the parameters used in the invention, i.e., the synchronization timing advance of the terminal, the signal reception delay of the base station and the angle of arrival of the signal of the terminal, are measured parameters already present in the system and no value of any additional measurement parameter is required, good compatibility with an existing system can be achieved with low implementation complexity, and all these parameters can be precise to an elementary time unit T s of the LTE system, approximately 1/(15000×2048) second, thereby resulting in high precision of positioning.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart of a general method according to the invention;
FIG. 2 is a flow chart of a specific method according to an embodiment of the invention;
FIG. 3 is a schematic diagram of measuring of an angle of arrival of a signal according to an embodiment of the invention;
FIG. 4 a is a schematic diagram of a distance without considering a height of a base station according to an embodiment of the invention;
FIG. 4 b is a schematic diagram of a distance while considering a height of a base station according to an embodiment of the invention;
FIG. 5 is a schematic diagram of a geometrical position relationship between a base station and a terminal according to an embodiment of the invention; and
FIG. 6 is a structural diagram of a device according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The invention will be described in details hereinafter with reference to the drawings and embodiments thereof to make the objects, technical solutions and advantages of the invention more apparent.
A method according to the invention may be as illustrated in FIG. 1 and generally include the following steps.
The step 101 is to calculate, from a synchronization timing advance of a terminal and a signal reception delay of a serving base station of the terminal, a transmission delay of the terminal to the base station.
The step 102 is to determine, from the calculated transmission delay, a distance of the terminal from the serving base station and to determine, from the distance and an angle of arrival of a signal of the terminal, a position of the terminal relative to the serving base station.
The method according to the invention will be detailed below with reference to the embodiments thereof. FIG. 2 is a flow chart of a specific method according to an embodiment of the invention, and as illustrated in FIG. 2 , the method may include the following steps.
In the step 201 , a positioning device determines a terminal to be positioned, searches for a serving base station of the terminal and acquires positional information (X, Y) of the base station.
Information on serving base stations of terminals can be retrieved from a data base of a system to which the terminals have already accesses.
Although positional information of the terminals can not be determined directly, positional information of the base stations in a network keeps unchanged, so the positional information of the terminals can be acquired indirectly from the positional information of the serving base stations of the terminals.
In this embodiment, the positional information of the serving base station of the terminal may be identified with coordinates (X, Y) in a coordinate system.
The step 202 is to determine a current status of the terminal, and if the terminal is in an unconnected status, the flow goes to the step 203 , or if the terminal is in a connected status, the flow goes to the step 204 .
In the step 203 , the positioning device transmits a paging message to the terminal through the base station to activate the terminal.
If the terminal is in an unconnected status, firstly the terminal shall be activated to perform a subsequent task of measuring parameters, or if the terminal is in a connected status, the subsequent task of measuring parameters may be performed directly.
Particularly in this step, the positioning device transmits to the base station a paging message including an ID of the terminal to be activated; and the base station transmits the paging message to the terminal to be activated according to the ID of the terminal included in the paging message upon reception of the paging message. In this step, the base station receives and transmits the paging message in a transparent transport process.
In the step 204 , the positioning device transmits a measurement command to the base station to instruct the base station to measure a signal reception delay T D for the terminal and an Angle of Arrival (AOA) of a signal of the terminal and to trigger the base station to instruct the terminal through Radio Resource Control (RRC) signaling upon reception of the measurement command to measure a synchronization timing advance T A of the terminal; and the positioning device acquires measurement results of the terminal and the base station.
The base station instructs the terminal through RRC signaling upon reception of the measurement command to measure the synchronization timing advance T A , and the base station measures, from an uplink signal of the terminal, the signal reception delay T D and the Angle of Arrival (AOA) of the signal of the terminal. Particularly, the base station may measure the signal reception delay T D from an uplink optical signal which may be an uplink Sounding Reference Signal (SRS), an uplink random access signal, an uplink data traffic signal, or an uplink control channel signal, etc.
The base station may measure the Angle of Arrival (AOA) of the signal of the terminal by estimating it from signal phase differences of antennas, and as illustrated in FIG. 3 , a distance between an antenna 1 and an antenna 2 is d 1 , the angle of arrival is AOA, and the phase difference of signals over the antenna 1 and the antenna 2 is θ, so d 1 ×cos(AOA)=λ×θ/2π, where λ is a wavelength of a carrier and π is the ratio of the circumference of a circle to its diameter, so
AOA
=
cos
-
1
(
λ
×
θ
2
π
×
d
1
)
.
Upon reception of the RRC signaling instructing to measure the synchronization timing advance, the terminal reports the synchronization timing advance T A which is an integer multiple of 16T S in the LTE system, where T S is an elementary time unit of the LTE system, typically T S =1/(15000×2048) second.
Furthermore, the foregoing measurement process may be one-time measurement or perform a plurality of measurements and then a smoothing process thereon, e.g., averaging thereof, or taking the median thereof.
The step 205 is to calculate a transmission delay T of the terminal to the serving base station via a formula T=(T A +T D )/2 and a distance d of the terminal from the serving base station via a formula d=T×c, where c is the velocity of light.
In the LTE system, the terminal acquires a downlink reference clock by receiving a downlink special signal transmitted periodically from the base station, and due to the transmission delay T from transmission of the base station to reception of the terminal, the transmission delay from transmission of the terminal to reception of the base station is also T. In order to synchronize exactly with the base station the time that the signal is transmitted from the terminal to the base station, the system may perform a closed-loop synchronization process to have the base station transmit a synchronization command to the terminal to have the terminal adjust the time of transmission by an adjusting amount which is the synchronization timing advance T A of the terminal in the LTE system. The terminal transmits the signal by the synchronization timing advance T A , which arrives at the base station after the transmission delay T, and ideally the time of reception at the base station is exactly synchronized with a clock of the base station. However, no ideal synchronization can be achieved, that is, the signal reception delay T D may arise, due to a delay of the synchronization command and mobility of the terminal. Therefore, both of the factors of T A and T D shall be considered for the transmission delay T of the terminal to the serving base station, that is, T=(T A +T D )/2.
Without considering a height of the base station, the distance between the terminal and the base station is d=T×c, as illustrated in FIG. 4 a ; and while the height H of the base station is considered, the distance of the terminal from the serving base station may be calculated via a formula d=√{square root over ((T×c) 2 −H 2 )}, as illustrated in FIG. 4 b.
The step 206 is to determine positional information (x, y) of the terminal via formulas x=X+d×cos(AOA) and y=Y+d×sin(AOA).
With a geometrical relationship in the grid coordinate, the relationship between the position (x, y) of the terminal and the position (X, Y) of the base station may be derived as x=X+d×cos(AOA) and y=Y+d×sin(AOA), as illustrated in FIG. 5 .
The embodiment has been described by taking the grid coordinate as an example, and of course the position of the terminal relative to the serving base station may alternatively be represented in the form of polar coordinate or another form under substantially the same principle without departing from the scope of the invention, and a repeated description thereof will be omitted here.
The method according to the invention has been described in details above, and a positioning device according to the invention will be described in details below. As illustrated in FIG. 6 , the device may include a first information acquisition unit 601 , a transmission delay calculation unit 602 , a distance calculation unit 603 and a position determination unit 604 .
The first information acquisition unit 601 is configured to acquire a synchronization timing advance of a terminal, a signal reception delay of a serving base station of the terminal and an angle of arrival of a signal of the terminal.
The transmission delay calculation unit 602 is configured to calculate, from the synchronization timing advance of the terminal and the signal reception delay, a transmission delay of the terminal to the base station.
The distance calculation unit 603 is configured to determine, from the transmission delay calculated by the transmission delay calculation unit 602 , a distance of the terminal from the base station.
The position determination unit 604 is configured to determine, from the distance determined by the distance calculation unit 603 and the angle of arrival of the signal of the terminal acquired by the first information acquisition unit 601 , a position of the terminal relative to the base station.
Furthermore, the device may further include a second information acquisition unit 605 configured to determine the terminal to be positioned, search for the serving base station of the terminal and acquire positional information of the base station, and provide the first information acquisition unit 601 with information on the determined terminal and base station, and provide the position determination unit 604 with the acquired positional information of the base station.
Furthermore, the first information acquisition unit 601 may include a measurement command transmission sub-unit 606 and a measurement result acquisition sub-unit 607 .
The measurement command transmission sub-unit 606 is configured to transmit a measurement command to the base station upon reception of the information on the determined terminal and base station to instruct the base station to measure the signal reception delay for the terminal and the angle of arrival of the signal of the terminal, and to trigger the base station to instruct the terminal through RRC signaling upon reception of the measurement command to measure the synchronization timing advance.
The measurement result acquisition sub-unit 607 is configured to acquire measurement results of the terminal and the base station.
Furthermore, the device may further include a status determination unit 608 and a paging processing unit 609 .
The status determination unit 608 is configured to determine whether the terminal is in an unconnected status upon reception of the information on the terminal and the base station transmitted from the second information acquisition unit 605 , and if so, transmit a processing instruction to the paging processing unit 609 ; otherwise, transmit the information on the determined terminal and base station to the first information acquisition unit 601 .
The paging processing unit 609 is configured to transmit the information on the determined terminal and base station to the first information acquisition unit 601 after transmitting a paging message to the terminal through the base station to activate the terminal upon reception of the processing instruction.
Particularly, the transmission delay calculation unit 602 may calculate the transmission delay T of the terminal to the serving base station via a formula T=(T A +T D )/2, where T A is the synchronization timing advance of the terminal and T D is the signal reception delay.
The distance calculation unit 603 calculates the distance d of the terminal from the serving base station via a formula d=T×c or d=√{square root over ((T×c) 2 −H 2 )}, where c is the velocity of light and H is the height of the base station.
The position determination unit 604 determines positional information (x, y) of the terminal via formulas x=X+d×cos(AOA) and y=Y+d×sin(AOA), where (x, y) and (X, Y) are coordinate values of the terminal and the base station in the same grid coordinate system respectively.
The foregoing positioning device according to the invention may be embodied as a separate device or by being arranged in the base station.
As can be apparent from the foregoing description, in the method and device according to the invention, the transmission delay of the terminal to its serving base station is calculated from the synchronization timing advance of the terminal and the signal reception delay of the serving base station of the terminal, the distance of the terminal from the base station is determined from the transmission delay, and the position of the terminal relative to the base station is determined from the distance and the angle of arrival of the signal of the terminal. The device according to the invention can position the terminal in a simple algorithm at a greatly lowered cost as compared with a GPS device, and since all the parameters used in the invention, i.e., the synchronization timing advance of the terminal, the signal reception delay of the base station and the angle of arrival of the signal of the terminal, are measured parameters already present in the system and no value of any additional measurement parameter is required, good compatibility with an existing system can be achieved with low implementation complexity, and all these parameters can be precise to an elementary time unit T s of the LTE system, approximately 1/(15000×2048) second, thereby resulting in high precision of positioning.
The foregoing description is merely illustrative of the preferred embodiments of the invention but not intended to limit the invention, and any modifications, equivalent substitutions and adaptations made without departing from the scope and principle of the invention shall be encompassed in the scope of the invention. | A method and an apparatus for terminal locating in long term evolution system are provided by the present invention, wherein, the method includes: calculating the propagation delay from the terminal to the base station to which the terminal belongs, according to the synchronization time advance of the terminal and the signal reception delay of the base station to which the terminal belongs ( 101 ); and determining the distance between the terminal and the base station by using said propagation delay, and determining the position of the terminal relative to that of the base station according to said distance and the direction of arrival of the signal from the terminal ( 102 ). By applying the method and the apparatus provided by the present invention, the terminal locating can be achieved with low cost, low implementation complexity, and high precision for location only by using a simple algorithm. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an apparatus and method for fabricating a powdery thermoelectric material in order to fabricate a thermoelectric module that performs the conversion between thermal energy and electric energy.
[0003] 2. Description of the Related Art
[0004] A “thermoelectric phenomenon” is the general term of the Seebeck effect, the Peltier effect and the Thomson effect, and elements utilizing the phenomenon are called a “thermoelectric element”, a “thermocouple”, an “electronic cooling element”, etc. The thermoelectric phenomenon was originally discovered between different kinds of metals, but in recent years, thermoelectric materials of semiconductors have come to be obtained, and conversion efficiencies not observed with metal materials have come to be attained. Elements employing the thermoelectric semiconductor materials are structurally simple and easy of handling, and can maintain stable characteristics, so that their uses in a wide range attract public attention. In particular, since the elements are capable of precise temperature controls at and near the room temperature, researches and developments have been extensively promoted for temperature regulations in optoelectronics, semiconductor lasers, etc., and for applications to local cooling, small-sized refrigerators, etc.
[0005] In the fabrication of the thermoelectric element, a method of weighing capacity of raw materials to a desired composition, preparing a solid solution ingot by heat-melting and solidifying, further powdering the solid solution ingot and then sintering, slicing and dicing the same has been adopted so far. As a method of powdering the thermoelectric material in the process described above, there is a method of pulverizing the solid solution ingot and the resulting powder is classified by sieving. With this method, however, in order to pulverize solidified solid material, the powdery grains are in the shape of flakes. Therefore the loading of a sieve at the process of the classification and decrease of filling rate in the case where a die is filled up with the powder in order to mold it in the process of compressing the powder are occurred. In order to resolve such problems, there is a method of using a globular powdery thermoelectric material to fabricate a thermoelectric element. For example, Japanese Publication of Unexamined Patent Application, No.293276/1992 discloses a method of fabricating a globular powdery thermoelectric material. Heretofore, the globular powdery thermoelectric material has been obtained by a method referred to as a rotating disk method (or a centrifugal atomization method) of mixing and melting predetermined raw materials, and dropping to scatter the obtained molten metal onto a rotating disk manufactured from a metal (material) or a ceramic (material).
[0006] By the way, when a thermoelectric module is fabricated by using a globular powdery thermoelectric material, it has been known that the smaller the diameter of the powder is, the better performance of the module can be attained. In view of the above, for fabricating a fine powdery thermoelectric material with a diameter, for example, of 40 μm or less, the disk has to be rotated at a high speed.
[0007] In order to obtain a powdery thermoelectric material by a disk rotating at high speed, the disk has to satisfy various conditions. That is, the disk is imposed conditions that (1) it has a reduced weight and a sufficient mechanical strength so as to withstand high speed rotation, (2) it has heat resistance and thermal shock resistance capable of withstanding high temperature of the heat-melted thermoelectric material and has small coefficient of thermal expansion, (3) heat capacity of the entire disk is small in order to prevent the molten metal of the thermoelectric material from solidifying on the disk, and (4) the disk has less reactivity with the molten metal of thermoelectric material so as to avoid contamination of impurities into the thermoelectric material.
[0008] However, since conventional disks have large disk diameter and mass, it is difficult to rotate them at high speed. In addition, since metal or ceramic is used for the material of the disk, the heat capacity of the disk is large so that the molten metal of the thermoelectric material is deprived of its heat by the disk and the molten metal is easy to solidify on the disk. As a result, the disk is further increased in the weight and difficult to be rotated at high speed, and it is easy to get off the rotational balance of the disk. Further, this lowers the yield of the powdery thermoelectric material.
[0009] In order to improve these points (subjects), for example, when the weight of the disk is decreased for enabling high speed rotation and reducing the heat capacity, mechanical strength is lost since the thickness of the disk is decreased. On the contrary if it intends to maintain the mechanical strength, the inertial mass and the heat capacity of the disk are increased. Further, when a metal (material) is used as the material for the disk, since the coefficient of thermal expansion is large, the material is strained by thermal stress to possibly worsen the durability. Particularly, when iron or titanium is used as the material, since the material is highly reactive with the molten metal of the thermoelectric material, the composition of the thermoelectric material is changed. As described above, materials for a disk capable of satisfying all of said conditions have not yet been found so far.
[0010] In view of the above, it has been also practiced to manufacture a disk by a combination of two kinds of materials. For instance, Japanese Publication of Unexamined Patent Application No. 145710/1990 discloses a structure in which a metal disk is covered with a heat insulating material and the circumference thereof is held by a metal holder. Further, Japanese Publication of Unexamined Patent Application No. 34102/1995 discloses a structure in which a ceramic layer is disposed on the surface of a lightweight titanium alloy. However, in the conventional structures described above, since the disk is relatively larger, it can not be rotated at a high speed and the maximum rotational speed is, for example, at about 15,000 rpm, and the minimum grain size particle diameter can be reduced to no more than about 130 μm as well. Further, there is still left a problem that the molten metal is deprived of its heat by the disk and is easy to solidify on the disk to lower the powder yield.
OBJECT OF THE INVENTION
[0011] In view of the foregoings, this invention intends to provide a method of fabricating a powdery thermoelectric material and a manufacturing apparatus therefor capable of fabricating a fine powder at a high yield, when fabricating a powdery thermoelectric material by a rotating disk method, by adopting a disk using a material having a reduced weight and a high strength, with lower thermal expansion coefficient and less reactivity with the material, and designed so as to decrease the heat capacity, thereby preventing the molten metal from solidification and capable of fabricating a powder at high speed rotation. In view of the foregoing, it is an object of the present invention to provide a method of fabricating powdery thermoelectric material and an apparatus for fabricating powdery thermoelectric material which can prevent from solidifying the molten metal and fabricate a fine powder at a high yield, because of using the disk manufactured by the material which has lightweight, high mechanical strength, lower coefficient of thermal expansion and less reactivity with the materials and designed to less heat capacity when fabricating a powdery thermoelectric material by a rotating disk method.
SUMMARY OF THE INVENTION
[0012] The foregoing subjects can be solved in accordance with the present invention by an apparatus for fabricating a powdery thermoelectric material comprising a container for mixing raw material having a predetermined composition and heating and melting the same, a funnel or a pouring port for pouring the molten metal of the heated and melted raw material and a rotating disk made of silicon nitride or a material containing silicon nitride for scattering the poured molten metal. In order to solve the subjects mentioned above, an apparatus for fabricating a powdery thermoelectric material related to the present invention comprises a container for mixing and heat-melting a raw material of predetermined composition, a funnel or a pouring port for pouring the heat-melted raw material, and a rotating disk made of silicon nitride or a material containing silicon nitride for scattering the poured molten metal. The rotating disk may be manufactured from a material containing 90% or more of silicon nitride.
[0013] Further, the foregoing subjects can be solved in accordance with this invention by a method of fabricating a powdery thermoelectric material comprising mixing a raw material having a predetermined composition and heating and melting the same, pouring the molten metal of the heated and melted raw material on a rotating disk manufactured from silicon nitride or a material containing silicon nitride and scattering the poured molten metal by a rotating disk into fine globular forms and cooling them. Further a method of fabricating a powdery thermoelectric material which related to the present invention comprises the step of mixing and heat-melting a raw material of predetermined composition; the step of pouring the heat-melted raw material onto a rotating disk made of silicon nitride or a material containing silicon nitride; the step of turning the heat-melted material into microglobules by scattering and then cooling the microglobules, thereby to prepare a globular powdery thermoelectric material. The said rotating disk may be manufactured from a material containing 90% or more of silicon nitride.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] [0014]FIG. 1 is a schematic view showing an apparatus for fabricating a powdery thermoelectric material according to a preferred embodiment of the present invention;
[0015] [0015]FIG. 2 is a flow chart showing a method of fabricating a powdery thermoelectric material according to a preferred embodiment of the present invention;
[0016] [0016]FIG. 3 is a perspective view, partially broken away, showing a structure of a thermoelectric module fabricated by using the powdery thermoelectric material prepared by the fabricating method according to the preferred embodiment of the present invention;
[0017] [0017]FIG. 4(A) is a view showing a cross sectional shape of a rotating disk used in a preferred embodiment according to the present invention;
[0018] [0018]FIG. 4(B) is a view showing the shape of a rotating disk used in an experiment for comparing; and
[0019] [0019]FIG. 5 is a table showing the result of an experiment for fabricating a powdery thermoelectric material by a rotating disk manufactured by using various kinds of materials.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0020] (This invention is to be described by way of preferred embodiments with reference to the drawings. Throughout the drawings, identical constituent elements carry the same reference numerals for which duplicate explanations are to be omitted.) Now, embodiments of the present invention will be described with reference to the drawings. By the way, same reference numbers shall be assigned to the same constituents, which shall be omitted from description.
[0021] [0021]FIG. 1 is a schematic view showing an apparatus for fabricating a powdery thermoelectric material in one embodiment according to this invention.
[0022] The apparatus includes a vessel 1 disposed in a chamber 8 , a funnel 2 , a rotating disk 3 , a motor 4 and a powder collecting portion (unit) 7 .
[0023] Further, FIG. 2 is a flow chart showing a method of fabricating a powdery thermoelectric material of one embodiment according to the present invention. The method of fabricating the powdery material in one embodiment according to this invention is to be explained with reference to FIG. 1 and FIG. 2.
[0024] At first, a raw material having a predetermined composition is weighed and is enclosed in a vessel 1 (step S 1 ). The raw material of the thermoelectric material contains, for example, antimony (Sb) or bismuth (Bi) being a group V element and Selenium (Se) or tellurium (Te) being a group VI element. Since the solid solution of the group V and group VI elements has a hexagonal system (crystal) structure, at least two of elements among Bi, Te, Sb and Se are used as the raw materials generally represented as follows:
[0025] (Bi 1-X Sb X ) 2 (Te 1-Y Se Y ) 3
[0026] in which 0≦X, Y≦1
[0027] Specifically, a mixed crystal system solid solution of bismuth telluride (Bi 2 Te 3 ) and antimony telluride (Sb 2 Te 3 ) with addition of a P-type dopant can be used as the material for a P-type element, while a mixed crystal system solid solution of bismuth telluride (Bi 2 Te 3 ) and bismuth selenide (Bi 2 Se 3 ) with addition of an N-type dopant can be used as the material for a N-type element.
[0028] Then, the raw material enclosed in the vessel 1 is heat-melted by a radio frequency coil or a heater or the like (step S 2 ). Further, the molten metal of the heat-melted raw material is poured through the funnel 2 on the rotating disk 3 (step S 3 ). The rotating disk 3 is connected with the motor 4 and controlled for the rotational speed. The poured molten metal 5 is scattered by the rotating disk (step S 4 ). The scattered molten metal 6 is cooled, dropped in the chamber 8 and then collected in the powder collecting portion (unit) 7 (step S 5 ). For the method of pouring in step S 3 , the molten metal may be dripped dropwise or may be flowed continuously from a pouring port.
[0029] [0029]FIG. 3 is a perspective view, partially broken away, showing a thermoelectric module fabricated by using such a globular powdery thermoelectric material. As shown in FIG. 3, a P-type element (P-type semiconductor) 13 and an N-type element (N-type semiconductor) 14 are connected through an electrode 15 to form a PN element pair between two ceramic substrates 11 and 12 . Further, a plurality of such PN element pairs are connected in series. A current introduction terminal (positive electrode) 16 is connected to the N-type element at one end of the series circuit of the PN element pairs, while a current introduction terminal (negative electrode) 17 is connected to the P-type element at the other end. When current is supplied from the current introduction terminal (positive electrode) 16 by way of the series circuit of the PN element pairs to the current introduction terminals (negative electrode) 17 by applying a voltage between the current introduction terminal 16 and 17 , the side of the ceramic substrate 11 is cooled, while the side of the ceramic substrate 12 is heated. As a result, flow of heat as shown by an arrow in the figure is generated.
[0030] The figure of Merit Z indicating the performance of the thermoelectric material is represented by means of Seebeck coefficient α, electric conductivity σ, and thermal conductivity κ, as follows
[0031] Z=α 2 σ/κ
[0032] Figure of Merit Z is higher, the performance of the thermoelectric material is better. The thermoelectric material is generally prepared from a sintered material and the heat conductivity can be decreased by reducing the crystal grain size of the sintered material finer. Accordingly, when the sintered material is prepared by using a fine powdery thermoelectric material fabricated in accordance with this invention, a thermoelectric material of a high Figure of Merit can be fabricated. That is, the performance of the thermoelectric material can be improved and the productivity of the high performance thermoelectric material can be improved.
[0033] Then, the material and the shape of the rotating disk for using in the apparatus for manufacturing the globular powder according to this embodiment is to be explained. FIG. 4(A) is a cross sectional view showing the shape of a rotating disk for using in the apparatus for fabricating the globular powder according to this embodiment. Further, FIG. 4(B) is a cross sectional view showing the shape of a rotating disk used as a comparative example.
[0034] In order that the molten metal poured onto the rotating disk is not solidified on the disk, it is necessary to decrease the heat capacity of the rotating disk. This object can be attained by using a material of lower specific heat or reducing the weight of the rotating disk. Further, the diameter has also to be decreased for increasing the rotational speed. Then, when it is intended to manufacture a rotating disk of a reduced thickness and of a small diameter, this results in a problem of thermal shock. A problem of thermal shock is occurred next. That is, when the molten metal of the raw material melted and dropped on the disk is in contact with the upper surface of the disk, the temperature of the contact portion rises abruptly. Since the lower surface of the disk still remains momentarily at an initial temperature at this time, a temperature gradient is caused in the inside of the disk. As the temperature gradient is larger, the internal stress due to thermal expansion is larger tending to cause destruction, so that a disk is liable to be broken more easily as the distance between the upper surface and the lower surface is smaller, that is, as the thickness is reduced.
[0035] In order to manufacture a disk having durability against thermal shock and having a reduced thickness, a material of a small coefficient of thermal expansion may be used. Alternatively, a material having a strength to endure the stress may also be used.
[0036] In the present invention, a material containing silicon nitride or sialon is used for manufacturing the rotating disk. Silicon nitride or sialon is a material having a same extent of specific heat as that of metals or ceramics but has small coefficient of thermal expansion and thermal stress. On the contrary, the bending strength is not lower even when compared with other materials.
[0037] Sialon is a mixture of silicon nitride mixed with aluminum oxide and other material and it is generally represented as β-sialon as below:
[0038] Si 6-Z N 8-Z Al Z O Z
[0039] in which the value for Z is preferably within a range from 0 to 3.8. In this embodiment, β-sialon in which Z≅0.34 was used. In this case, since the molecular weight for Si 6-Z N 8-Z is 266.2 and the molecular weight for Si 6-Z N 8-Z Al Z O Z is 280.8, the ratio of silicon nitride Si 43 N 4 contained in the β-sialon is 94.8% being calculated as:
[0040] 266.2÷280.8×100=94.8
[0041] Further, in this embodiment, about 90% of the sialon mixed with about 10% of yttrium oxide Y 2 O 3 or SiO 2 glass was used as the material for the rotating disk. Accordingly, the ratio of silicon nitride Si 3 N 4 to the entire material is 85.3 % being calculated as:
[0042] 94.8×0.9=85.3
[0043] [0043]FIG. 5 shows a result of an experiment for comparing in which powdery thermoelectric materials were fabricated by using rotating disks related to the embodiment of the present invention manufactured from silicon nitride or sialon and rotating disks of comparative examples manufactured from conventional materials. In Examples 1 to 4, a rotating disk of the shape shown in FIG. 4(A) was used. The operation was conducted under the conditions at a diameter of the rotating disk of 30 mm, rotational speed of 60,000 rpm, a molten metal temperature of 720° C. and a molten metal amount of 2 kg. Further, regarding the composition of the thermoelectric material, there were used two kinds of materials namely, a mixed crystal solid solution of bismuth telluride and bismuth selenide: Bi 2 (Te 0.9 Se 0.1 ) 3 as the raw material for the N-type element, and a mixed crystal solid solution of bismuth telluride and antimony telluride: (Bi 0.25 Sb 0.75 ) 2 Te 3 as the raw material for the P-type element.
[0044] The material and the shape of the rotating disks used for comparison are to be explained. As shown in FIG. 5, an experiment for comparing was conducted by using the rotating disk of the shape shown in FIG. 4(A) manufactured from each of titanium-aluminum-vanadium series alloy, boron nitride and graphite respectively shown in Comparative Examples 1 to 6. Further, for fragile boron nitride and graphite in view of the result of the experiment, a holder made of titanium was attached to a disk made of boron nitride or graphite as shown in FIG. 4(B) as Comparative Examples 7 to 10.
[0045] Then, the result of experiment is to be studied (examined) with reference to FIG. 5.
[0046] At first, taking notice on Comparative Examples 1 and 2, since rotating disks made of titanium-aluminum-vanadium series alloy had high coefficient of thermal expansion but, on the other hand, the bending strength was also large, it could endure thermal shock and high speed rotation. However, since the ingredients contained in the alloy are reactive with the molten metal of the raw material, reaction corrosion was observed on the surface of the rotating disk. Accordingly, the fabricated powder can not be used. Particularly, in Comparative Example 2, the disk was abraded by heavy corrosion.
[0047] Then, taking notice on boron nitride and graphite shown in Comparative Examples 3 to 6, the rotating disks using the materials were poor in the operation stability and the powder yield was as low as 2 to 3%. Further, the average particle diameter could not be measured. This is because the bending strength is lower against the thermal expansion thereof and, accordingly, the disk is damaged instantly upon pouring of the molten metal and the powder was scarcely fabricated. In view of the above, a titanium holder was attached to boron nitride and graphite in Comparative Examples 7-10. While the mechanical strength of the rotating disk could be maintained by this measure, the mass and the heat capacity of the rotating disk also are increased and the molten metal tends to be solidified on the disk. When the molten metal was solidified, the operation stability was also lowered such as occurrence of vibrations and the powder yield was also poor as shown in Comparative Examples 7 to 10. Further, the average particle diameter was about 70 μm.
[0048] Compared with the comparative examples described above, since the rotating disks of the examples using silicon nitride and sialon as the material had small coefficient of heat expansion and large bending strength, they could endure the thermal shock sufficiently even when the thickness of the disk was reduced. Further, since the specific gravity is not large even compared with metals or the like, the heat capacity was not increased so much and the poured molten metal was less solidified on the disk. Accordingly, a long-time operation stability was kept. Further, since the shape for the reduced size and weight could be maintained, high speed operation could be maintained and the powder of small grain size could be fabricated at a good yield. As described above, satisfactory result could be obtained by using rotating disks made of silicon nitride or sialon as the material.
[0049] As has been described above, according to the present invention, a powdery thermoelectric material of smaller average particle diameter than usual can be fabricated at a good yield by using a rotating disk manufactured from a material containing silicon nitride in the manufacture of the powdery thermoelectric material by a rotating disk method. Accordingly, the performance and the productivity of the thermoelectric element can be improved. | An apparatus for fabricating a powdery thermoelectric material comprising a rotating disk having durability to thermal shock, having no reactivity with raw material and capable of high speed rotation, the apparatus comprising a container for mixing raw material of predetermined composition and heating and melting the same, a funnel or a pouring port for pouring the molten metal of the heat-melted raw material and a rotating disk made of silicon nitride or a material containing silicon nitride for scattering the poured molten metal. | 8 |
BACKGROUND OF THE INVENTION
The present invention pertains generally to needled sutures. More particularly, the invention relates to the utilization of a shrink sleeve heat shrunk-fit to couple together a needle and a suture. A shrink sleeve or shrink sleeves might additionally be utilized to couple a needle and a number of sutures for providing a linked tandem suture or a controlled release suture or for linking a number of sutures.
There exist in the art a variety of teachings pertaining to the attachment of a suture to a suture needle. Exemplary of needle suture connection might be the placement of an end of a suture into a hole or channel in the blunt end of a needle whereinafter the hole or channel is mechanically swaged or crimped onto the suture so that the suture is firmly held within the needle. Another teaching for anchoring a suture to a needle might be the placement of a suture tip into a recess in the blunt end of a needle whereafter the needle is heated to expand the suture tip within the recess into tight engagement with the recess walls. Yet another teaching for connecting a needle and a suture might be by means of a needle shank portion of smaller diameter than the needle diameter, with the shank being inserted into an internal or central bore provided in the suture for tight fitting engagement and anchoring therein. Still another teaching to effect a needle-suture connection might be the use of the techniques of heating, soldering, brazing or gluing a hollow metal tubular suture for coupling the tubing to a surgical needle. Another teaching might be the use of an eyeless surgical needle in the butt end of which is an opening wherein a flexible suture leader is crimped and a connector sleeve of high strength metal is crimped to capture a surgical suture.
Suture needles are formed from a relatively soft metal wire-like material. A segment of wire of sufficient length for both the needle and a handle (for holding the needle during the manufacture thereof) is cut from the main wire source. The length is then straightened, formed with a point at the front end, and a part of the shank to the rear of the point may be flattened to provide a place for the surgeon to grip the needle.
When using the channel method for attaching the suture to the needle, a channel is formed in the needle, rearward of the shank while the needle is still in its initial, relatively soft condition. This groove is stamped into the needle by means of a V-shaped die. The V-shape of the die is necessary to assure that a sufficient force is concentrated at the appropriate place on the channel to form a groove of a sufficient depth without damaging the walls of the newly formed channel.
The needle shaft is now bent to the desired curvature and the needle is hardened. This may be accomplished by placing the needles into a vacuum furnace at approximately 980° C. to 1040° C. followed by tempering at about 260° C. to take out the brittleness. The finished needle may have a Rockwell hardness of approximately 49 to 55.
Since the suture could not withstand the heat treatments, it must of course be attached to the needle after hardening. However, it is impossible to bend the hardened channel walls to close them onto a suture without cracking or twisting the walls. Thus, before closing the channel walls onto suture it is necessary to soften the channel walls by annealing. Of course, care must be taken to prevent the softening effect of the annealing procedure from being felt forward of the channel walls along the shank or the needle point.
Following annealing the needle is electroplated, and the handle part is chopped off leaving the channel open to the rear. The suture is then inserted and the channel walls are closed onto the suture, preferably by crimping to hold the suture.
Notwithstanding the necessity of the annealing procedure, it has been found that annealing has several detrimental effects. First, there is an inevitable drift of heat down the shank of the needle causing some undesirable annealing effect on the shank of the needle itself. In addition, the annealing process invariably decreases the "stainlessness" of the needle, that is the ability of the needle to resist rust, especially at the softened channel.
Further, the "chop off" of the handle from the main part of the needle is less clean with a softer annealed needle than with a harder needle. This "chop off" is accomplished through that portion of the needle which has the channel formed into it. The harder the material of the channel, the cleaner the chop off, and the smaller the resultant burr. The annealing process, by softening the channel, prevents a clean chop off and makes it more likely for burrs to occur.
Moreover, the above disadvantages can become even more significant when the needle is treated to obtain a very high Rockwell hardness. In this case it may be necessary to anneal the needle several times, thereby significantly increasing the above noted undesirable effects.
Indeed, with a very hard needle, it is frequently impossible or difficult to accomplish the necessary softness for bending the needle material without cracking or twisting the same regardless of the number of annealing steps.
Thus, there exists a need for improvements which will permit the use of a superior means for attaching a suture to a needle while eliminating or substantially reducing the detrimental effects of annealing.
Accordingly, herein disclosed is the coupling of a needle to a suture and a suture to a suture by means of a heat shrinkable sleeve which has numerous advantages over known couplings. Specifically, attachment time is significantly less, handling and equipment costs are reduced, needle quality is improved, needle to suture and suture to suture attachment is enhanced, and a more economical needle to suture and suture to suture coupling means is presented.
SUMMARY OF THE INVENTION
The present invention is directed toward a needle-suture combination comprising a needle having first and second ends, a suture, and a heat shrunk sleeve surrounding and securing therewithin a first end of the needle and an end of the suture. One of the ends of the needle might include a hub and the suture might be positioned substantially coaxially with and have an end disposed face to face with the hub in proximate or contiguous relationship. Also contemplated is the placement of the end portion of the suture in juxtaposed relationship with at least a portion of the hub and the sleeve securing therewithin at least a portion of the juxtaposed suture and hub. The hub might include one or more grooves or flanges peripherally disposed about the hub length. The suture could be positioned in a hub groove before sleeve placement. The end portion of the suture might be stiffened by means of a coating of nylon or polyester. The sleeve might further include an adhesive disposed internally along at least a portion of the length surrounded by the sleeve.
The invention additionally embodies a needle-suture combination comprising a needle having first and second ends, a first suture, a first heat shrunk sleeve surrounding and securing therewithin a first end of the needle and a first end of the first suture, and a second heat shrunk sleeve surrounding and securing therewithin a second end of the first suture and a first end of a second suture. An adhesive means might further be disposed internally along at least a portion of the length surrounded by at least one of the first and second sleeves.
In another form of the invention, the combination might comprise a needle having first and second ends with one of the ends having a recess, a suture, and a heat shrunk sleeve at a first end surrounding and securing therewithin an end of the suture with the sleeve at a second end being located and secured within the recess. The sleeve might further include an adhesive disposed internally along at least a portion of the length of the first end of the sleeve surrounding the end of the suture.
Further embodied within the invention is a needle-suture combination comprising a needle having first and second ends, a first suture, and linking means for coupling a first end of the first suture with a first end of the needle, the linking means being capable of separating the needle from the first suture by application of a predetermined axial force along the linking means, with the force being substantially less than the force necessary to break the first suture. The linking means might comprise a second suture, a first heat shrunk sleeve surrounding and securing therewithin a first end of the needle and a first end of the second suture, and a second heat shrunk sleeve surrounding and securing therewithin a second end of the second suture and the first end of the first suture. Alternatively, the linking means might comprise a second suture having a first end located and secured within a recess in a first end of the needle, and a heat shrunk sleeve surrounding and securing therewithin a second end of the second suture and a first end of the first suture.
Also embodied within the invention is a suture-suture combination. The combination might comprise a first suture having opposing end portions, a second suture having opposing end portions, and a heat shrunk sleeve surrounding and securing therewithin a first end portion of the first suture and a first end portion of the second suture.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the present invention depicting a needle-suture combination embodying a heat shrunk sleeve coupling a needle and a suture.
FIG. 2 is an enlarged, partial, perspective view, in exploded form, of the component parts of the combination illustrated in FIG. 1 but prior to assemblage.
FIG. 3 is an enlarged, schematic view of the components of FIG. 2 positioned for assemblage and showing the sleeve, in section, prior to heat shrinking.
FIG. 4 is a view like that illustrated in FIG. 3 but now showing the application of heat to the sleeve to shrink fit the sleeve to provide the coupled needle and suture of FIG. 1.
FIG. 5 is an enlarged, perspective view of the sleeve prior to heat shrinking and further including a layer of adhesive located therewithin.
FIG. 6 is a partial, schematic view of a linked, tandem needle-suture combination showing two heat shrunk sleeves, in section, coupling a needle and two sutures.
FIG. 7 is a partial, schematic view of a coupled needle and suture embodying a heat shrunk sleeve, with the sleeve shown in section and a portion of the needle shown cut away to illustrate the sleeve end located in a needle recess.
FIG. 8 is a view much like that of FIG. 7 but showing a first suture located in a needle recess and a heat shrunk sleeve coupling the first suture to a second suture.
FIG. 9 is an alternate embodiment much like that of FIG. 2 but further illustrating a groove at the needle end location.
FIG. 10 is a view like that of FIG. 9 but now depicting the suture positioned in the groove at the needle end.
FIG. 11 is a view of the components of FIGS. 9 and 10 positioned for assemblage but prior to heat shrinking the sleeve.
FIG. 12 is a schematic view of the components of FIG. 11, showing the needle end in partial section and tile sleeve in full section, with the sleeve shrunk fit to couple the suture to the needle.
FIG. 13 is an enlarged, cross-sectional view of the needle-suture combination, taken along line 13--13 of FIG. 12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The description herein presented refers to the accompanying drawings in which like reference numerals refer to like parts throughout the several views. Referring to FIG. 1, in accordance with the principles of the present invention, there is illustrated a schematic representation of needle-suture combination 10 wherein needle 12 and suture 14 are coupled in coupling area 16.
Turning next to FIG. 2, there is shown an enlarged, exploded view of area 16 depicting the components of the coupling area before the components are coupled. Illustrated are end portion of needle 12 having hub 18 and flange 20, end of suture 14, and heat shrinkable sleeve 22. Hub 18 may include one or more flanges 20 along its length. Either alternately or additionally, hub 18 may include at least one groove 21 disposed peripherally along its length. Preferably, groove 21 is disposed transversely as shown. However, the groove may be longitudinally disposed, if desired, with the groove assuming either a substantially straight or a spiral pathway. Although hub 18 is shown of reduced diameter, which is preferred, it should be understood that the diameter could approximate the diameter of the main body of needle 12. Although not shown, hub 18 could include a groove peripherially located along its length. The groove may be longitudinal but preferably it is circumferentially disposed. Sleeve 22 should be of a body compatible material which may be selected from, but not limited to, a number of heat shrinkable polymers such as a polyolefin, polyethylene and ethyl vinyl acetate, or ethyl vinyl acetate, to name but a few. Sleeve 22 might further include an adhesive 24 located within the sleeve (FIG. 5) but adhesive could be placed along any portion of the length enclosed by the sleeve in use, that is, adhesive could be placed along either hub 18 or suture 14 or both. Any number of adhesive materials would be acceptable, such as, for example, a synthetic polymer classified as a polyolefin.
Now turning to FIG. 3, the components of FIG. 2 are shown positioned for assemblage. Hub 18 and suture 14 are positioned within sleeve 22. Here the end of hub 18 and the end of suture 14 are shown approximated but the ends may be contiguous. The end of suture 14 is preferably stiffened by means of a coating such as nylon or polyester or comparable coating for ease of insertion into sleeve 22. Sleeve 22 has not yet been shrunk fit around hub 18 and suture 14. FIG. 4 depicts that components of FIG. 3 but further illustrates the application of heat to sleeve 22 which causes the sleeve to shrink to tightly surround and secure therewithin hub 18 and the end of suture 14.
Sleeve 22 is initially extruded with a generally uniform wall diameter, internal diameter, and external diameter. The sleeve is then irradiated at a predetermined diameter and memory is set. Thereafter the sleeve is heated to glass transition temperature and expanded with air pressure to a second diameter and then cooled to maintain the expanded diameter. Sleeve 22 is now ready for use in coupling needle 12 and suture 14.
Needle-suture combination 10 includes hardened unannealed or uniformly annealed needle 12 with a small pin-like extension or hub 18 protruding from the back end of the needle. The needle has been hardened in a conventional manner, for example, by heating in a vacuum furnace at 980°-1040° C. followed by tempering at about 260° C. to remove brittleness. The needle can then be attached to suture 14 without annealing (or if working with a very hard needle, with a substantially reduced number of annealings) and without compromising the structural integrity of the needle as a whole. With the needle hub 18 and the suture 14 positioned inside opposite ends of sleeve 22, coupling area 16 is subjected to heat for approximately thirty minutes at a predetermined temperature. The temperature will be in a range of approximately 100°-160° C. for a polyolefin sleeve. The heat shrink temperature, however, will vary depending upon the sleeve material used. The application of heat will cause pre-treated sleeve 22 to shrink and lock hub 18 of needle 12 and the end of suture 14 in position, forming a suture to needle attachment on a non annealed needle or on a uniformly annealed needle.
In the present invention, since there is no annealing, there is no drift of heat down the shank to cause an annealing effect on the shank of the needle. The needle is now uniformly hard along its length and it is possible to place the needle holder at any position along the length of the needle. The resistance to bending is now as high as possible since the needle is as hard as possible, without brittleness. This is in contrast with annealed needles wherein the surgeon had to be careful in the placement of the needle holder on the needle to be sure that he did not grasp a spot which had become soft from the annealing. Also, the ability of the needle to resist rust (the stainlessness) is maintained and the tendency for burr formation at the chop off is greatly decreased or eliminated.
By way of example and not of limitation, polyolefin sleeve 22 having an extruded inside diameter of 0.025 centimeters is irradiated to set the memory at 0.025 centimeters inside diameter. The sleeve is then heated and expanded to 0.050 centimeters inside diameter and cooled to maintain the 0.050 centimeters inside diameter. Needle 12 having hub 18 with a 0.030 centimeters diameter is placed in one end of sleeve 22 and the end of suture 14 having a 0.036 centimeter diameter is placed into the opposite end of sleeve 22. Sleeve 22 with enclosed hub and suture end is then heated at 155° C. for thirty minutes. The sleeve permanently shrinks toward its primary memory setting diameter, locking the needle hub and suture end, securely attaching the needle and suture. In this example, the finished inside diameter of the sleeve over the hub would be 0.030 centimeters and over the suture approximately 0.025 centimeters.
Returning now to the figures, FIG. 6 illustrates a linked, tandem needle-suture combination 100. The connection of needle 12 with hub 18 to suture 15 by means of sleeve 22 is the same as heretofore presented in respect to FIGS. 1-4. Here, however, a second end of suture 15 is connected to an end of another suture 26 by means of sleeve 22 following the same technique as above for the needle to suture coupling. Combination 100 might be useful, for example, when a needle has a first diameter connected to a suture of a lesser diameter followed by a suture having a diameter greater than the diameter of the needle. In this instance, the trailing suture will fully fill a tissue hole made by the needle during use. Typically, the smaller diameter suture will be the weak link in the combination to allow a surgeon to remove the needle from the suture with a sharp snap after the needle has passed through tissue.
FIG. 7 presents alternate embodiment 10' of the needle-suture combination depicted in FIG. 4 and FIG. 8 presents alternate embodiment 100' of the tandem needle-suture combination of FIG. 6. In FIG. 7, sleeve 22 is first heated to shrink to its set memory diameter to capture end of suture 14 at one end of the sleeve while the other end of the sleeve collapses to its shrink diameter. The non suture containing end of sleeve 22 is then placed into a recess in needle 12' for connection thereto by any number of convenient means, such as, gluing, swaging or crimping, to name but a few. In FIG. 8, suture 28 is connected to needle 12' in much the same manner as sleeve 22 of FIG. 7. The end of suture 28 can be placed in a recess in needle 12' for containment therein, for example, by friction fitting, gluing, swaging or crimping. The other end of suture 28 can be coupled to suture 26 by means of shrink sleeve 22 as heretofore disclosed.
Turning next to FIGS. 9-13, there is depicted yet another means for providing a needle-suture combination which has here been designated 10". Here, needle 12 has hub 30 including groove 32 which accommodates the end portion of suture 14. It should be understood that, if desired, the groove could follow a spiral pathway about the hub and the suture end portion could be placed in the groove so disposed. Sleeve 22 surrounds the end of suture 14 placed in groove 32 of hub 30 (FIG. 11) and, upon application of heat, sleeve 22 shrinks to secure therewithin the end portion of suture 14 and hub 30 for coupling together the needle and the suture. Although not here specifically illustrated, hub 30 could be a full section without groove 32 and the end portion of suture 14 could be juxtaposed with the hub, and sleeve 22 could be shrunk to capture the juxtaposed suture and hub.
Previously, in respect to FIGS. 6 and 8, there was mention of detaching the needle from the suture. This can be accomplished by providing a linking means interposed between and coupling a suture and a needle. The linking means can be a suture having a tensile breaking strength less than the tensile breaking strength of the main suture. Upon application of a tensile axial force, such as that easily applied by a surgeon, along the linking suture of a magnitude sufficient enough to break the linking suture, but less than that force required to break the main suture, the needle can become detached from the suture. In this disclosure, suture 15 in FIG. 6 and suture 28 in FIG. 8 can serve as the linking sutures having an axial tensile rupture strength less than that of suture 26.
In a typical example, a 2-0 intestinal needle is attached to a 2-0 suture having a knot break strength in excess of 2.72 kg. Interposed between the needle and the suture is an 7-0 suture having a 0.25 kg straight break strength. With the coupling of needle and suture as herein presented in respect to either of the embodiments of FIGS. 6 and 8, the assembly is held with the needle in one hand and the 2-0 suture in the other hand. The assembly is then snapped or pulled and the size 7-0 suture which forms the linking means breaks at 0.25 kg. One section of the broken 7-0 suture will remain firmly attached to the needle and the other section will remain firmly attached to the 2-0 suture. Each needle-suture combination so constructed will break at 0.25 kg along the 7-0 weak link section between the needle and the 2-0 suture giving substantially reproducible results.
The present invention has been described herein with specific reference to the preferred embodiments thereof. However, those skilled in the art will understand that changes may be made in the form of the invention covered by the claims without departing from the scope and spirit thereof, and that certain features of the invention may sometimes be used to an advantage without corresponding use of the other features. | A needle-suture combination employing a heat shrunk sleeve to attach a needle to a suture. One or more heat shrunk sleeves might also be incorporated into the combination to provide a controlled release suture or to provide a linked tandem suture. | 0 |
BACKGROUND OF THE INVENTION
The invention is concerned with a device for machine communication in examining and changing of data in data carriers exhibiting a memory, especially in the identification of persons, in checking the right to entry etc., at at least one control station. Such devices are used for various purposes, for example, at ski lifts for checking or devaluating tickets, in parking garages to permit entering and exiting.
Up until now, primarily cards with magnetic stripes and punch cards were used for the identification of persons or for entry control, that is to say, passive data carries. These must be inserted into a slot of a reading device at the control station which leads to a relatively large expenditure of time and inconvenience for the user.
Active data carriers are known in which the data carrier itself contains electronic components, such as computers, displays, etc. Examples of this are EP-B-19280 (ID card and electrical contact surfaces), EP-A-142013 (Data carriers with inductive data transfer and destruction of the data upon mechanical intervention), EP-A-168836 (Data card for cash dispensers with optical data transfer), EP-A-196028 (Value card with electrical contact surfaces), and, WO-A-86/04705 (Telephone value card with inductive data transfer). The data carriers which are expensive as compared with magnetic stripe or punch cards cannot be used for general purposes of the type mentioned in the beginning especially because of their high cost. In mass use for admission of limited cost, for example, for single tickets at ski lifts, they would not be accepted by the public. For this reason, the control devices up to now have been indispensable. Because, however, control through active data carriers would considerably increase the productivity of every control station, it is the goal of the invention to create a control system without the disadvantages mentioned above.
SUMMARY OF THE INVENTION
This is achieved according to the invention insofar as the control station exhibits a first control device for communicating with active data carriers which contain a microcomputer and a second control device for controlling passive data carriers in which the data are stored in, for example, magnetic or optical form.
The device according to the invention therefore allows for an efficient combination of both control systems, reduces waiting time and increases comfort for all users.
The data to be controlled are in an initializing station stored into the data carriers and checked by the control station. Active data carriers can be used repeatedly by erasing and through the input of new data. Thus they can be used as yearly cards, permanent ID cards for repeating events and so forth, whereby simply the expiration date has to be checked by the control station, which date has to be newly stored after expiration for reuse. Such a data carrier could also be handed out upon deposit, or could be bought back again after its use.
These data carriers are particularly economical for season tickets or yearly passes for large scale use because the generating costs represent only an acceptable percentage of the embodied value.
In contrast, for services of limited value, for which deposit or buy-back does not provide any advantages, for example, single admission tickets, single fares, short term parking garage tickets, etc., the usual passive data carriers, which can be discarded after devaluation by the second control device, can be used. Both control devices of the control station exhibit preferably parallel outputs to which a conversion unit is connected, to which peripheral devices, for example, a signal lamp, a barrier, a turnstile, or a central computer for the settlement of accounts, etc., are connected to the conversion unit.
A preferred execution, which allows for a considerable acceleration of the control of active data carriers provides for the first control device of the control station to have a transmitter-receiver unit for communication at a distance with an approached data carrier exhibiting a transmitter-receiver unit.
For identification or admission, the data carrier which can be read at a distance must be simply be brought into the control range of the transmitter-receiver unit of the first control device, where in a very short time, preferably less than 1 second, the entitlement and the validity of the entitlement can be examined. It is clear that thus passing through the control station is accelerated considerably and waiting times are reduced. The time saved becomes especially apparent, for example, at highway tool booths or at ski lifts.
Thus, it is provided for in one of the executions that the control station be combined with a multicolored light for displaying the result of the control, whereby the transmitter and the receiver of the first reading and writing device as well as the lights of the signal are arranged in one housing which has a matt glass cover. Thus, room-saving construction closed off from the outside can be achieved.
In the preferred execution, every data carrier equipped with a transmitter-receiver unit exhibits a stand-by circuit which can be activated by means of a signal given off by the first control device of the control station, and thus, there is a minimum of energy use. Therefore, the device can be used for several years even with high frequency of use.
Further, a preferred execution provided for the transmitter-receiver unit to be designed for radio transmission in a preferred carrier frequency range of up to 250 kHz. This requires little transmission energy, which is essential for the energy supply of the data carrier. It further makes possible the use of magnetic antennas, thus, no undesired shielding effects occur.
In order not to disturb the exchange of communication, a preferred execution provides for a difference in carrier frequencies for the data transfer between the control station and the data carrier and the data carrier and the control station. Thus, with a transmission oscillator in the control station will be sufficient if the transmitter-receiver unit contains a frequency divider.
The space for communication is chosen to be much smaller than the object to be acquired, so that data transfer within the acquisition space only occurs as the data carrier approaches the region of the control station.
By limiting the communication area to a size which excludes with certainty the circumstantial presence of a data carrier which must not respond and thus makes much more difficult a deliberate disturbance by such a carrier, a comfortable, time-saving remote control is achieved. This requires a conscious and deliberate handling of the data carrier, comparable to the insertion into an intake slot.
The limited communication area, the dimensions of which are in accordance with the object to be acquired, is already secured from foreign influences by the object itself. Therefore, the device exhibits a great deal of operational security in spite of the data transfer at a distance.
For areas for the entry of persons to be passed through in one lane, the largest range of the communication space is provided vertical to the lane at, for example, 10 cm to 30 cm, preferably 20 cm.
For motor vehicles to be passed through in one lane, the largest range of the communication space can be between 50 cm and 200 cm, preferably 100 cm. The communication space will be ball-shaped or cylindrical.
In another execution data transfer is provided for by means of light waves, whereby here the infrared range in particular is chosen, however, laser light could be used.
In data transfer by means of light waves, the limited transfer area can be shielded from outside influences without much difficulty. This can occur simply by means of a limiting blind for the control area provided at a distance to the transmitter and the receiver.
The application possibilities can be increased considerably if, for example, a continuous devaluation takes place at each control station until a "stock" is used up. Such a data carrier can be used, for example, as a coupon for several rides or as an admission ticket for events with consumption (restaurants, leisure areas and open-air areas). It is advantageous in this execution that the remaining value can be displayed, whereby the remaining value is in accordance with the type of use, for example, the expiration date can be shown, the next-to-last ride of a transportation coupon or the like, in order to make timely re-valuation in an initialization station possible. With the aid of the computer provided in the data carrier, information and functions that complement one another or overlap can be split between the data carrier and the control station at will.
In a further execution, the second read-write device of the control station contains an insertion slot with a read-write head and a print head. Thus, changes of the magnetic or optical designation or uses of the passive data carriers can also be printed on the carrier and can be seen visually.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following, the invention will be described in more detail with the aid of the figures but is not limited to such.
FIG. 1 shows a schematic representation of an acquisition space of a control station.
FIG. 2 a control station in schematic partial-section.
FIG. 3 an active data carrier for communicating with the control station according to FIG. 2.
FIG. 4 a block diagram of the control station according to FIG. 2.
FIG. 5 a block diagram of the data carrier according to FIG. 3.
FIG. 6 a two-lane control station with gates.
FIG. 7 a schematic cut through a second execution of a control station.
FIG. 8 shows a top view of a second execution of an active data carrier for communicating with the control station according to FIG. 7.
FIG. 9 a longitudinal section of the data carrier according to FIG. 8 and
FIG. 10 a block diagram of the data carrier according to FIG. 8.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Devices according to the invention serve the purposes of communicating between a control station 70 and data carriers 50, 50' within a real or assumed limitation 61 in an acquisition space 60 which corresponds in its dimensions with the object 51 (person or object) provided with the data carrier 50, 50'. For example, the acquisition space 60 can form a lane for persons to pass through of size a in which the border 61 is at a distance from the control station 70.
The control station 70 is designed for selective communication with active data carriers 50 and passive data carriers 50' and thus contains two control devices 31 and 32 which are located together in a common housing 30. The first control device 31 is thus provided for communication with active data carriers 50 which contain a microcomputer (FIGS. 5 and 10) and the second control device 32 processes passive data carriers 50', especially magnetic stripe cards, punch cards, cards with bar codes, etc. such as are already in use. A passive data carrier 50' is thus just indicated in broken lines in FIG. 1.
In the execution shown more closely in FIGS. 2-5, the transfer of data to the first control device 31 occur by means of radio, whereby the transmitter-receiver frequencies preferably lie in the range of 100 kHz and under. Thus magnetic antennas for transmitter 15 and receiver 16 can be used, so that no undesired shielding effects occur. Limited transmission energy limits the communication space to a region 80 of the control station 70.
Region 80 exhibits a maximum range b which is much smaller than size a of the acquisition space and, therefore, for data transfer between the data carrier 50 and the control station 70, the data carrier 50 must be brought into region 80 of the control station. This means that object 51 comes so much into the vicinity of the control station 70 that the possibility of a communication disturbance caused by another data carrier which happens to be in the acquisition space 60 or is there deliberately, can, in all practicality, be excluded. If measurement is a 50-70 cm, for example, then a suitable maximum range b of the region 80 would be approximately 10 to 30 cm.
As can be seen from FIGS. 2 and 3, the transmission antennas 71, 48 and the receiver antennas 72, 49 in both the first control device 31 of the control station 70 (FIG. 2) and in the data carrier 50 (FIG. 3) are placed at a 90° angle to one another, so that they do not influence one another magnetically. Because of the limited range b of the communication space, it is not necessary to provide undirectional antennas. It would, however, be conceivable to provide two receiver coils 72, 49 placed against one another in the control station 70 and/or in the data carrier 50. On the back, the housing 30 is provided with a shield. With the aid of both block diagrams shown in FIGS. 4 and 5 of the first control device 31 of the control station 70 and the data carrier 50, the communication between the control station and the data carrier 50 moved into range 80 is explained in more detail.
The control station 70 emits a designation number with a carrier frequency f o (for example 100 kHz) (FIG. 4). To this the central processing unit 75 (CPU) of the the control station transfers the corresponding data to a shift register 76 (SR) from which these are read serially in an encoder 77. The encoder 77 is connected with an oscillator 74 for the carrier frequency f o . The transmission antenna 71 is driven via corresponding amplifiers 78. The signals emitted from control station 70 (FIG. 5) are received in the data carrier 50 by the receiver antenna 49 which is turned to the carrier frequency f o . The signals are brought to a low-pass filter 54 via a delimiter 52 and an amplifier 53. The low-pass filter is connected to a decoder 56.
Between the low-pass filter 54 and the decoder 56 a time function element 55 (t) is arranged which prevents signals which are coincidentally received from "awakening" the processor 20 (CPU) in the data carrier 50. The decoder 56 sends the decoded data to shift register 57 (SR) which awakens the process 20 via an interrupt so that the processor can take over the read recognition received.
The process 20 recalculates the read recognition with a set algorithm and then sends its own additional data carrier number to the control station 70 retour. For the transmitting the data carrier 50 requires the carrier frequency f o . This frequency is led via a frequency divider 58 ##EQU1## to an encoder 63 which receives the corresponding data from the processor 20 via a shift register 62 (SR). The transmission frequency is now f o /2. This circuit has the advantage that in the data carrier 50, no individual constant oscillator is required which must be turned to the control station 70. The signals arrive via an amplifier 64 and the transmission antenna 48 of the data carrier 50 to the receiver antenna 72 of the first control device 31 of the control station 70. From there they are fed to a decoder 83 via an amplifier 81 and a low-pass filter 82.
From the decoder the data arrive at a shift register 84 to the CPU 75. The CPU calculates the data received with the same algorithm as in the data carrier 50, and it therefore can recognize any attempts at manipulation, whereby a frequency divider 79 is provided for the transmission oscillator 74. The same transmission frequency f o /2 coming from the data carrier 50 can thus be compared directly.
If, for example, either the control station 70 or especially the data carrier 50 are stimulated by a fraud, then the true partner can interrupt the data transfer for a certain time or permanently after a certain number of attempts at transfer. After this first data exchange, the control station 70 and the data carrier 50 are recognized by one another and at the same time an examination of the authenticity of both partners has taken place, so that the real data traffic can begin, dependent upon its concrete application. At the close of this data transfer, the control station 70 clears itself for the next application and calls with its identifier again until the next answer is received from a following data carrier 50.
As already mentioned, the processor 20 of the data carrier is normally in the sleep-mode, an inactive operational state with minimum electricity consumption. It only springs into action when valid data are received.
It is further possible to awaken the processor 20 by means of a built-in key 65 and for example, to display on display 8 the current status (number and value of the stored entitlements), as well as the transaction carried out (FIG. 5).
Finally, it is even possible to connect a keyboard 66, for example, for computer functions, to enter personal ID numbers (PIN) etc. And certain actions can be made dependent on the entry of the ID number. Provision is also made for connection with the process 20 via a serial interface 59.
The data carrier 50 exhibits is own commutation, in order to consume as little electricity as possible during inactive operation. This circuit consists of a clock oscillator 67, (fx), a programmable divider 68 (fn/fx) and a multiplexer 69 (MUX) for the LDC display 8. Cycle inaccuracies can be remedied by program control. The memory of the processor 20 has the advantage of possessing a relatively small ROM-range and a relatively large RAM-range (for example, 1 kb and 4 kb). In ROM only the basic routines for serving the periphery module and for data traffic are stored. In the RAM, application-specific programs and all data are stored. Thus, all changes can easily take place and all transactions can be examined even after the fact. The modules as described, of the data carrier 50, with the exception of the quartz, the LCD-display 8 and the transmitter/receiver antennas 48, 49 as well as some periphery building blocks are integrated to advantage in a single chip.
In FIGS. 8 through 10, an execution of a data carrier for optical data transmission, especially by means of infra-red waves is displayed. The electronics contained in the data carrier 50 can be seen in the block diagram in FIG. 10. The central microprocessor 20 (uc) is connected with infra-red transmission diodes as transmitter 15 with the corresponding transmission logic 18, with an infra-red receiver diode as receiver 16 with the corresponding receiver logic 19 which is assigned to a ready logic 17 and with an electricity source 7, whereby the electricity source 7, especially when it consists of a battery is provided with a control logic 22. The data to be input into the data carrier 50 are stored in a write-read storage 21, especially in an EEPROM or RAM and can be made visible via a liquid crystal display by pressing a button 13. The electricity source 7 can also be a rechargeable battery or a solar cell.
In FIG. 7 a control station 20 is shown, the first read-write device 31 of which is intended for infra-red data transfer. It contains a transmission diode 27 and a receiver diode 47, an infra-red filter 45, a selection 35 and an evaluation electronics 38 as well as the two-color signal light 33 with a red and a greem lamp 34. The transmission and receiver diodes 27, 47, the colored lamps 34 and an optics 36, which is arranged ahead, are in a pick-up area 29 which is covered to the outside by a matt glass plate 37. The second control device 32 services to control data carriers 50, for example for signal entry, on which the data are stored, for example, in magnetic or optical form, whereby the stored data are read by a write-read head 43 and are fed to an evaluation electronics 46. A printer head 44 is connected to this so that the control can be made visible. The signals emitted from the evaluation electronics 38, 46 depending upon the type of the data carrier 50, 50' to be tested are passed on via a conversion unit 39 to the signal 33 and peripheral devices connected with the equipment, for example, a computer, a gate, a turnstile 41, etc. The latter is shown in FIG. 6 in the example of a two-lane ski lift control station.
Each data carrier 50 exhibits a housing which consists of a bottom portion 1 and a top portion 2 (FIGS. 3, 8 & 9). The housing is plastic, whereby both parts 1 and 2 are preferably welded with one another. The bottom portion 1 of the housing can be present in various executions. As is shown on the bottom portion 1 there are uptakes for an armband 12, so that the data carrier 50 can be worn similarly to a watch on the forearm or the wrist. (Object 51, FIG. 1) The bottom portion 1 can also have a pin and can carry an extra incription field. The housing can also be constructed in the form of a keychain, whereby in the lower portion, a string attached to the key ring is rolled onto a spring roller. The bottom portion 1 can also have a self-stick coating. Both of these latter executions are intended especially for motor vehicles (parking garages, toll booths, etc.)
The top portion 2 exhibits a mounting 28 for a photo 5 or the like which is closed by a cover 3. The cover 3 caries an adhesive coating 4 on the inside on which the photo 5 is glued. The kind of adhesive is thereby chosen so that when the photograph 5 is separated, the photo is destroyed and thus any exchange for another photo becomes apparent. Underneath the cover 3 in the upper portion 2, a cover 11 is placed under which the liquid crystal display 8 is arranged. Next to the display or the photo cover 3, the transmitter 15 and the receiver 16 for the reception and emission of signals are located. They key 13 serves, as mentioned, to make visible the data contained in the data carrier 50 on the display 8. On the display 8 there is also a number field 14 with a visually readable, individual number which can be engraved or printed. This same "current number" can also be on the cover 3 or on the photo 5. The display 8 is fed by a chip 9 in normal fashion by pressing a key via contact 10. The chip is arranged on a substrate. The electricity supply comes from an electricity source 7, for example, a battery, a solar cell, etc.
For the control of an active data carrier 50, the carrier is held in the communication area in region 80 of the first control device 31 of control station 70, (FIG. 1) whereby a transmission signal of the control station activates the ready logic of the data carrier 50, and the stored data can be queried.
If the data carrier is a multiple ride car or a card to be punched, then at control station 80, not only is the validity examined, but the card also is partially devalued. With this sort of data carrier, the additional storage of its individual number is particularly advantageous because the control station can keep account of the continuous devaluation if the control station is hooked up to a computer and the numbers are transferred to a number log. The data carrier 50 contains a microcomputer and information, and functions can thus be divided as desired between the data carrier 50 and the control station 70, which supplement one another or overlap, as the case may be. Accelerated control is made possible by the distance transfer of the data whereby the use is made much simpler and more pleasant for the owner of the data carrier 50 because he must only bring the carrier into the communication space of region 80 of the control station 70. Because new initialization is possible after expiration date, the higher production costs of the active data carrier 50, especially for early passes or season tickets or ski passes, etc. are of lesser meaning.
Single entries, such as single fares and so forth are controlled using the cards up to now, that is, passive data carriers 50', which are inserted into the second control device 32 of the control station 70 in the usual fashion. | In order to control or identify an authorization of access, use is made of a control station which has two different read-write systems. The first unit is designed in particular for remote control of active date carriers comprising a microcomputer. The second read-write system is designed for the control of passive data carriers, on which the data are stored in a magnetic or optical form. Preferably both read-write systems are provided with parallel outputs, to which a switching system is connected, which passes to the peripheral systems the output signals produced by means of the desired data carrier. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to a method for the preparation of oil-containing microcapsules and more particularly to a method for inducing a readily filterable state in the microcapsules such that the microcapsules can be easily removed from the aqueous slurry in which they are prepared and redispersed in an aqueous or oil based printing vehicle to form a coating composition.
A number of microencapsulation techniques have been used to prepare oil-containing microcapsules. Some of the principal techniques are complex coacervation (typically used to prepare gelatin capsules), in situ polymerization (typically used to prepare melamine-formaldehyde and urea-formaldehyde capsules), and interfacial polymerization (typically used to prepare polyurethane and polyurea capsules).
For some applications it is desirable to separate the microcapsules from the dispersion in which they are prepared. One such application is the preparation of coating compositions which are designed to be printed on or spot coated on paper to provide a carbonless form.
A number of techniques have been used to separate microcapsules. One of the principal techniques is spray drying. U.S. Pat. No. 4,139,392 to Davis et al. discloses a hot melt coating composition containing microcapsules in which microcapsules are spray dried to form a free flowing powder which is dispersed in a wax composition with the aid of an anionic dispersing agent.
U.S. Pat. No. 4,171,981 to Austin et al. describes another method for preparing a print on composition containing microcapsules in which an aqueous slurry of microcapsules is mixed with a hot melt suspending medium and a wiped film evaporator is used to remove the water.
U.S. Pat. No. 4,729,792 to Seitz discloses yet another method in which microcapsules are prepared by interfacial crosslinking of a polysalt formed by reaction of a polyamine and a polyanionic emulsifier with a polyisocyanate. The microcapsules are separated by adding a lipophilizing agent to the capsule slurry. The lipophilizing agent reacts with the polyanionic emulsifier and renders it non-polar such that the microcapsules precipitate from the slurry. The microcapsules can then be dispersed in an ink vehicle with the aid of a dispersing agent. It should be noted that dispersing agents are necessary for dispersing in both polar and non-polar printing ink vehicle.
SUMMARY OF THE INVENTION
In accordance with the present invention, an aqueous slurry of microcapsules containing an ionic emulsifier is prepared and the microcapsules are separated from the slurry by adding to the slurry a compound which coulombically interacts with the emulsifier and causes the slurry to separate into an aqueous phase and a microcapsule rich phase. The term "coulombically interact" is used herein to include ionic interaction as well as hydrogen bonding and is to be distinguished from reactions which produce a covalent bond. Hereinafter the compound which coulombically interacts with the emulsifier will be referred to as a "de-emulsifier".
In accordance with the preferred embodiments of the invention, the coulombic reaction of the emulsifier and the de-emulsifier is reversible and, more particularly, it is a pH dependent reaction which can be initiated or reversed by a change in pH such as a change from an alkaline pH to a neutral or acid pH or vice-versa. In one of the preferred embodiments of the invention reversal of de-emulsification is accomplished by mixing the microcapsules with a printing ink vehicle containing a low molecular weight glycol which complexes preferentially with borax to form a liquid complex which is then part of the printing vehicle.
In accordance with one of the preferred embodiments of the invention, the emulsifier is a compound such as gum arabic which contains vicinal cis-hydroxyl groups and the de-emulsifier is a compound such as sodium borate decahydrate (borax), the borate anion of which forms a pH reversible ionic complex with the cis-hydroxyl groups. Under alkaline conditions (pH about 8 to 10) the borate ion complexes with gum arabic to form a gel, in the manner described by Percival, "Structural Carbohydrate Chemistry," J. Garnet Miller, Ltd., London 1962, pages 33-34. The slurry separates and the microcapsules can be removed by filtration centrifugation or other means. This method is particularly advantageous because the filtered microcapsules can be mixed with an ink vehicle containing propylene glycol or other low molecular weight glycols. In the presence of the glycols, the borate de-complexes from the gum arabic and the microcapsules can be readily dispersed in the ink vehicle.
Accordingly, one manifestation of the present invention is a method for preparing microcapsules which comprises the steps of:
preparing a slurry of microcapsules containing an ionic or polar emulsifier,
adding a de-emulsifier to said slurry which coulombically interacts with said emulsifier and causes said slurry to separate into an aqueous phase and a microcapsule rich phase,
and separating said microcapsules from said slurry.
Another manifestation of the present invention is a method for preparing a coating composition containing microcapsules which comprises:
preparing a slurry of microcapsules containing an ionic or polar emulsifier,
adding a de-emulsifier to said slurry which coulombically interacts with said emulsifier and causes said slurry to separate into an aqueous phase and a microcapsule rich phase,
separating said microcapsules from said slurry,
adding said microcapsules to a coating vehicle, and
dispersing said microcapsules in said coating vehicle to form a coating composition.
In accordance with a preferred embodiment of the invention the reaction of the de-emulsifier is reversible, the microcapsules are added to a coating vehicle and the reaction is reversed.
Still more preferably the emulsifier is a compound containing cis-hydroxyl groups, the de-emulsifier is a borate salt and the ink vehicle contains propylene glycol.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention can be used in conjunction with known processes for preparing microcapsules, however, it is particularly useful in conjunction with the preparation of polyurea, polyurethane, hydroxyalkylcellulose (e.g., hydroxyethylcellulose or hydroxypropylcellulose), urea-formaldehyde or melamine formaldehyde microcapsules.
The invention relies upon the use of an ionic or polar emulsifier. Ionic or polar emulsifiers stabilize a slurry of microcapsules by imparting an ionic charge or polarity to the microcapsules which prevents the microcapsules from agglomerating and maintains them in dispersed state. In accordance with the present invention, after the microcapsules are formed and it is desired to remove the microcapsules from the slurry, a de-emulsifier is added to the slurry. The de-emulsifier reacts ionically or through the formation of hydrogen bonds with the emulsifier. This alters the ionic character of the emulsifier and destabilizes the slurry such that the slurry separates into an aqueous phase and a microcapsule rich phase.
Emulsifiers useful in the present invention include anionic, cationic, amphoteric and polar emulsifiers. These emulsifiers are typically characterized in that they contain pendant amino, hydroxyl, carboxylic, sulfonic and/or phosphoric acid groups. In accordance with the preferred embodiments of the invention, these compounds contain pendant groups which reversibly interact with the deemulsifying agent in a pH dependent reaction. In accordance with the still more preferred embodiments of the invention, the emulsifiers contain pendant hydroxyl and/or amino groups.
Representative examples of emulsifiers useful in the present invention include polysaccharides, such as pectin, guar gum, other gums, cellulose derivatives, alginates, gum arabic, guar gum, etc.; proteins such as casein; polyvinyl alcohol and the like. The emulsifiers are typically used in an amount of about 1-5% in aqueous solution.
The de-emulsifying agents used in the present invention are compounds which are capable of forming ionic or hydrogen bonds with the emulsifier. Typical examples are salts such as alkali or alkaline earth metal borates and, more particularly, sodium borate and borax, calcium salts such as calcium chloride, aluminum salts such as aluminum sulfate, aluminum nitrate, ferric salts such as ferric chloride.
In addition to the foregoing salts, ionic or polar non-ionic polymers such as polymers conventionally used as flocculating agents in the papermaking industry may be used as de-emulsifiers. In particular, cationic polymers such as poly (diallyl dimethylammonium chloride), cationic polyamines, cationic polyacrylamides, etc. may be used. Representative polymers include homopolymers, and copolymers of such monomers as quaternary diallyl diallylammonium chlorides such as diallyl dimethylammonium chloride N-alkylammonium chloride, methacrylamidopropyl trimethylammonium chloride, methacryloxyethyl trimethylammonium chloride, vinylbenzyl trimethylammonium chloride, etc. Commercially available cationic polymers include Warcofix 808 from Sun Chemical Company, Calgon 261 LV and Calgon 7091 RV from Calgon Corporation, Nalco 8674 from Nalco Corporation, Cat Floc C from Calgon Corporation. Particularly useful are Percol 406, a poly(diallyl dimethylammonium chloride) having a molecular weight of 1.5 ×10 6 and a 50% charge density; Percol 1401, a cationic polyamine having a molecular weight of about 500,000 and a charge density of 50%; and Percol 181, a polyacrylamide having a molecular weight of 9×10 6 and a charge density of 30%, all available from Allied Colloids Inc. Non-ionic polymers such as poly (alkylene oxides) can also be used through hydrogen bonding with the emulsifier.
Microcapsules prepared using emulsifiers such as pectin, sodium alginate and gum arabic can be coagulated by crosslinking with divalent and trivalent metal ions such as calcium (II) and aluminum (III) ions available from calcium salts such as calcium chloride and aluminum salts such as aluminum sulfate and aluminum nitrate.
In a preferred embodiment of the invention, the ability of borates to form pH dependent ionic complexes with vicinal cis-glycols is used to separate the microcapsule slurry (hereafter "the cis-hydroxyl borate system"). This reaction is pH dependent and can be represented as follows: ##STR1##
At alkaline pH, the microcapsule slurry can be thickened through the addition of the borate. The hydrated borate anions form hydrogen bonds with the cis-hydroxy groups of the emulsifier. Thickening of the slurry can be induced through the addition of a base. After separation, the microcapsules can be re-dispersed in a coating vehicle with the pH adjusted to acid or neutral. With the pH adjusted to neutral or acid, crosslinking reverses and the capsules readily are dispersible in the ink vehicle. It is particularly preferred to add the microcapsules to an ink vehicle containing propylene glycol as described below.
If redispersion of microcapsules separated through the interaction of an emulsifier and metal salts is difficult, chelating agents such as EDTA. (ethylene diamine tetracetic acid), citric acid, tetrasodium polyphosphate may be added to the printing vehicle. The chelating agent preferentially interacts with the metal ion to free the emulsifier thereby rendering the microcapsules redispersible.
The microcapsules can be formulated into a printing ink using commercially available printing ink vehicles. The microcapsules may be incorporated into the print vehicle to provide an ink suitable for wet or dry offset by merely substituting the microcapsule filtercake for the pigment of the ink and using a wetting agent if necessary.
Representative examples of useful ink vehicles include waxes and mineral oils such as paraffins, isoparaffins, and aromatic hydrocarbons having a boiling point greater than 180° C. Waxes such as carnauba wax, microcrystalline wax, and mixtures thereof examples of which are described in U.S. Patent 4, 139,392 to Davis, phenolic resins, alkyd resins, modified alkyd resins, etc., vegetable waxes, mineral waxes and/or synthetic waxes may be used.
The solids content of the printing ink may range from about 15 to 70% and preferably 30 to 60% percent.
Other useful waxes are described in U.S. Pat. No. 4,640,847 and include montan wax and polyethylene wax. The wax compositions described in U.S. Pat. No. 4,371,634 may also be used.
In addition to the binder material, the ink vehicle may contain other additives conventionally used in printing ink compositions including but not limited to biocides, pigments, stilt materials such as starch granules or cellulose fiber particles, anti-skinning agents may also be used as well as printing oils, printing pastes, and the like siccatives or drying accelerators such as organic acid salts in a conventional manner.
It is particularly desirable to add the microcapsules to a glycol based ink vehicle because any water retained in the microcapsule filtercake is miscible with the ink vehicle and the borate complex releases the capsules while the borate complexes with the low molecular weight glycol (to form a liquid complex). A representative example of a glycol based vehicle is propylene glycol. Other vehicles which may be used include latexes such as Dow Latex 30711 which is a carboxylated styrene-butadiene latex. A preferred latex is another carboxylated styrene-butadiene latex, Polysar Latex 1164, available from BASF. This latex is especially suitable in combination with the propylene glycol in that it gives low viscosity, high solids mixtures. To facilitate dispersion of the microcapsules in the latexes, a dispersant such as sodium polyacrylate (Dispex 40 available from Allied Colloids, Inc. Suffolk, Va.) may be used. Another useful acrylic vehicle is Versacryl, which is commercially available from Johnson Wax.
The present invention is illustrated in more detail by the following non-limiting example.
EXAMPLE 1
Preparation of Polyurea Microcapsules Using Pectin as Emulsifier
______________________________________Solution ASure-Sol 290 (alkyl biphenyl mixture 23,308 gfrom Koch Chemical Co., CorpusChristi, TX.)Sure-Sol 210 (alkylaromatic hydrocarbon 15,539 gfrom Koch Chemical Co., CorpusChristi, TX.)Pergascript blue I-2G (blue color 3,410 gformer)PAPI 27 (mixture of diphenylmethane di- 906 gisocyanate and polymethylenepolyphenyl isocyanate from DowChemical Co.)Desmodur N-100 (aliphatic polyiso- 2,848 gcyanate from Mobay Chemical Corp.)Solution BPectin (Sigma Chemical) 863 gWater 47,480 g______________________________________
Solution A was emulsified into solution B over a period of 5 minutes. Total emulsification time was 32 minutes at 7650 rpm. Final mean capsule diameter was 5.4 microns. After emulsification was completed the emulsion was pumped into the reactor and the following solution C was added slowly.
______________________________________Solution C______________________________________CMC 7 L1T (sodium carboxymethyl- 252 gcellulose, low molecular weightD.S. = 0.7, Technical grade fromHercules, Inc., Wilmington, DE.)Diethylenetriamine 1,043 gWater 4,316 g______________________________________ HCl @ 38% till pH 4.35 where the amine is present as a hydrochloric acid salt.
The pH was then adjusted to 10 with a 50% solution of sodium hydroxide and the batch was cured for 3 hours at 60°-65° C.
EXAMPLE 2
To 100g of the polyurea microcapsules slurry (41-42% solids) prepared in Example 1 was added five drops of 1% aqueous solution of calcium chloride dihydrate. The slurry thickened immediately. It was suction filtered to a filtercake containing 70% solids. This filtercake (40 g) was redispersed in Dow Latex 30711 (20 g) this mixture was somewhat grainy. Five drops of a 1% solution of citric acid was added to the mixture followed by one drop of a 50% aqueous solution of sodium hydroxide. This smoothed out the composition. The composition was coated on a base stock and dried to provide a carbonless recording sheet which imaged very well against a conventional developer sheet.
EXAMPLE 3
To 100g of microcapsules prepared as in Example 1 was added 0.4g of poly (diallyl dimethylammonium chloride) having a molecular weight of approximately 1.5×10 6 and a 50% charge density. This mixture was stirred and warmed slightly for 15 to 20 minutes whereafter it was suction filtered for 15 minutes to produce a filtercake containing 68% solids.
EXAMPLE 4
To 100 g of the polyurea capsule slurry prepared in Example 1 was added 0.4 g Percol 401 (a polyamine having a molecular weight of 500,000 and a 50% charge density commercially available from Allied Colloids, Inc.) This mixture was filtered 20 minutes to provide a filtercake.
EXAMPLE 5
To 100 g of the polyurea capsule slurry prepared in Example 1 was added 0.4 g Percol 181 (a poly (acrylamide) having a molecular weight of 9×10 6 and a 30% charge density). The slurry was filtered 1.5 hours to provide a filtercake.
EXAMPLE 6
To 100g of the polyurea capsule slurry prepared in Example 1 was added 0.4g Polyox N-12K (a poly (ethylene oxide) having a molecular weight of approximately 1×10 6 commercially available from Union Carbide Corp.). Approximately two hours was required to provide a filtercake.
EXAMPLE 7
Preparation of Polyurea Microcapsules
Solutions A and B were prepared as follows.
______________________________________Solution ASure-Sol 290 22,356 gSure-Sol X-210 14,904 gCrystal Violet Lactone 3,622 gPX1 SF-50 (toluene diisocyanate based 1,043 gadduct from Polyblends, Inc.,Livonia, MI.)Desmodur N-100 3,273 gSolution BGum Arabic 2,312 gWater 11.65 gal.______________________________________ Solution B has a pH of 5.
Solution A is emulsified into B over a period of 6 minutes. Emulsification is continued another 24 minutes for a total of 30 minutes, in line rpm 7,650. After emulsification is complete, the emulsion is pumped to reactor and the following Solution C is added.
______________________________________Solution C______________________________________CMC 7 L1T 241.5 gDiethylenetriamine 1,200.6 gWater 12,075.0 g______________________________________ HCl till pH 4.35 where the amine is blocked as a hydrochloride salt.
The pH is adjusted to 10 with a 50% solution of sodium hydroxide and the batch was cured at 60°-65° C. for three hours.
EXAMPLE 8
Polyurea microcapsules prepared as in Example 7 were diluted to 43.2% solids with distilled water and the pH was adjusted to 9 using 10% aqueous sodium hydroxide. To 100 g of the microcapsule slurry was added 0.5 g sodium borate decahydrate (borax) under stirring. The dispersion thickened considerably and became somewhat lumpy. It was suction filtered in ten minutes to from a filtercake having 75% solids. This filtercake (40 g) was mixed with 20 g Dow Latex 3071 (carboxylated styrene-butadiene latex available from Dow Chemical Co.) A few drops of HCl solution were added to adjust the pH to neutral. A smooth, relatively fluid composition was obtained having a solids content of 68.4%. A drawdown of this material was prepared using a hand proofer gravure offset roll combination (100 lines/inch) to give a recording sheet which imaged well on a conventional developer sheet.
EXAMPLE 9
To 100 g capsule slurry as prepared in Example 7 there was added 20 g of a 2.5% borax solution. The thickened, slightly lumpy dispersion was suction filtered to a filtercake of 65% solids. This filtercake (36.4 g) was mixed with 6.83 g Polysar 1164 latex, 17.08 g propylene glycol and 0.034 g Dispex N40 dispersant (salt of a polymeric acid in aqueous solution). The final mixture was low in viscosity, smooth and had 71.2% non aqueous components. A drawdown of this material was prepared using a hand proofer gravure offset roll combination (100 lines/inch) to give a recording sheet which imaged well on a conventional developer sheet.
Printing inks prepared in accordance with the present invention are particularly useful because they contain a high amount of microcapsules, e.g. 55 to 70% other negotiable instruments in place of carbon based compositions to eliminate the black "carbon" bars which interfere with efficient check processing.
Having described the invention in detail and by reference to preferred embodiments thereof, ti will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. | A method for forming microcapsules which comprises the steps of:
preparing a slurry of microcapsules containing an ionic or polar emulsifier;
adding a de-emulsifier to said slurry under such conditions that said de-emulsifier coulombically interacts with said emulsifier and said slurry separates into an aqueous phase and a microcapsule rich phase; and
separating said microcapsules from said slurry. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to the controlled formation of vapor and liquid droplet jets from liquids.
DESCRIPTION OF THE RELATED ART
[0002] Various methods are known for the formation of vapors from liquids. Of special interest in the present invention is a class of liquid vaporization devices that generate a jet of vapor at pressures higher than the source liquid. Such devices are described in detail in U.S. Pat. No. 6,634,864, issued 19 Feb. 2002; and U.S. Ser. No. 10/691,067, filed 21 Oct. 2003. For ease of understanding, we refer to this class of liquid vaporization devices as capillary force vaporizers or CFVs. CFVs create vapor by vaporizing a liquid in a vaporization member having capillary-sized pores, with the vaporization member being substantially surrounded by a vapor impermeable enclosure with the exception of one or more vapor ejection orifices. The vaporization member is also referred to as a vaporizer. Because of the large volume expansion that accompanies a liquid-gas phase transition, pressure is generated within the vaporizer. This pressure causes the vapor to be ejected at high speed at the vapor ejection orifice(s).
[0003] Some earlier generation vaporizer devices were employed in combustion settings. Stoves and lanterns are two representative examples of such combustion appliances. These combustion appliances used an atomizing spray and required exposure of the atomized spray to the heat of the flame to volatilize the fuel. Liquid fuel was injected into a combustor and broken up either pneumatically or mechanically into a spray of fine droplets. Vaporization of the fuel occurred on the surface of the droplets due to absorption of heat from the flame. The diffusion of air to the droplet resulted in ignition of the vaporized gases surrounding individual droplets, referred to as “droplet burning.” Where groups of droplets were ignited, this was referred to as “cloud burning.” Either droplet burning or cloud burning further heats the droplets and releases additional combustible vapors. A flame zone is formed where volatile gases mix with air supplied through the burner. Droplet evaporation and complete burnout of the gases must occur prior to absorption of heat from the flame and subsequent cooling.
[0004] In actual operation of prior art vaporizer devices employed in combustion settings, vapor jets occasionally tended to not remain as a vapor, since air was readily entrained and the vapor jets would be cooled rapidly. The result was that burning droplets of fuel tended to become extinguished prior to complete vaporization, leading to the formation of soot particles. Furthermore, droplet and cloud burning occurred near stoichiometric conditions, resulting in high flame temperatures and generation of high levels of NO x . It is therefore desirable to deliver liquid fuel as a vapor instead of a spray in combustion settings. More generally, it is also desirable to be able to deliver any liquid as a vapor instead of a spray from a capillary device.
SUMMARY OF THE INVENTION
[0005] A typical capillary force vaporizer 100 is shown in FIGS. 1A and 1B . FIG. 1A shows a perspective view of device 100 . Orifice 102 , through which a jet of vapor is ejected, is located at the top of the device. Liquid is supplied through bottom surface 104 . Device 100 is shown in greater detail in FIG. 1B , which corresponds to a cross section along line B-B′ of FIG. 1A . In this case, device 100 essentially consists of optional liquid transport component 106 , thermal insulator component 108 , vaporizer component 110 , and orifice component 112 . These components are held together with peripheral seal 116 , which forms a seal around the periphery of device 100 . Seal 116 is preferably impermeable to vapors and liquids. Optional liquid transport component 106 , thermal insulator 108 , and vaporizer component 110 are all porous 30 members that are located along the liquid flow path in device 100 .
[0006] The purpose of optional liquid transport component 106 is to transport liquid upward from liquid supply surface 104 , which may be in direct contact with a liquid. An example of a liquid transport component is a porous wick. Generally, the temperature of optional liquid transport component 106 is below the liquid's vaporization temperature, such as ambient temperature. The next component in the liquid flow is thermal insulator component 108 , which serves the purposes of transporting liquid upward and resisting heat flow downward. In some cases, optional liquid transport component 106 is eliminated and thermal insulator component 108 is brought directly into contact with the liquid. Therefore, the bottom side of thermal insulator component 108 must be below the liquid's vaporization temperature. On the other hand, the top side of thermal insulator component 108 is in contact with vaporization component or vaporizer 110 , where liquid vaporization occurs. Vapor ejection from the device is controlled by orifice component 112 , which collects the vapor stream. Orifice component 112 has at least one orifice 102 for ejection of vapor at a substantial speed. In device 100 , it is convenient to place a heater element in thermal communication with orifice component 112 . An electrical resistance heater is one example of a suitable heater element. Heat is transmitted through orifice component 112 towards vaporizer 110 . In a typical capillary force vaporizer, the pressure of the vapor as it emerges from orifice 112 is several kPa. As the vapor travels through the ambient, the pressure is greatly reduced. This is different from prior art capillary vaporizers that do not generate significant pressure.
[0007] The speed of exit of the vapor through orifice 102 is dictated by the pressure generated in the device. A high pressure can be generated by applying heat and vaporizing the liquid; however, the pressure cannot exceed the capillary pressure of the liquid feed. If the pressure exceeded the capillary pressure, vapor would escape through vaporizer 110 . During operation of the device, a vapor front is established in vaporizer 110 . The vapor front is the boundary between a liquid-filled region and a gas-filled region, where the liquid-filled region is closer to the thermal insulation component and the gas-filled region is closer to the orifice component. Since vaporizer 110 has capillary-sized pores, a capillary pressure arises in the liquid-filled region. The capillary pressure prevents the incursion of vapor into the liquid supply.
[0008] FIG. 2 is a schematic cross sectional view of capillary force vaporizer 200 . One difference of device 200 from device 100 is that heater element 222 is positioned directly in thermal contact with vaporizer 210 . This structure may reduce response time and power requirements when heater 222 is initially engaged. Device 200 has a stacked cylindrical geometry similar to device 100 of FIGS. 1A and 1B . Device 200 comprises optional liquid transport component 206 , thermal insulation component 208 , vaporization component 210 , and orifice component 212 . Orifice component 212 has at least one orifice 202 for ejection of vapor at a substantial speed. These components are bound at their periphery by peripheral seal 216 . Liquid is supplied to the bottom surface 204 of liquid transport component 206 . It is also possible to eliminate liquid transport component 206 . In that case, the bottom of thermal insulation component 208 is the liquid feed surface. Heater element 222 is situated in close thermal contact with vaporizer 210 and positioned so that substantially the entire area of vaporizer 210 is heated when heater 222 is ON.
[0009] FIG. 3 is a schematic cross sectional view of a capillary force vaporizer 300 . Device 300 is similar to device 200 of FIG. 2 . An important difference is that vaporization component 310 also functions as an electric resistance heater. This may be accomplished, for example, by fabricating the vaporization component from an electrically conducting or semiconducting material. Therefore, the manufacturing process may be simplified compared to device 200 . Device 300 also comprises optional liquid transport component 306 , thermal insulation component 308 , vaporization component 310 , orifice component 312 having at least one vapor ejection orifice 302 , and peripheral seal 316 .
[0010] Other structures for capillary force vaporizers are also possible. Regardless of the detailed device structure, however, capillary force vaporizers generate a high speed jet of vapor from a source liquid. It is believed that the speed may be as high as the speed of sound. This means that the vapor readily entrains the surrounding air and helps to create a lean fuel vapor-air mixture that is suitable for combustion appliances. The mixing length is the distance that a vapor jet must travel in order to be sufficiently mixed with the surrounding air. Therefore, in a combustion appliance, the flame holder and the capillary force vaporizer should be separated by the mixing distance.
[0011] The mixing distance depends on the speed of the vapor jet, which in turn depends on the pressure generated in the capillary force vaporizer and the orifice dimensions. The pressure may be lowered, for example, by increasing the area of the orifice(s). It should be noted that the vapor jet does not necessarily remain a vapor since it readily entrains air and cools rapidly. Therefore, there is a problem in that although the capillary force vaporizer generates a vapor jet and the jet readily entrains air, the cooling effect from mixing with ambient air may cause the vapor to rapidly condense into liquid droplets. Therefore, in some cases the vapor from a capillary force vaporizer may condense into liquid droplets before reaching the burner. In such cases, the burner may emit high levels of soot or NO x .
BRIEF DESCRIPTION OF THE FIGURES
[0012] FIG. 1A is a perspective view of a first capillary force vaporizer device.
[0013] FIG. 1B is a cross sectional side view of the capillary force vaporizer device of FIG. 1A .
[0014] FIG. 2 is a cross sectional side view of a second capillary force vaporizer device.
[0015] FIG. 3 is a cross sectional side view of a third capillary force vaporizer device.
[0016] FIG. 4 is a simplified perspective view of a device in accordance with a first preferred embodiment of the present invention.
[0017] FIG. 5 is a cross sectional side view of a device in accordance with a second preferred embodiment of the present invention.
[0018] FIG. 6 is a cross sectional side view of a device in accordance with a third preferred embodiment of the present invention.
[0019] FIG. 7 is a cross sectional side view of a device in accordance with a fourth preferred embodiment of the present invention.
[0020] FIG. 8 is a cross sectional side view of a device in accordance with a fifth preferred embodiment of the present invention.
[0021] FIG. 9 is a cross sectional side view of a device in accordance with a sixth preferred embodiment of the present invention.
[0022] FIG. 10 is a cross sectional side view of a device in accordance with a seventh preferred embodiment of the present invention.
[0023] FIG. 11 is a simplified schematic view of a device in accordance with an eighth preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] FIG. 4 is a simplified schematic diagram of device 400 in accordance with a first embodiment of the present invention. In this device, the vapor jet output from a CFV is contacted with a gas stream of a known temperature to prevent the condensation of vapor or control the condensation of the vapor to a range of liquid droplet diameters. Device 400 comprises conduit 402 , wherein capillary force vaporizer (CFV) 404 is positioned. A liquid is supplied to capillary force vaporizer 404 from a liquid supply source (not shown). The liquid source may be a liquid tank or a pipe or tube that carries the liquid. Attached to or integrated into CFV 404 is a heater, which supplies heat for vaporization of the liquid. Under suitable conditions, a vapor jet emerges from orifice 406 . The device is also equipped with optional fan 408 and motor 410 for said fan. Optional fan 408 pushes air from conduit inlet 412 towards conduit exit 418 .
[0025] Fan 408 can be used to make the appearance of the vapor jet more uniform or pleasing to the eye. For instance, when the source of power to the CFV is turned off, there may be a lag time before vapor stops emanating from the CFV completely. During this lag time, there may be some latent heat to vaporize only a portion of the supply liquid. This latent heat is insufficient to permit the CFV to vaporize the liquid with a vigorous plume. Instead, during this period of so-called secondary vaporization, the latent heat is insufficient to cause the CFV to fully vaporize the supply liquid, and a non-vigorous plume results. Alternately, the secondary vaporization might make it appear as if the CFV were spurting random mixtures of vapor and condensed droplets of liquid. This less vigorous plume might also have an appearance that can be characterized as a swirling column of smoke or a trailing cloud of incense, for example. According to one embodiment of the present invention, therefore, optional fan 408 may be used to modify the appearance of the plume or vapor jet as it is emitted from the CFV, by quickly dispersing or dissipating any secondary vaporization. According to a preferred embodiment of the invention, fan 408 is located in close proximity to CFV 404 .
[0026] In a preferred embodiment, element 414 is an electric resistance heater. The air is heated by electrical resistance heater 414 before reaching capillary force vaporizer 404 . While this particular embodiment uses an electrical resistance heater, alternative heating means may also be used. In particular, another combustion device, such as a lighter, can be used to heat region 414 . In the case that the vapor output of device 400 is supplied to a burner, some fraction of the heat output of the burner can be transmitted to region 414 . The heated air is entrained by the vapor jet that emerges from orifice 406 . The vapor jet and heated air mix thoroughly in mixing region 416 . If the ambient air is sufficiently heated it is possible to prevent vapor condensation while the vapor travels in mixing region 416 . Alternatively, the temperature of heater 414 may be adjusted to obtain fine liquid droplets having diameters within a desired range. Instead of a heater, element 414 may be a heat exchanger that is cooled by a thermoelectric cooler or other cooling device, or it may comprise any other suitable mechanism familiar to those skilled in the art for controlling the gas temperature within mixing region 416 . By controlling the temperature of the ambient air that contacts the vapor jet, condensation of vapor can be controlled.
[0027] FIG. 5 illustrates a side schematic view of device 500 in accordance with a second embodiment of the present invention. In device 500 , the vapor jet output from CFV 502 passes through substantially enclosed chamber 504 that is at a predetermined temperature. A vapor jet is emitted by CFV 502 through orifice 512 into chamber 504 . Chamber 504 comprises enclosure 506 , gas inlets 508 and 510 , orifice 512 and outlet 514 . Ambient air enters chamber 504 through gas inlets 508 and 510 . Optionally, it is possible to arrange for ambient air or some other external gas to be heated or cooled to a predetermined temperature before entering through gas inlets 508 and 510 . For the purpose of the present invention, “ambient air or other gases” refers to an external gas that may be derived from sources other than capillary force vaporizer 502 . Therefore, compressed propellant gases fall within the scope of “external gases.” Another possible source of an “external gas” is a second capillary force vaporizer (not shown) that generates a vapor jet, this vapor jet being configured to enter device 500 through gas inlets 508 and 510 . A heater or cooler maintains the interior surface of chamber 504 at a desired temperature. Chamber 504 thus functions as a vapor condensation controller in the following manner. The vapor jet can entrain input ambient air or other external gases. Liquid droplets can then be formed by condensation during the residence time of the vapor jet in chamber 504 . Alternatively, the temperature of chamber 504 may be sufficiently high such that vapor condensation during residence time of the vapor jet is prevented. Further discussion of vapor condensation control may be found with reference to FIGS. 6 and 11 , below.
[0028] Chamber 504 may comprise a metallic interior part, an insulating exterior part, and an optional thin film electric resistance heater between the two parts. The surface area of the metallic interior surface can be enhanced by adding a wire mesh or a perforated metal. The metallic interior can be a bilayer structure comprising a contiguous metallic sheet and a reticulated metal such as wire mesh or perforated metal. The enhanced surface area improves the heat exchange between the chamber and the interior gas. For water and other liquids, it may be preferable to use stainless steel for the interior part.
[0029] FIG. 6 illustrates a side schematic view of a device 600 in accordance with a third embodiment of the present invention. In this device, the vapor jet output from CFV 602 passes through a plurality of regions with each region having a predetermined temperature. A predetermined temperature is maintained in each region by using a temperature regulator, such as a heater or a cooler (not shown). The combination of a heater and a cooler may also be used. In a typical capillary force vaporizer, the vapor would emerge from CFV 602 at orifice 612 into chamber 604 with a pressure of several kPa. As the vapor travels through condensation control chamber 604 , pressure is reduced. That is, pressure of the vapor emitted from CFV 602 tends to fall of in chamber 604 with distance from orifice 602 . In general, pressure within chamber 604 can be modified or regulated through selection and variation of various pressure parameters or pressure regulators. These pressure regulators may comprise the size, volume and geometry of the pathway that the emitted vapor from CFV 602 is made to travel within control chamber 604 . Additionally, pressure of the vapor in chamber 604 may also be modified or regulated by adjusting the pressure of any other external gases that are allowed to enter chamber 604 through the gas inlets. Accordingly, therefore, both pressure and temperature can be used to control condensation in chamber 604 .
[0030] A vapor jet is emitted by CFV 602 through orifice 612 into chamber 604 . Ambient air enters into chamber 604 through gas inlets 608 and 610 . Optionally, it is possible to arrange for ambient air or some other external gas to be heated or cooled to a predetermined temperature before entering through gas inlets 608 and 610 . Chamber 604 has enclosure 606 and temperature zones 620 , 630 , and 640 . As will be understood by those knowledgeable in the relevant physical arts, the pressure of the vapor jet emitted from CFV 602 in zone 620 may be higher than the pressure in zone 630 , which in turn may be higher than the pressure in zone 640 . These pressures and temperatures in combination can be used to control condensation. For example, the temperatures of the foregoing zones may be chosen to effect a decrease in jet temperature and controlled condensation into liquid droplets.
[0031] A cooling configuration may be useful when it is desirable to cool the vapor jet over relatively short distances. For example, CPAP, continuous positive airway pressure, devices have been developed to supply humidified air under constant positive pressure to a patient's nasal passages during sleep. This therapy is useful for patients suffering from obstructive sleep apnea, which is characterized by an obstruction of a patient's upper airway during sleep. A conventional CPAP device is generally comprised of a separate ventilator circuit, and compressor powered humidifier unit. The compressor powered humidifier unit is not portable and must be located remotely from the patient, connected to the patient by the long hoses and delivery passageways of the ventilator circuit. A frequent problem with such configurations is a phenomenon known as “rainout”, where water vapor generated by the humidifier condenses inside the tubing and delivery passageways of the ventilator circuit, eventually coalescing into large droplets that stagnate and become a health hazard. In the present invention, however, the device of FIG. 6 can be configured to generate humidified air without the need for a compressor. Moreover, due to its portability, it can be located in the ventilator circuit very close to the patient point of entry. By controlling the cooling rate of the vapor jet, the temperature of the humidified air entering the patient can be reduced to a safe and comfortable level, while condensing the vapor into liquid droplets of an optimum size to avoid the rainout problem mentioned previously.
[0032] FIG. 7 illustrates a side schematic view of device 700 in accordance with a fourth embodiment of the present invention. In this device, the vapor jet output from CFV 702 passes through a substantially enclosed chamber having a predetermined temperature. This device differs from previously mentioned devices of FIGS. 5 and 6 in that the chamber is shaped to increase the probability that the vapor molecules will collide with the chamber, which promotes nucleation and growth of droplets, thereby providing an additional control means for optimizing droplet size distribution. A vapor jet is emitted by CFV 702 through orifice 712 into chamber 704 . Chamber 704 comprises solid enclosure 706 , gas inlets 708 and 710 , orifice 712 and outlet 714 . Ambient air enters into chamber 704 through gas inlets 708 and 710 . Note also that chamber outlet 714 is smaller than capillary force vaporizer orifice 712 . The geometry of the chamber is configured to increase the speed of the vapor jet. Higher speed results in increased entrainment of ambient air or other external gases. Therefore, the geometry of the chamber is another means for controlling condensation.
[0033] FIG. 8 illustrates a side schematic view of device 800 in accordance with a fifth embodiment of the present invention. This embodiment illustrates the possibility of designing devices to meet the requirements of medical inhalation applications application. A medical inhaler is a delivery device that generates droplets of medical formulations for therapy used in the treatment of respiratory ailments. In such treatments, the optimum size distribution for the liquid droplets produced from the medical formulation depends on the specific ailment and prescribed treatment regimen. For example, in the treatment of certain upper respiratory ailments it is desirable for the medical formulation to be deposited in the patient's throat region, in which case the optimum droplet size is in the 10-20 μm range. Alternatively, in cases where it is desirable to deliver a drug or pharmaceutical compound into the patient's blood stream by absorption through deep lung tissues, it is optimal for the droplet size to be in the 3-5 μm range; larger droplets deposit in the throat and never penetrate deep into the lungs whereas smaller droplets are simply exhaled. In either case, droplets not having the optimal size are ineffective and result in the waste of high cost medical formulations. For ease of use, the exit of the inhaler should be in the shape of a mouthpiece.
[0034] A conventional inhaler typically uses a compressed propellant, such as a chlorofluorocarbon (CFC) or hydrofluorous alkane (HFA). Usually, these inhalers are operated by operating a switch that releases a short charge of the compressed propellant which contains the medicament through a spray nozzle. A drawback to conventional methods is that they typically produce a wide droplet size distribution, meaning large quantities of medical formulations are not satisfactorily delivered in a form having a high degree of efficacy because of the large fraction of inappropriate liquid droplet sizes. Device 800 of the present invention overcomes this limitation by allowing generation of vapors from medical formulation without the use of compressed propellants, and by controlling the condensation of the liquid droplets affords the ability to optimize the liquid droplet diameters to achieve maximum efficacy in the prescribed treatment of specific ailments. In FIG. 8 , chamber 804 is shaped like a mouthpiece and is configured for drug delivery to the human pulmonary system. A vapor jet is emitted by CFV 802 through orifice 812 into chamber 804 . Chamber 804 comprises a solid enclosure 806 , gas inlets 808 and 810 , orifice 812 and outlet 814 . In this embodiment, chamber 804 , along with gas inlets 808 and 810 , may be designed to achieve a fixed optimum droplet size distribution, or alternatively, the size and shape of these features may be designed to be adjustable allowing flexibility to tune the device for different medical uses.
[0035] The term “medical formulation” is used to mean a liquid formulation that contains at least one pharmaceutically active compound. A pharmaceutically active compound is a compound that has a therapeutic effect when provided to a mammal, preferably a human mammal. In the present example, a pharmaceutically active compound is delivered to a human pulmonary system via a mouthpiece. It should be noted that pharmaceutically active compounds are not limited to treatments of the pulmonary system. Pharmaceutically active compounds that are conventionally delivered by injection may possibly also be delivered by the devices of the present invention. In addition to the pharmaceutically active compounds, there may be inactive compounds, also called a “carrier”, in the medical formulation. The inactive compounds are preferably in liquid form and do not adversely interact with the pharmaceutically active compound, the patient, the container for the medical formulation, or the delivery device. As mentioned above, a medical formulation as used herein is understood to contemplate a liquid formulation. A liquid formulation is a formulation that is in a flowable form having viscosity, vaporization, and other characteristics such that the formulation can flow through a suitably designed capillary force vaporizer device and be vaporized. Liquid formulations may be solutions such as aqueous solutions, ethanolic solutions, as well as mixtures of the foregoing.
[0036] FIG. 9 illustrates a side schematic view of device 900 in accordance with a sixth embodiment of the present invention. This embodiment illustrates an alternative method of controlling the condensation of vapors. A vapor jet is emitted by CFV 902 through orifice 912 into chamber 904 . Chamber 904 comprises enclosure 906 , gas inlets 908 and 910 , orifice 912 and outlet 914 . Ambient air or other external gases, with or without prior temperature adjustment, enters into chamber 904 through gas inlets 908 and 910 . A reticulated element 916 spans the entire cross section of chamber 904 . The reticulated element could preferably be a wire mesh that has high permeability. Since the vapor jet must pass through reticulated element 916 , vapor condensation can be controlled or prevented by adjusting its permeability and temperature.
[0037] FIG. 10 illustrates a side schematic view of a device 1000 in accordance with a seventh embodiment of the present invention. This device is configured for vaporization of two liquids and mutual entrainment of their respective vapors. Vapor jets are emitted by CFVs 1002 and 1022 through orifices 1012 and 1032 , respectively, into chamber 1004 . Chamber 1004 comprises enclosure 1006 , gas inlets 1008 and 1010 , orifices 1012 and 1032 and outlet 1014 . Ambient air enters into chamber 1004 through gas inlets 1008 and 1010 . Where the liquid being vaporized in CFV 1002 vaporizes a liquid L 1 having boiling temperature T 1 , and CFV 1022 vaporizes liquid L 2 having boiling temperature T 2 , such that T 1 <T 2 , then chamber 1004 may be configured to have several temperature profiles, as follows:
1) T 1 <T 2 <T chamber . This is a configuration to prevent condensation over macroscopic distances. The two vapor jets mix in the chamber. 2) T 1 <T chamber <T 2 . This configuration induces condensation of L 2 droplets, which subsequently act as nucleation sites for the condensation of L 1 . 3) T chamber <T 1 <T 2 . This configuration induces condensation of both L 1 and L 2 .
[0041] The concept of vaporization and condensation control of multiple supply fluids is illustrated in FIG. 11 . FIG. 11 illustrates an eighth embodiment of the present invention. Device 1100 comprises a hydrocarbon fuel reformer 1140 that supplies hydrogen gas to the anode of a fuel cell (not shown) via exit opening 1148 . Capillary force vaporizers 1102 and 1122 are supplied with methanol and water sources, respectively. Vapor jets are emitted at orifices 1112 and 1132 and enter manifold 1130 . Manifold 1130 comprises passageway 1134 that combines the methanol and water vapor jets together. Furthermore, manifold 1130 comprises a temperature regulator, such as a heater (not shown), that is configured to increase the temperature of the vapor jet. Since the vaporization temperature of methanol is approximately 64.7° C., the presence of the methanol vapor may cause the water vapor (boiling temperature 100° C.) to condense. It is necessary to prevent the condensation of water and methanol vapors. Temperature regulators, such as heaters, located in manifold 1130 may be used to raise the temperature of the mixture to above the boiling temperature of both liquids to prevent condensation. One reason for this requirement is that a liquid condensate may block the flow passages. Another reason is that catalytic activity is optimal in the gas phase.
[0042] The exit of passageway 1134 is connected to fuel reformer inlet 1142 . As the mixture flows through the serpentine-configured passages of the fuel reformer, methanol is converted to hydrogen (H 2 ) and CO 2 gases in the presence of a catalyst. The catalytically active regions 1134 have been denoted by gray and the catalytically inactive regions 1136 have been denoted white. Serpentine-configured flow passages are preferred to maximize the residence time of the methanol and water vapor in the vicinity of the catalyst. A long residence time results in a high conversion ratio of methanol to hydrogen. Furthermore, flow passages with small cross sectional areas are often preferred to obtain high flow velocities. The flow passages of the fuel reformer have a length L, a width or a diameter d, with the ratio L/d >>1. In order to satisfy these requirements, a pressure that is generated at the inlet must be sufficiently high for overcoming the pressure loss in the flow passages. However, a conventional compressor is energetically inefficient and lowers the overall efficiency of the fuel cell system. In this embodiment of the present invention, the capillary force vaporizer eliminates the need for a separate compressor or pump and is therefore a more energy efficient means for generating the vapor for a fuel reformer.
[0043] Before starting the operation of the fuel reformer the catalytically active regions 1134 may be at ambient temperature. Therefore, in order to prevent liquid condensation, it may be preferable to apply starter heat, such as by electrical resistance heaters, in the passageways of the fuel reformer immediately before starting the operation of the fuel reformer. It is preferable to include electrical resistance heaters in fuel reformer 1140 . FIG. 11 illustrates an example of a vapor condensation controller having a first part and a second part: the first part is a manifold for combining multiple vapor jets; and the second part is a flow passageway for catalytic reactions. The flow passage is preferably configured to be serpentine in form.
[0044] Combustion appliances such as stoves and lanterns can be made in accordance with the present invention. The problem to be solved is to prevent the condensation of fuel vapor before it is combusted. This problem may arise when the ambient air is cold or before startup when the burner area is cold. A combustion device may comprise a liquid fuel supply, a capillary force vaporizer, a condensation controller and a burner. The condensation controller either prevents condensation or limits condensation to fine droplets of less than 10 μm (micron) in diameter before the jet reaches the burner. The various condensation control mechanisms that have been described above can be used.
[0045] The present invention has been described above in detail with reference to specific embodiments, Figures, and examples. These embodiments, Figures and examples should not be construed as narrowing the scope of the invention, but rather serve as illustrative examples to facilitate an understanding of the invention and ways in which the invention may be practiced, and to further enable those of skill in the pertinent art to practice the invention. It is to be further understood that various modifications and substitutions may be made to the described capillary force vaporizers, devices and systems, as well as to materials, methods of manufacture and use, without departing from the broad scope of the invention contemplated herein. The invention is further illustrated and described in the claims that follow. | Devices for generating a vapor jet from a source liquid comprise a capillary force vaporizer and a condensation controller. Generally, a capillary force vaporizer comprises a porous vaporizer having capillary-sized pores, an enclosure and a vapor egress orifice. The capillary force vaporizer forms a vapor jet from unpressurized liquid by heating the liquid to vaporization in a substantially confined volume. Vapor output from the liquid vaporization section enters the condensation controller, which may be configured to prevent the condensation of vapor or promote the controlled formation of fine liquid droplets, which are generally less than about 100 μm diameter. The condensation controller may be maintained at a predetermined temperature. Alternatively, ambient air or other external gases may be introduced into the condensation controller. Various architectures for the vapor condensation controller are disclosed. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a gas-driven chest compression apparatus for cardiopulmonary resuscitation.
BACKGROUND OF THE INVENTION
[0002] Sudden cardiac arrest is commonly treated mechanically and/or by electrical defibrillation. Mechanical treatment may be given manually or by a chest compression apparatus. A number of chest compression apparatus are known in the art, such as the pneumatically driven LUCAS™ mechanical chest compression system (“Lucas™ system”; an apparatus for compression and physiological in Cardio-Pulmonary Resuscitation, CPR, manufactured by Jolife AB, Lund, Sweden). Specifically the Lucas™ system comprises a support structure and a compression unit. The support structure includes a back plate for positioning under the patient's back posterior to the patient's heart and a front part for positioning around the patient's chest anterior to the heart. The front part has two legs, each having a first end pivotally connected to a hinge of the front part and a second end removably attachable to the back plate. The front part is devised to centrally receive the compression unit, which is arranged to repeatedly compress the patient's chest. The compression unit comprises a pneumatic means arranged to drive and control compression, an adjustable suspension means to which a compression pad is attached, and a means for controlling the position of the pad in respect of the patient's chest. The use of a pneumatic means as the driving force relies on a reciprocating piston providing compressions on the chest by the pad, driven by pressurized gas. The system utilizes pressurized gas for driving the piston both ways, i.e. in the direction of the patient's chest (compression phase, gas being supplied to a compression chamber) and then in the opposite direction (gas being supplied to a decompression chamber), whereby the sternal portion of the chest is brought back to its original position (decompression phase). The consumption of pressurized gas can be substantial and is a limiting feature on the use of the apparatus in places where supply of pressurized driving gas is limited. The consecutive supply of driving gas to the two chambers of the known apparatus requires a complex and thus expensive valve system and a correspondingly complex control.
OBJECTS OF THE INVENTION
[0003] It is an object of the present invention to provide an apparatus of the aforementioned kind, which only consumes pressurized gas when the chest compression pad imposes a force on the patient's sternum.
[0004] It is another object of the invention to provide an apparatus of the aforementioned kind, in which the control of driving gas is simplified.
[0005] Further objects of the invention will be evident from the following summary of the invention, the description of preferred embodiments thereof illustrated in a drawing, and the appended claims.
SUMMARY OF THE INVENTION
[0006] According to the present invention is disclosed the use of an axially contractible pneumatic actuator as a driving force generator for an apparatus for cardiopulmonary resuscitation by administration of chest compressions to a patient in need thereof. In this application “actuator” refers to an axially contractible flexible pneumatic actuator.
[0007] An axially contractible flexible pneumatic actuator suitable for the use in the present invention is disclosed in EP 0 146 261. The actuator comprises a hose body extending between two spaced head pieces. The hose body is flexible whereas the end pieces are solid and generally of a metal. When a fluid under pressure, such as a driving gas, is adduced to its lumen the hose body expands radially. Thereby the distance between the head pieces is shortened. This shortening or contraction can be used as a pulling force. The contraction force of the known actuator is proportional (however not linearly) to the pressure of the driving gas. An actuator of this kind can be used, for instance, to lift or pull weights. An improved pneumatic actuator of this kind is disclosed in U.S. Pat. No. 6,349,746, which is incorporated herein by reference.
[0008] According to the present invention is also disclosed a CPR apparatus comprising one or more axially contractible flexible pneumatic actuators driven by pressurized gas, in particular pressurized breathing gas. It is preferred for the CPR apparatus to comprise a back plate on which a patient in need of CPR is resting with his back, one or both ends of the one or more actuators being fixed at the back plate. The back plate is preferably oblong in a transverse direction, in particular about rectangular. Fixation of the one or more actuators at the back plate is preferably at the short sides of the plate, which is of a transverse length so at to extend at both sides of the patient. It is also preferred for the CPR apparatus to comprise a chest compression pad on which the one or more actuators act for compression of the patient's chest. It is also preferred to arrange a base plate between the compression pad and the actuator. The back plate and the compression pad may be integral or separate.
[0009] According to a first preferred aspect of the invention the CPR apparatus comprises an actuator fastened at the back plate at its both ends, at least one end being releasably fastened. In such case it is preferred for the actuator to abut to the base plate or to an element in abutment with the base plate. Particular preferred is the disposition of the portion of the actuator abutting the base plate in a slot or groove in the upper face of the base plate. It is preferred for the portions of the base plate or of an element disposed between the base plate and the actuator that are in contact with the actuator to have a smooth surface and a low coefficient of friction, such as a coefficient of friction of a polyfluorinated hydrocarbon polymer, in particular Teflon®. The element disposed between the base plate and the actuator can, for instance, be a coat of such polyfluorinated hydrocarbon.
[0010] According to a second preferred aspect of the invention the CPR apparatus comprises two actuators fixed to opposite sides of the back plate with the first ends and to the base plate with their second ends. In this context “fixed to” comprises fixation via intermediate connection means, such as hooks, rods with eyes, straps, belts, etc. At least one of the fixations should be releaseable to facilitate the mounting of the apparatus to the patient.
[0011] According to a third preferred aspect the one or more actuators of the CPR apparatus of the invention are enclosed by optionally resiliently flexible shielding tubes. It is preferred for the one or more actuators to be arranged displaceable in the shielding tubes; in such case it is also preferred for the portion(s) of the inner face of the shielding tubes in contact with an actuator to have a low coefficient of friction, such as one of a polyfluorinated hydrocarbon polymer, in particular Teflon®. It is also preferred for such inner face to have a coat of a polyfluorinated hydrocarbon or other low-friction polymer.
[0012] A preferred polymer for any of base plate, back plate, and compression pad is polyamide reinforced with carbon, glass or other fibre.
[0013] According to a fourth preferred aspect of the invention an actuator is provided at its one end with a quick coupling of known kind by which it can be releasably fixed to the driving gas line or a gas conduit in the base plate or the back plate. If fixed to a gas conduit in the base plate or the back plate, the quick coupling must be one that withstands the pulling strain exerted on it during contraction of the actuator. Quick couplings suitable for use in the invention are, for instance, low pressure monocouplings series LS manufactured by Carl Kurt Walther GmbH & Co. KG (Haan, Germany).
[0014] According to a fifth preferred aspect of the apparatus of the invention comprises a releaseable means for adjustment of the position of the base plate/compression pad assembly in respect of the patient, so as to fix the compression pad in a position in which it abuts the breast of the patient while not compressing it and while the one or more unloaded actuator are kept in a straightened state. The adjustment means is preferably selected from means for adjusting the position of the compression pad in respect of the base plate or/and the position of the base plate in respect of the back plate.
[0015] According to a sixth preferred aspect of the invention an actuator is provided with a resiliently compressible means such as a steel coil that accelerates the return from an inflated state to a non-inflated state. It is preferred for the resiliently compressible means to partially or fully enclose the actuator.
[0016] According to a seventh preferred aspect of the invention the CPR apparatus comprises a means for control of driving gas of constant pressure supplied by a driving gas source such as a gas cylinder provided with a pressure reduction valve, the means comprising a valve for adducing and venting drive gas to/from the actuator controlled by a timing module optionally coupled to pressure sensor, and optionally comprising a mechanically operated safety valve.
[0017] According to a further preferred aspect of the invention the gas for driving the actuator is air. Air vented from the actuator can be adduced to the lungs of the patient by a breathing mask or by intubation.
[0018] According to the present invention is also disclosed the use of an axially contractible flexible pneumatic actuator in a CPR apparatus for providing chest compression to a patient in need thereof. The CPR apparatus may additionally comprise a means for providing electric stimulation to the heart.
[0019] The invention will now be explained in more detail by reference to preferred embodiments illustrated in a rough drawing.
DESCRIPTION OF THE FIGURES
[0020] FIG. 1 a is a sectional view (in part; section A-A in FIG. 1 c ) of a first embodiment of the apparatus of the invention, with the actuator in a non-inflated state (passive);
[0021] FIG. 1 b is the apparatus of FIG. 1 a and in the same view, with the actuator in an inflated (active) state;
[0022] FIG. 1 c is a top view of an actuator/compression plate/compression pad assembly of the embodiment of FIGS. 1 a and 1 b;
[0023] FIG. 1 d is a enlarged sectional view B-B ( FIG. 1 b ) of the assembly of FIG. 1 c;
[0024] FIG. 2 a is a sectional view (in part, in a section corresponding to that of FIG. 1 a ) of a second embodiment of the apparatus of the invention, with the actuator in a non-inflated (passive) state;
[0025] FIG. 2 b is the apparatus of FIG. 2 a and in the same view, with the actuator in an inflated (active) state;
[0026] FIG. 2 c is sectional enlarged view C-C ( FIG. 2 b ) of an actuator/compression plate/compression pad assembly of the embodiment of FIGS. 2 a and 2 b including a shielding tube;
[0027] FIG. 3 a is a sectional view (in part, in a section corresponding to that of FIG. 1 a ) of a third embodiment of the apparatus of the invention, with the actuator in a non-inflated (passive) state;
[0028] FIG. 3 b is the apparatus of FIG. 3 a and in the same view, with the actuator in an inflated (active) state;
[0029] FIG. 4 is a sectional view (in part, in a section corresponding to that of FIG. 1 b ) of a fourth embodiment of the apparatus of the invention, with the actuator in an inflated (active) state;
[0030] FIG. 5 is an partial view of a fifth embodiment of the apparatus of the invention, in a section corresponding to that of FIG. 1 a , with the actuator in an inflated (active) state;
[0031] FIG. 6 a is a sectional view (in part, in a section corresponding to that of FIG. 1 b ) of a fifth embodiment of the apparatus of the invention, with the actuator in a non-inflated (inactive) state;
[0032] FIG. 6 b is the apparatus of FIG. 6 a and in the same view, with the actuator in an inflated (active) state;
[0033] FIG. 7 is a sectional view (in part, in a section corresponding to that of FIG. 1 b ) of a sixth embodiment of the apparatus of the invention, with the actuator in an inflated (active) state;
[0034] FIG. 7 a is a top view of the compression plate of the embodiment of FIG. 7 ;
[0035] FIG. 7 b is a short side view of the compression plate of FIG. 7 a;
[0036] FIG. 8 is a variation of the compression plate of FIG. 7 a , in a top view;
[0037] FIG. 8 a is a sectional view D-D ( FIG. 8 ) of the compression plate of FIG. 8 ;
[0038] FIG. 8 b is a partial view of the compression plate of FIG. 8 in a state mounted on the chest of a patient, the view corresponding to that of FIG. 1 a;
[0039] FIG. 9 is a variation of the compression plate of FIG. 8 , in a sectional view corresponding to that of FIG. 8 a;
[0040] FIG. 10 is a pneumatic control scheme for an apparatus of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0041] The chest compression apparatus of FIGS. 1 a and 1 b comprises a flexible oblong pneumatic actuator 1 (“Fluid Muscle”, Festo AG, Esslingen, Germany; inner diameter 20 mm, length 60 mm; model DSMP-20-550N) of the kind disclosed in U.S. Pat. No. 6,349,746 B1. A reference number provided with an asterisk indicates that the referenced element is physically changed by inflation of a actuator or is the inflated actuator. By hooks 2 , 3 extending in opposite directions from head pieces 4 , 5 the actuator 1 is attached to eyes 6 , 7 mounted at opposite short sides of a glass fibre reinforced polyamide back plate 8 on which a the chest 20 of a patient under cardiopulmonary resuscitation is resting in a recumbent position. The actuator 1 partly encloses the chest 20 at the height of the sternum 21 . In this mounted state the actuator 1 is bent so as to form an inverse U. The central portion of the actuator 1 corresponding to the base of the inverse U is disposed in a transversal slot 9 in the upper face of an generally rectangular base plate 10 of same material as the back plate 8 ( FIGS. 1 c , 1 d ). During inflation and deflation portions of the actuator's 1 outer face glide in the slot 9 . To facilitate gliding the slot 9 surface should be as smooth as possible and preferably of a material or covered by a coat of low friction. A suitable coat material is Teflon® or another polyfluorinated hydrocarbon polymer. From the lower face of the base plate 10 extends a circular compression pad 11 provided with a flexible circumferential lip (not shown) at its lower face, which abuts the breast of the patient above the sternum 21 . A short radial pneumatic connection pipe 12 extends from one head piece 4 . Compressed air for inflating the actuator 1 is adduced by a flexible high-pressure air hose 13 mounted at the pipe 12 .
[0042] In FIG. 1 b the actuator 1 * is shown in a state inflated by air of 5 bar. The actuator 1 *, which has been inflated against the resistive force of the chest 20 of about 350 N, is shortened by about 16%. Thereby the chest 20 * has been compressed to a depth of about 50 mm. The actuator 1 * can be deflated via the air hose 13 or a venting valve (not shown) arranged, for instance, at the opposite head piece 5 .
[0043] The second embodiment of the apparatus of the invention shown in FIGS. 2 a - 2 c of a patient shares its general design with that of the first embodiment of FIGS. 1 a - 1 d . It comprises a back plate 108 , a pneumatic actuator 101 releasably fastened to the back plate 108 at its both ends, a base plate 110 and a compression pad 111 . It differs from the first embodiment in that the actuator 101 , except for its end portions, is disposed in shielding tube 130 . The aim with the shield tube 130 is to protect the patient from damage by an exploding actuator 101 *, and also from contact with the moving actuator 101 , 101 *. The shielding tube 130 is disposed in a slot 109 of the base plate 110 corresponding to the slot 9 of the embodiment of FIGS. 1 a - 1 d . The shielding tube 130 is held in the slot 109 clamped by the actuator 101 , 101 * but can also be attached to the slot wall by, for instance, an adhesive or welding. The inner face of the shielding tube 130 , against which the actuator 101 , 101 * glides during inflation and deflation, should have a low-friction surface. The shielding tube 130 of FIGS. 2 a - 2 c is somewhat flexible to allow it to adapt to the slightly changing angle of the actuator 101 , 101 * legs during a compression cycle. Alternatively the shielding tube 130 can be of a stiff material provided that its lumen is wide enough to accommodate the changing angle and diameter of the actuator 101 , 101 * over a compression cycle.
[0044] The third embodiment of the apparatus of the invention shown in FIGS. 3 a and 3 b comprises two pneumatic actuators 201 , 231 of equal length and properties (inner diameter: 20 mm; length: 40 cm). The actuators 201 , 231 have hooks 203 , 202 extending axially from their first ends 205 , 204 , by which they are attached to eyes 207 , 206 fixed to and extending from opposite short sides of a rectangular back plate 208 . From the second ends of the actuators 201 , 231 rods carrying terminal eyes 226 , 225 extend in axial directions. The eyes 226 , 225 are mounted on bars 228 , 227 bridging slits 230 , 229 in a base plate 210 . The rod 239 of a compression pad 211 is mounted displaceably in a central through bore of the base plate 210 , of which a portion extending from the upper end is threaded. Compressed air is fed to the actuators 201 , 231 by branches 213 , 223 of a flexible high pressure gas hose. The apparatus is mounted to the patient's chest 220 in the following manner: the compression pad 211 with the rod 239 disposed in the base plate 210 is placed on the patient's chest and centred on the sternum. It is held there while sliding the base plate 210 upwards along the rod 239 until further displacement is hindered by the straightened actuators 201 , 231 . A threaded stop 222 is screwed into the bore until stopped by the end face of the rod 239 . This arrangement allows to adapt the apparatus to the size of the chest 220 of an individual patient. In the inflated state of the actuators 201 *, 231 * shown in FIG. 3 b , the compression pad 211 has compressed the chest 220 * of the patient by about 50 mm at a driving gas pressure of 4 bar.
[0045] In a fourth embodiment of the apparatus of the invention shown in FIG. 4 comprising a single actuator 301 , the hook means of the embodiments described in the foregoing are replaced by a polyester belt 333 . One end of the belt 333 is fastened at an eye 305 of one end piece 303 of the actuator 311 . A belt portion extending from the other end of the belt 333 is provided with a row of holes 335 , by any of which the belt 333 can be fasted at a mandrel 332 extending radially from the other end piece 304 . The intermediate portion of the belt 333 is disposed in a channel 336 extending from one short side of the back plate 308 to the other side. Most of the load working on the belt 333 is taken up by deflection pins 307 , 306 disposed in a manner corresponding to the eyes 7 , 6 of the first embodiment. Reference numbers 310 , 311 designate a base plate and a compression pad of same design as those of the first and second embodiments.
[0046] In a fifth embodiment of the apparatus of the invention similar to that of FIGS. 3 a , 3 b in respect of the use of two actuators of same size and properties, the actuators, of which only one actuator 401 * is shown in FIG. 5 in an inflated state, are working against a resiliently compressible means. One reason for this arrangement is to make the first inflated actuator 401 * and the second inflated actuator (not shown) return to their original non-inflated configuration as soon as they are deflated. In the embodiment of FIG. 5 , the resiliently compressible means is a steel coil 440 held between first and second support flanges 441 , 442 of the actuator's 401 first and second end pieces, respectively. A hook 405 , by which the apparatus is fastened at an eye 407 of the back plate 408 , is mounted in a central bore of the first end piece. The female part 426 of a ball-and-socket joint is mounted at the actuator's 401 * second end piece, while the male part 428 is mounted in a threaded bore a base plate 410 . A conduit 413 in the base plate 410 provides communication between a source of compressed air and the actuator 401 *. The ball-and-socket joint of the embodiment can be exchanged for a series LS quick coupling of a width of 23 mm (Carl Kurt Walther GmbH & Co. KG (Haan, Germany) the nipple and the coupling housing provided with threaded end portions matching the thread of an axial bore of the second end piece and of the bore in the base plate. The coupling housing and the nipple may be mounted at the base plate or the actuator, respectively.
[0047] A CPR apparatus of the invention that comprises only one pneumatic actuator, such as the apparatus of FIGS. 1 a - 1 d , can be provided with a resiliently compressible means of the aforementioned kind by, for instance, arranging one compressible steel coil each around the arms of the U-formed actuator. At their one end the coils are supported by a flange of the respective end piece. At their other end the coils are supported by a flange mounted at lateral sections of the base plate, in particular close to the respective end of the groove in which the base of the actuator is disposed. Alternatively a single compressible steel coil extending from a support flange of one end piece to a support flange the other end piece could be used, an intermediate section of the coil being disposed in the groove of the base plate.
[0048] The fifth embodiment of the apparatus of the invention illustrated in FIGS. 6 a , 6 b corresponds generally to that of FIGS. 1 a , 1 b . The chest 520 of the patient is strapped by a single actuator 501 to a back plate 508 but without any interposed element. At both ends the actuator 501 is fastened to eyes 506 , 507 extending laterally from the back plate 508 by means of hooks 502 , 503 extending from head pieces 504 , 505 of the actuator 501 . Compressed air is adduced to the actuator 501 via a flexible tube 513 mounted at a connection pipe 512 of head piece 504 . The actuator 501 is vented by a solenoid valve 515 arranged at the other head piece 515 ; an advantage with this arrangement is that the temperature of the actuator 501 does rise less than if it is vented via the same end. In its expanded state 501 * the actuator has shortened enough to compress the chest by about 30 mm which, while not optimal, is an acceptable compression depth. A major advantage of this and the following embodiments is its simplicity.
[0049] The sixth embodiment of the apparatus of the invention illustrated in FIG. 7 with its actuator 601 * in a an expanded (active) state comprises a compression plate 611 * disposed between the chest 620 * of a patient and the actuator 601 * in a bended state. The resiliently flexible oblong compression plate 611 , which is shown in a top view and a side view in FIGS. 7 a and 7 b , respectively, in an unloaded (not bended) state, is substantially flat except for a longitudinally extending slot 612 . In a mounted state the actuator 601 is disposed in the slot 612 to keep the compression plate 611 from moving in a cranial or opposite direction in respect of the actuator 611 . The resilient nature of the compression plate 611 , which seeks to regain its original flat state from the bended state shown in FIG. 7 , supports the actuator in assuming its full length or inactive state 611 at the end of the compression phase. Elements identified in FIG. 7 by reference numbers 604 , 608 , 615 correspond to elements 504 , 508 , 515 in FIG. 6 a.
[0050] Variations of the compression plate 611 are shown in FIGS. 8 , 8 a , 8 b , and FIG. 9 , respectively. The first variation is U-formed in a longitudinal section D-D and comprises a centrally disposed slot 714 in which the actuator 701 can be disposed. The wings 712 , 713 extending from either side of the base 711 increase the resilient spring action of the compression plate when mounted in-between the actuator 701 shown in an expanded state 701 * in FIG. 8 b . In the mounted state of the compression plate the wings 712 *, 713 * are bent downwards. When the compressed air is vented from the actuator 701 *, the wings 712 *, 713 * flap back to their original state 712 , 713 , thereby lifting up and thus extending the actuator 701 *. The V-formed variation of the compression plate 811 , 812 , 813 shown in FIG. 9 exerts an uplifting effect on an actuator also by its central portion 811 when mounted between the actuator and the chest of a patient in a manner corresponding to that of compression plate 711 .
[0051] In the pneumatic control scheme for an apparatus of the invention illustrated in FIG. 10 compressed air is provided from a gas flask 50 to expander module 51 in which the gas is expanded to the driving pressure. The driving pressure can vary depending on the length and diameter of the actuator and on the design of the apparatus, but will generally be in the interval of from about 2 to about 4.5 bar. Via a flexible pressure line 52 the driving gas is adduced to the apparatus 60 , where it passes a safety valve 53 that is mechanically vented at a selected pressure. A 3/2 solenoid-actuated valve 54 controlled by a timing module 57 optionally comprising a pressure sensor 58 supplies driving gas to one or several actuators of which only actuator 56 is shown. A self-sealing quick-coupling 55 is provided in the line between the 3/2-valve 54 and the actuator 56 . Over a compression/decompression cycle the driving gas supply and control system of FIG. 6 provides driving gas to the actuator 56 to make it expand and thereby displace the compression pad of one of the aforementioned embodiments in contact with the sternal region of a patient towards the heart of the patient, thereby providing heart massage and expelling air from the lungs. The actuator 56 is kept in an expanded state for a selected period of time and then deflated by via the venting outlet of the 3/2 valve 54 . The 3/2 valve 54 then is switched to the starting position of a new compression/decompression cycle. The actuator 56 can also be driven in a manner, in which equilibrium between the pressure of the driving gas provided to the actuator 56 and the pressure of the driving gas set by the expander module is not established. In such case a higher driving gas pressure than at equilibrium conditions will be used but will be provided to the actuator 56 only during an initial portion of the compression phase. An alternative exhaust path is indicated in broken lines. In the alternative path the actuator is vented, optionally to an intubation set or a breathing mask (not shown) via its end opposite to that coupled to valve 55 via a solenoid actuated exhaust valve 59 controlled by the timing module 57 ; in this variation the exhaust function of valve 54 is inoperative. | A gas-driven chest compression apparatus for cardiopulmonary resuscitation (CPR) comprises a flexible pneumatic actuator, capable of axial contraction when fed with a pressurized driving gas, and means for controlling the contraction thereof. Also disclosed are methods of providing chest compressions to a patient by means of a CPR apparatus comprising actuator(s) of this kind, and a corresponding use of the actuator. | 0 |
FIELD OF THE INVENTION
[0001] This invention relates to chain rollers or load skates that are capable of transporting heavy objects, and more particularly to motorized or self-propelled chain rollers or load skates for transporting heavy objects.
BACKGROUND
[0002] Heavy objects must be transported in various environments, including manufacturing and repair facilities. However, transporting heavy loads is a difficult and often time consuming undertaking due to the weight of the object(s) and also often due to the bulkiness of the object(s). It is desired to transport such heavy objects as time efficiently as possible, with as little machinery as possible, and as safely as possible. To achieve those goals, it is often desired that the transporter have the lowest possible profile.
[0003] Typically, a transporter for heavy objects has a tread assembly including tread segments wrapped around one or more driven gears and a number of stationary axles. The driven gear(s) and the stationary axles define the path of the tread assembly. Only the tread segments contact the ground or floor surface; neither the driven gear(s) nor the stationary rollers contact the ground or floor surface. A significant number of the tread segments contact the ground or floor surface. The tread segments are stationary relative to the ground or floor surface when they engage the ground or floor surface.
[0004] A horizontal force in the direction that the transporter is to travel is applied to the transporter or a force is applied to one or more of the gears to rotate the gears in the desired direction. That force causes the transporter to move in the desired direction with the tread segments serially engaging the ground or floor surface. The engagement of the tread segments with the ground or floor surface propels the machine in the desired direction.
[0005] Other heavy load transporters include chain roller assemblies that utilize a series of rollers linked together to form the track.
SUMMARY
[0006] According to preferred embodiments of the invention, there is provided a motorized chain roller for transporting heavy loads that includes a frame, a roller chain assembly movably disposed with the frame that includes a plurality of interconnected cylindrical rolls arranged in a continuous series, a first sprocket that engages the roller chain assembly to apply a transmission force to the roller chain assembly, a motor coupled to the frame and configured to transmit a rotational force to the first sprocket, and a load-bearing member coupled to and located within the frame. In these embodiments, the roller chain assembly is configured such that the rolls engage the load-bearing member to cause movement between the roller chain assembly and the load-bearing member perpendicular to the axes of rotation.
[0007] In some embodiments of the invention, the load-bearing member may be a plate. The rolls may engage one surface of the plate.
[0008] In other embodiments, the motorized chain roller may include a second sprocket spaced from the first sprocket. The roller chain assembly may form a loop around the first and second sprockets. The load-bearing member may be located within the loop, between the first and second sprockets. Two motors may be used to transmit a rotational force to the two sprockets. Alternatively, one of the sprockets may be an idler sprocket.
[0009] In yet other embodiments of the invention, the roller chain assembly may include a “chain” comprised of a plurality of overlapping links that connect the plurality of rolls to one another. The “chain” may include (1) a first set of links, wherein each link of this first set of links extends between and connects a pair of adjacent rolls (each link is attached to a different pair of rolls) and (2) a second set of links, wherein each link of this second set of links also extends between and connects a pair of adjacent rolls (again, each link is attached to a different pair of rolls). A pair of rolls connected to a link of the first set is never the same as a pair of rolls connected to a link of the second set. That is, a pair of rolls connected to a link of the second set always includes a roll that is also connected to one link of the first set and a roll that is also connected to a second link of the first set. The first sprocket may engage the second set of links to apply transmission force to the roller chain assembly.
[0010] In further embodiments of the invention, the cylindrical rolls of the roller chain assembly may be configured to contact the ground, pavement or a floor surface and a bottom surface of the load-bearing member and propel the motorized chain roller when the roller chain assembly moves in its loop. The direction and path of the motorized chain roller may be controlled by a rail, bar, or other elongated member. At least one guide block may be provided that mates with the rail, bar, or other elongated member so that the motorized chain roller moves along a path defined by the rail, bar, or other elongated member. Alternatively, the rail, bar, or other elongated member may be part of a track that is mounted on the ground, pavement or floor surface, such that the motorized chain roller moves along and is supported by the track.
[0011] Furthermore, some of the embodiments of the motorized chain rollers of this invention may have two modes of operation. In the first mode, the chain roller assembly rests of the ground, pavement or floor surface and the object to be transported in placed on the motorized chain roller. Movement of the chain roller assembly in its loop causes the motorized chain roller to move in a lateral direction perpendicular to the axes of rotation of the rolls because the rolls simultaneously engage the load-bearing surface and the ground, pavement or a floor surface. In the second orientation, the load-bearing surface of the motorized chain roller is placed on the ground, pavement or floor surface, with the chain roller assembly being exposed upward. The object(s) to be transported is placed on the chain roller assembly. Movement of the chain roller assembly in its loop causes the object(s) to be moved laterally across the top of the motorized chain roller, perpendicular to the axes of rotation of the rolls.
[0012] In this manner, this invention provides a motorized chain roller assembly that is compact, is self-sufficient, has a high load carrying capacity and reduces the time and machinery necessary to transport heavy loads.
[0013] Other advantages, benefits and features of the present invention will become apparent to those skilled in the art upon reading the detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a perspective view of a motorized chain roller of one embodiment of this invention.
[0015] FIG. 2 is an exploded view of the motorized chain roller illustrated in FIG. 1 .
[0016] FIG. 3 is a perspective view of the roller chain assembly and the sprocket assemblies of the motorized chain roller illustrated in FIGS. 1 and 2 .
[0017] FIG. 4 is a partially exploded view of the roller chain assembly and the sprocket assemblies illustrated in FIG. 3 .
[0018] FIG. 5 is a perspective view of the roller chain assembly, the sprocket assemblies and the load-bearing member of the motorized chain roller illustrated in FIGS. 1-4 .
[0019] FIG. 6 is a side view of the motorized chain roller illustrated in FIGS. 1-5 with selected components removed for clarity.
[0020] FIG. 7 is an exploded view of the frame and the load-bearing member of the motorized chain roller illustrated in FIGS. 1-6 .
[0021] FIG. 8 is a perspective view of a motorized chain roller of a second embodiment of this invention with selected components removed for clarity.
[0022] FIG. 9 is a partially exploded view of the roller chain assembly, the sprocket assemblies and the motors of the motorized chain roller illustrated in FIG. 8 .
DETAILED DESCRIPTION OF EMBODIMENTS
[0023] Referring to the accompanying drawings, motorized chain rollers according to the invention will be described.
[0024] Motorized chain roller (MCR) 1 is illustrated in FIGS. 1-7 and includes a frame 3 , a load-bearing member 11 attached to the frame 3 , motor stacks 9 attached to the frame 3 , sprocket assemblies 7 driven by the motors of motor stacks 9 and rotatably supported by the frame 3 , a roller chain assembly 5 that engages and forms a loop around the sprocket assemblies 7 , and guide block assemblies 33 that are also attached to the frame 3 .
[0025] I. The Frame
[0026] In this embodiment, the frame 3 includes a top load-bearing plate 13 , two top cover plates 15 , two side plates 17 , a front plate 19 , a back plate 21 and a tension member 57 . See FIGS. 1 , 2 and 7 . Any combination of plates and other rigid members can be used to form the frame of other embodiments of this invention as long as the members provide the structural strength and integrity to support the heavy loads to be transported and adequately support the roller chain assembly, the sprocket assembly(ies), the motor(s) and the load-bearing member.
[0027] The two side plates 17 , the front plate 19 and the back plate 21 are connected at their edges to form a basic rectangular frame. The top load-bearing plate 13 and the top cover plates 15 are attached to the top of the rectangular frame formed by the two side plates 17 , the front plate 19 and the back plate 21 and enclose the top of that rectangular frame. The side plates 17 , the front plate 19 , the back plate 21 , the top load-bearing plate 13 and the top cover plates 15 may be attached to each other by screws, bolts and nuts, pins or welding, with or without braces.
[0028] The side plates 17 are parallel. In this embodiment, each side plate 17 includes apertures 23 and 27 and an indentation 28 (see FIGS. 2 and 7 ).
[0029] As discussed below, the drive shafts 25 of the motor stacks 9 are received through apertures 23 to engage sprocket assemblies 7 . Apertures 27 are provided for access to the sprocket assemblies 7 and the roller chain assembly 5 . In this embodiment, the aperture 23 in a first of the side walls 17 is opposite the aperture 27 in the other side wall 17 . Likewise, the aperture 27 in the first side wall 17 is opposite the aperture 23 in the other side wall 17 . In other embodiments, the side walls 17 may not have any apertures 27 or may have additional apertures to access the sprocket assemblies 7 and/or the roller chain assembly 5 .
[0030] Closing plates 31 are removably attached to side walls 17 to cover apertures 27 . The closing plates 31 prevent exposure of the roller chain assembly 5 housed inside the frame 3 .
[0031] The edges of the load-bearing member 11 are received within the indentations 28 of side walls 17 , as shown in FIG. 7 and discussed below.
[0032] In this embodiment, the top load-bearing plate 13 extends beyond the side walls 17 , but does not extend all the way between the front plate 19 and the rear plate 21 . Moreover, in this embodiment, the top load-bearing plate 13 has a rectangular shape. In other embodiments, the top load-bearing plate may be of any shape and size that can support the heavy loads to be transported without a risk of the motorized chain roller tilting if a load is not centered on the top load-bearing plate.
[0033] The top load-bearing plate 13 may be made of steel or any other material with high strength that does not substantially deform under heavy loads.
[0034] As stated, in this embodiment, the top load-bearing plate 13 does not extend all the way between the front plate 19 and the back plate 21 . Thus, one or more top cover plates 15 are provided to fully enclose the top opening of the rectangular frame formed by the two side plates 17 , the front plate 19 and the back plate 21 . The top cover plates 15 abut the top load-bearing plate 13 on opposite sides of the top load-bearing plate 13 .
[0035] While this embodiment includes two top cover plates 15 of the same shape and size, other embodiments may not have any top cover plates or may have any number of top cover plates of the same or different shape and size.
[0036] The tension member 57 is attached to the top load-bearing plate 13 and extends downwardly from the top load-bearing plate 13 . In this embodiment, the tension member 57 has an arcuate lower surface that engages the roller chain assembly 5 , as discussed below.
[0037] II. The Load-Bearing Member
[0038] The load-bearing member 11 is illustrated in FIGS. 5-7 . In this embodiment, the load-bearing member 11 is a substantially rectangular plate that extends between and is attached to the sidewalls 17 . Specifically, the side edges of the load-bearing member 11 are received in the indentations 28 of the side walls 17 . Those side edges of the load-bearing member 11 are coupled to the side walls 17 as illustrated in FIG. 7 and as explained below. Bars 59 with apertures are placed on the underside of the edges of the load-bearing member 11 . Fastening members 59 a extend upward through those apertures, through holes in the side edges of the load-bearing member 11 , into and through holes in the side walls 17 . Fastening members 59 a may be screws, bolts, pins, a combination thereof, or any other suitable fasteners.
[0039] While in this embodiment, the load-bearing member 11 is a substantially rectangular plate, in other embodiments, the load-bearing member can have any shape and may be a structural member other than a plate. Further, in yet other embodiments, the load-bearing member can comprise multiple components joined and/or acting together to perform the load-bearing function described herein.
[0040] III. The Motor Stacks
[0041] Motor stacks 9 are illustrated in FIGS. 1 and 2 . Motor stacks 9 include a motor, a brake, a gear head or series of gear heads, and a drive shaft 25 . The drive shaft 25 is rotated by the motor via the gear head or series of gear heads. The motors may be hydraulic motors, electric motors, or any other type of motor that is capable of providing the requisite torque.
[0042] Motor stacks 9 are attached to side walls 17 of the frame 3 . In this embodiment, a motor stack 9 is attached to each side wall 17 , at opposite ends of the MCR 1 . Other embodiments of this invention may include a single motor stack, or more than two motor stacks. In yet other embodiments, the motor stacks can be attached to the same side wall of the frame, such as in the embodiment illustrated in FIGS. 8 and 9 and described below.
[0043] The drive shaft 25 extends inward through the aperture 23 in the side wall 17 to which the motor stack 9 is attached. The drive shafts 25 engage the sprocket assemblies 7 to rotate the sprockets of those assemblies with the necessary torque, as discussed below.
[0044] IV. The Sprocket Assemblies
[0045] The sprocket assemblies 7 are illustrated in FIGS. 2-6 . In this embodiment, there are two sprocket assemblies 7 , with each sprocket assembly 7 being driven by the motor of a motor stack 9 . In other embodiments, only one of the sprocket assemblies may be driven by a motor and the other sprocket assembly may include an idler sprocket. Further, while in this embodiment, the sprocket assemblies 7 are located at the ends of the loop formed by the roller chain assembly 5 with the load-bearing member 11 located between the sprocket multiple load-bearing members located on opposite sides of the intermediate driven sprocket assembly.
[0046] Further, in this embodiment, each sprocket assembly 7 includes a cylindrical member 50 , a drive shaft socket 51 , two teethed rings 47 , and a bearing ring 53 . The cylindrical member 50 , the drive shaft socket 51 , and the teethed rings 47 are an integral member. In other embodiments, the cylindrical member 50 , the drive shaft socket 51 and/or the teethed rings 47 can be separate members attached together.
[0047] The drive shaft socket 51 receives and engages the drive shaft 25 of motor stack 9 , such that the drive shaft socket 51 , and thus the cylindrical member 50 and the two teethed rings 47 rotate with the drive shaft 25 .
[0048] The teethed rings 47 include teeth 48 that engage the roller chain assembly 5 , to drive the roller chain assembly 5 , as discussed below.
[0049] The bearing ring 53 is located around the drive shaft socket 51 . The bearing ring 53 permits rotational movement of the cylindrical member 50 and the teethed rings 47 relative to the side walls 17 of the frame 3 . While in this embodiment, that relative movement is permitted due to the bearing ring 53 , other bearing members can be used in other embodiments.
[0050] V. The Roller Chain Assembly
[0051] The roller chain assembly 5 is illustrated in FIGS. 2-6 . In this embodiment, the roller chain assembly 5 includes a series of parallel and interconnected cylindrical roller sleeves 37 . More specifically, the roller chain assembly 5 includes a plurality of roller axles 45 , of cylindrical roller sleeves 37 , of inner links 39 , of engaging links 43 , and of outer links 41 (see FIG. 4 ). There is a series of the inner links 39 , the engaging links 43 and the outer links 41 on each end of the roller axles 45 and the roller sleeves 37 .
[0052] A cylindrical roller sleeve 37 is rotatably mounted on each axle 45 . Each of the cylindrical roller sleeves 37 has its own axis of rotation (see FIG. 4 ), with all the axes of rotation being parallel. The cylindrical roller sleeves 37 may rotate in a clock-wise direction or a counter-clockwise direction, depending on the direction of movement of the roller chain assembly 5 .
[0053] Each inner link 39 and each outer link 41 receives the ends of a pair of adjacent roller axles 45 . The same pair of ends of the roller axles 45 that is received in an inner link 39 is also received in an outer link 41 . Each engaging link 43 also receives the ends of a pair of adjacent roller axles 45 ; however, the pair of adjacent roller axles 45 whose inner link 39 is also received in an outer link 41 . Each engaging link 43 also receives the ends of a pair of adjacent roller axles 45 ; however, the pair of adjacent roller axles 45 whose ends are received in an engaging link 43 is not the same as any pair of roller axles 45 whose ends are received in an inner link 39 and an outer link 41 . Rather, the pair of roller axles 45 whose ends are received in an engaging link 43 includes a roller axle 45 whose end is received by one inner link 39 and one outer link 41 and a roller axle 45 whose end is received by an adjacent inner link 39 and outer link 41 . As a result, the roller sleeves 37 are interconnected through the axles 45 , the inner links 39 , the engaging links 43 , and the outer links 41 .
[0054] As illustrated in the Figures, the series of engaging links 43 are located between the series of the inner links 39 and the series of the outer links 41 . The teeth 48 of the teethed rings 47 of the sprocket assemblies 7 engage the engaging links 43 , as discussed below.
[0055] While in this embodiment, the roller axles 45 are connected by “chains” consisting of the inner links 39 , the engaging links 43 and the outer links 41 , in other embodiments, the roller axles can be connected by any link assembly that permits movement of the roller chain assembly 5 in the loop around the sprocket assemblies. Moreover, while this embodiment has two “chains,” a single “chain” may suffice.
[0056] VI. The Guide Block Assemblies
[0057] This embodiment includes two guide block assemblies 33 that are coupled to the front plate 19 of the frame 3 . See FIGS. 1 and 2 . The guide block assemblies 33 include guide stops 35 that extend downwardly in a spaced relationship. Each guide block assembly 33 includes a pair of guide stops 35 . In this embodiment, guide stops 35 are cam followers, which include a mechanical bearing. In other embodiments, the guide stops can be other mechanical work pieces, including work pieces that include a bearing function.
[0058] Guide stops 35 guide MCR 1 along a track (not shown) that may resemble the shape and configuration of a single train track. When used in that manner, the MCR 1 is positioned relative to the rail such that one of each pair of guide stops 35 is on each side of the rail. When the MCR 1 translates, the guide stops 35 keep the MCR 1 properly positioned vis-à-vis the rail.
[0059] While in this embodiment there are two guide block assemblies 33 attached to the front wall 19 , in other embodiments, such as the embodiment illustrated in FIGS. 8 and 9 (discussed below), there may be one or more guide block assemblies attached to the front wall and the back wall of the motorized chain rollers. Additionally, guide stops may protrude downward from other components of the frame or from guide block assemblies attached to other components of the frame, such as the sidewalls.
[0060] VII. Assembly and Operation
[0061] The MCR 1 is assembled as follows. The frame 3 is assembled as discussed above. The load-bearing member 11 is attached to the side walls 17 of the frame 3 by plates 59 and fastening members 59 a, as also discussed above (see FIG. 7 ). As further discussed above, the motor stacks 9 are attached to the exteriors of the side walls 17 such that the drive shafts 25 of the motor stacks 9 extend through the apertures 23 in side walls 17 into the interior of the frame 3 . The drive shaft sprockets 51 of the sprocket assemblies 7 are attached to the drive shafts 25 , such that those sprockets 51 and the cylindrical members 50 , teethed rings 47 and brake sockets 52 are driven by the drive shaft 25 . The roller chain assembly 5 forms a loop around the sprocket assemblies 7 and the load-bearing member 11 . The engaging links 43 of the roller chain assembly 5 are engaged with the teeth 48 of the teethed rings 47 of the sprocket assemblies 7 .
[0062] The MCR 1 operates as follows.
[0063] When the motors of motor stack 9 are activated, the drive shafts 25 rotate. The rotation of the drive shafts 25 causes rotation of the cylindrical members 50 and the teethed rings 47 of the sprocket assemblies 7 due to the drive shaft 25 /drive shaft sprocket 51 engagement. Because the teeth 48 of the teethed rings 47 engage the engaging links 43 of the roller chain assembly 5 , the rotation of the cylindrical member 50 and the teethed rings 47 causes the roller chain assembly 5 to move in its loop around the sprocket assemblies 7 and the load-bearing member 11 .
[0064] The cylindrical roller sleeves 37 engage the underside of the load-bearing member 11 . That engagement causes propulsion of the MCR 1 or of objects being conveyed by the MCR 1 , depending on the mode in which the MCR 1 is being used (the two modes are discussed below), as the roller chain assembly 5 is driven in its loop.
[0065] The MCR 1 has two modes of operation.
[0066] The first mode of operation is in the orientation illustrated in the Figures. The chain roller assembly 5 is in contact with the ground, pavement or building floor and the object(s) to be transported are on top of the top load-bearing plate 13 . Activation of the motors of motor stacks 9 causes movement of the roller chain assembly 5 in its loop around the sprocket assemblies 7 and the load-bearing member 11 , as discussed above. Because the cylindrical roller sleeves 37 in the lower portion of the loop formed by the roller chain assembly 5 are “pinched” between (or in engagement with) the load-bearing member 11 and the ground, pavement or floor of a building, movement of the roller chain assembly 5 in its loop causes translation of the MCR 1 along the ground, pavement or floor of a building. More specifically, the cylindrical roller sleeves 37 in the lower portion of the loop are in engagement with both the load-bearing member 11 and the ground, pavement or building floor. Movement of those roller sleeves 37 in the loop causes those roller sleeves 37 , and thus the entire MCR 1 , to move laterally, because the individual roller sleeves 37 “roll” along the ground, pavement or building floor.
[0067] The motors of motor stacks 9 are reversible, such that MCR 1 can go forward or backward.
[0068] In the second mode of operation, the MCR 1 is inverted from the orientation illustrated in the Figures such that the top load-bearing plate 13 of the frame 3 rests on the ground, pavement or floor surface and the underside of the roller chain assembly 5 is facing upward. In this orientation, the MCR 1 functions as a load conveyor, because the MCR 1 does not move.
[0069] In this second mode of operation, the object(s) to be conveyed are placed on top of the exposed portion of the roller chain assembly 5 . When the motors of motor stacks 9 are activated, the cylindrical members 50 and the teethed rings 47 are still rotated by the drive shafts 25 of the motor stacks 9 . That again causes the roller chain assembly 5 to move in its loop around the sprocket assemblies 7 and the load-bearing member 11 . Because the roller chain assembly 5 is in firm engagement with the load-bearing member 11 and the underside of the object(s) being conveyed, movement of the roller chain assembly 5 in the loop causes the objects being conveyed to move laterally with the roller chain assembly 5 .
[0070] Multiple MCRs 1 may be aligned such that an object or objects may be transported on top of the cylindrical roller sleeves 37 of multiple roller chain assemblies 5 .
[0071] The interplay of the load-bearing member 11 and the roller sleeves 37 in contact with the load-bearing member 11 causes the force from the load being transported to be evenly distributed on the load-bearing member 11 , the frame 3 and the roller chain assembly 5 . That is advantageous because heavier loads may be transported with the same amount of lateral force as compared to conventional moving mechanisms that do not equally distribute the weight force of the loads.
[0072] Regardless of the orientation of MCR 1 , the tension member 57 applies a tension force to the roller chain assembly 5 to prevent slack in the roller chain assembly 5 and ensure that the roller chain assembly 5 efficiently transmits force from the sprocket assemblies 7 into lateral movement.
[0073] A second embodiment of the invention is illustrated in FIGS. 8 and 9 —MCR 1 a. The components of the MCR la are given the same reference numbers as the corresponding components of the MCR 1 , except that a suffix “a” is added.
[0074] In this embodiment, the motor stacks 9 a include direct motors. That is, the drive shaft 25 a is directly driven by the motor, without any intervening gears. This embodiment also includes brakes that are external to the motor stacks 9 a, brakes 61 . Also in this embodiment, the sprocket assemblies 7 a include brake socket 52 . The brakes 61 engage the brake sockets 52 . Each brake 61 is operated by a brake solenoid 63 . The brakes 61 may be drum brakes, disc brakes, or any other type of brakes that retards rotation of the cylindrical members 50 a and the teethed rings 47 a.
[0075] Also, in this embodiment, motor stacks 9 a are attached to the same side wall 17 a. Moreover, guide block assemblies 33 are replaced by guide flanges 33 a, with a guide flange 33 a being attached to each of the front wall 19 a and the back wall 21 a. The guide stops 35 a extend downward from the guide flanges 33 a in a spaced relationship, such that a track can be received between each pair of the guide stops 35 a.
[0076] Due to the arrangement of the frames, motors, sprocket assemblies, load-bearing members and chain roller assemblies of the embodiments illustrated in the Figures, the height of the illustrated motorized chain rollers can be less that 20 inches and preferably as low as approximately 13 inches, but may be even lower.
[0077] What has been described and illustrated herein are preferred embodiments of the invention along with some variations. The terms, descriptions and figures used herein are set forth by way of illustration only and are not meant as limitations. Those skilled in the art will recognize that many variations are possible within the spirit and scope of the invention, which is intended to be defined by the following claims—and their equivalents—in which all terms are meant in their broadest reasonable sense unless otherwise indicated. | A motorized chain roller includes a frame, a roller chain assembly movably disposed within the frame, a first sprocket that engages the roller chain assembly to apply a transmission force to the roller chain assembly, at least one motor coupled to the frame and configured to transmit a rotational force to the first sprocket, and a load-bearing member coupled to and located within the frame. The roller chain assembly includes a plurality of interconnected cylindrical rolls arranged in a continuous series. Each of the cylindrical rolls has an axis or rotation. The roller chain assembly engages the load-bearing member to cause movement between the roller chain assembly and the load-bearing member perpendicular to the axes of rotation. | 1 |
This is a continuation of co-pending application Ser. No. 805,391 filed on Dec. 2, 1985, which is a continuation of application Ser. No. 545,313 filed on Oct. 24, 1983, both now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to pressure pulse generators in general, and in particular to pressure pulse generators such as the "mud siren" type used in oil industry MWD (measurements-while-drilling) operations to transmit downhole measurement information to the well surface during drilling by way of a mud column located in a drill string.
2. Description of the Prior Art
Many systems exist for transmitting data representative of one or more measured downhole conditions to the surface during the drilling of a well borehole. One such system, described in Godbey U.S. Pat. No. 3,309,656, employs a downhole pressure pulse generator or modulator and is operated to transmit modulated signals carrying encoded data at acoustic frequencies to the surface by way of the mud column in the drill string. In such a system, it has been found useful to power the downhole electrical components by means of a self-contained mud-driven turbine generator unit (known as a "mud turbine") positioned downstream of the modulator.
Existing modulators of the mud siren type usually take the form of "turbine-like" signal generating valves positioned in the drill string near the drill bit and exposed to the circulating mud path. A typical such modulator is comprised of a fixed stator and a motor-driven rotatable rotor, positioned coaxially of each other. The stator and rotor are each formed with a plurality of block-like radial extensions or lobes spaced circumferentially about a central hub so that the gaps between adjacent lobes present a plurality of openings or ports to the oncoming mud flow stream. When the respective ports of the stator and rotor are in direct alignment, they provide the greatest passageway for flow of drilling mud through the modulator. When the rotor rotates relative to the stator, alignment between the respective ports is shifted, interrupting the flow of mud to generate pressure pulses in the nature of acoustic signals. Rotation of the rotor relative to the stator in the circulating mud flow produces a cyclic acoustic signal that travels up the mud column in the drill string to be detected at the drillsite surface. By selectively varying the rotation of the rotor to produce changes in the signal, modulation in the form of an encoded pressure pulse is achieved which carries information from downhole instruments to the surface for analysis.
The lobe configuration and the relative placement of the stator and rotor elements of conventional modulators is such as to subject the rotor to fluid dynamic forces due to the mud stream that cause the rotor to seek a "stable closed" position in which the lobes of the rotor block the ports of the stator. There is thus an undesirable tendency for the modulator to assume a position that blocks the free flow of drilling mud whenever the rotor becomes even temporarily inoperative. This increases the likelihood that the modulator will jam, as solids carried by the mud stream are forced to pass through restricted modulator passages. Rotor restart is made more difficult because the reduced mud flow interferes with the generation of rotor power by the mud turbine below. Prolonged modulator closing can obstruct mud flow to such an extent that lubrication of the drill bit and other vital functions of the mud become so adversely affected, that the entire drilling operation is jeopardized.
A number of approaches have been proposed to solve the problem caused by the tendency of existing modulators to assume the closed position described above. One such approach, described in Patton, et al. U.S. Pat. No. 3,792,429, is to use magnetic force to bias the modulator toward an open position and hold it there in the event the rotor becomes inoperative. Magnetic attraction between a magnet attached to the modulator housing and a cooperating magnetic element positioned on the rotor shaft develops sufficient torque to overcome the fluid dynamic torque caused by the drilling mud stream. This approach has the disadvantages that the tool must be lengthened to accommodate the magnets and that introduction of an extraneous magnetic field downhole can interfere with measurements of the earth's magnetic field (used to derive tool orientation).
In commercial MWD operations, the spacing between the rotor and stator components of the modulator must be narrow in order to produce satisfactory acoustic signals. This requirement makes the modulator particularly susceptible to jamming or obstruction by solids present in the mud stream. A system for avoiding such jamming, described in Manning U.S. Pat. No. Re. 29,734, includes control means responsive to conditions tending to slow the motor (such as an increase in pressure differential across the modulator or an increase in driving torque requirement) for temporarily separating the rotor and stator in order to allow debris to be cleared from the modulator by the flowing mud. Such a system can be employed to provide some relief from the decreased mud flow experienced with a closed modulator by separating the modulator parts in response to the pressure differential increase experienced when the modulator assumes a closed position.
SUMMARY OF THE INVENTION
The present invention provides an improved pressure pulse generator or modulator of the type used for communicating information between points of a wellbore by way of fluid flowing in a tubing string which includes means responsive to the flow of fluid in the string for establishing fluid dynamic forces that bias the generator into a stable open position.
A pressure pulse generator structured in accordance with one aspect of the present invention comprises a fixed stator and a rotatable rotor both mounted within a housing adapted to be connected in a tubing string so that fluid flowing in the string will at least partially flow through the housing. The rotor is mounted adjacent to and downstream of the stator. Both stator and rotor are formed to have a plurality of radial extensions or lobes, with intervening gaps between adjacent lobes serving to present a plurality of ports or openings for the passage of fluid flowing through the housing. Rotation of the rotor relative to the stator will vary the blocking effect of the rotor extensions to flow issuing from the stator ports, shifting the relative alignment of the respective stator and rotor ports between a position providing the greatest passageway for fluid flow through the housing ("open" position) and a position providing the least passageway for fluid flow through the housing ("closed" position). This valve action interrupts fluid flow in such a manner as to cause the generation and transmission through the flowing fluid upstream of a pressure pulse signal. The relative placement of the stator and rotor and the specific configuration of their respective lobes are such that fluid dynamic forces are established in response to the flow of fluid in the housing that bias the rotor into an orientation providing the greatest fluid passageway through the generator. Should the generator fail or otherwise become inoperative, fluid forces will urge it into a position of minimum flow blockage.
In general, the forces are developed from the fluid flow by providing each lobe of the rotor with sides outwardly tapered in the downstream direction and with underlap relative to the stator lobes. The taper of each side on the rotor lobes is preferably in the range of about 8° to 30° with respect to a vertical axis.
In another aspect of the present invention, the rotor lobes are configured in such a manner as to cause the rotor to oscillate between an open position and a partially closed position due to fluid dynamic action. This serves to prevent debris from blocking the flow of fluid through the modulator and provides a periodic motion and signal whose frequency varies with flowrate. The oscillation takes the form of aerodynamic flutter created by providing the sides of each rotor lobe with reduced width, untapered regions at their trailing edges adjacent to the base of the lobe. The sides of the rotor lobes may also be provided with untapered regions at their leading edges adjacent to the top of the lobe so as to provide a cutting action upon debris passing into the ports and into the gap between the stator and rotor.
The modulator of the present invention provides an improved signal source having good obstruction avoidance capabilities. It has particular application in the oil industry in measurements-while-drilling, well testing and completed well monitoring operations as a signal source for communications from downhole to surface, from surface to downhole, or between intermediate points of a well. Other applications include its use as a sound source for underwater seismological explorations, use as a flow monitoring device and use as a unidirectional flow valve.
BRIEF DESCRIPTION OF THE DRAWINGS
The construction, operation, and advantages of the invention can be better understood by referring to the drawings forming a part of the specification, in which:
FIG. 1 is a schematic view of a pressure pulse generator in accordance with the present invention, shown coupled in a drill string of a typical drilling operation in its application for communication between a downhole MWD tool and a well surface;
FIG. 2 is a side view, in partial section, of the generator of FIG. 1;
FIG. 3a is a perspective view of the generator of FIGS. 1 and 2;
FIG. 3b is an unwrapped end view of the stator and rotor lobes of the generator of FIG. 3a;
FIG. 4a is a top plan view of the stator of FIG. 3a;
FIG. 4b is a section view taken along the line 4b--4b of FIG. 4a;
FIG. 5a is a top plan view of the rotor of FIG. 3a;
FIG. 5b is a section view taken along the line 5b--5b of FIG. 5a;
FIG. 5c is a partial end view as seen from the line 5c--5c of one of the lobes of the rotor of FIG. 5a;
FIG. 6 is a schematic perspective view identifying reference characters helpful in understanding relative dimensions;
FIG. 7a is a top plan view of a modified embodiment of the pressure pulse generator of FIGS. 1-5c;
FIG. 7b is an end view as seen from the line 7b--7b of one set of the stator and rotor lobes of FIG. 7a;
FIG. 8 is a fragmented perspective view of a further modification of the generator of FIGS. 1-5c, in which the rotor has a reduced portion adjacent the rotor hub;
FIG. 9 is a top plan view of the rotor of FIG. 8;
FIG. 10a is a perspective view of a yet further modification of the generator of FIGS. 1-5c, illustrating a design which gives rise to aerodynamic flutter; and
FIG. 10b is an unwrapped end view of the stator and rotor lobes of FIG. 10a.
Throughout the drawings, like reference numerals are used to identify like parts.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 of the drawings shows a tubular measurements-while-drilling (MWD) tool 20 connected in a tubular drill string 21 having a rotary drill bit 22 coupled to the end thereof and arranged for drilling a borehole 23 of a well through various earth formations. As the drill string 21 is rotated by a conventional drilling rig (not shown) at the surface of the borehole 23, substantial volumes of a suitable drilling fluid (known as "drilling mud") are continuously pumped down through the drill string 21 and discharged from the drill bit 22 to cool the bit and to carry away earth cuttings removed by the bit. The mud is returned to the surface up along the annular space existing between the walls of the borehole 23 and the exterior of the drill string 21. The circulating mud stream flowing through the drill string 21 serves as a medium for transmitting pressure pulse signals carrying information from the MWD tool 20 to the surface, as described more fully below.
A downhole data signaling unit 24 has transducers mounted on the tool 20 that take the form of one or more condition responsive devices 26 and 27 coupled to appropriate data encoding electrical circuitry, such as an encoder 28, which sequentially produces encoded digital data electrical signals representative of the measurements obtained by the transducers 26 and 27. The transducers 26 and 27 are selected and adapted as required for the particular application to measure such downhole parameters as the downhole pressure, the temperature, and the resistivity or conductivity of the drilling mud or adjacent earth formations, as well as to measure various other downhole conditions similar to those obtained by present day wireline logging tools.
Electrical power for operation of the data signaling unit 24 is provided by a typical rotatably-driven axial flow mud turbine 29 which has an impeller 30 responsive to the flow of drilling mud that drives a shaft 31 to produce electrical energy.
The data signaling unit 24 also includes a modulator 32 which is driven by a motor 35 to selectively interrupt or obstruct the flow of the drilling mud through the drill string 21 in order to produce digitally-encoded pressure pulses in the form of acoustic signals. The modulator 32 is selectively operated in response to the data-encoded electrical output of the encoder 28 to generate a correspondingly encoded acoustic signal. This signal is transmitted to the well surface by way of the fluid flowing in the drill string 21 as a series of pressure pulse signals which preferably are encoded binary representations of measurement data indicative of the downhole drilling parameters and formation conditions sensed by the transducers 26 and 27. When these signals reach the surface, they are detected, decoded and converted into meaningful data by a suitable signal detector 36, such as shown in U.S. Pat. Nos. 3,309,656; 3,764,968; 3,764,969; and 3,764,970.
The modulator 32 includes a fixed stator 40 and a rotatable rotor 41 which is driven by the motor 35 in response to signals generated by the encoder 28. Rotation of the rotor 41 is controlled in response to the data-encoded electrical output of the encoder 28 in order to produce a correspondingly encoded acoustic output signal. This can be accomplished by applying well-known techniques to vary the direction or speed of the motor 35 or to controllably couple/uncouple the rotor 41 from the drive shaft of the motor 35.
The stator 40 has a plurality of evenly-spaced block-like lobes 71 circumferentially arranged about a central hub. The gaps between adjacent lobes 71 provide a plurality of ports to pass the incident drilling mud through the stator as jets or streams directed more or less parallel to the stator hub axis. The rotor 41 has a similar configuration to that of the stator 40 and is positioned adjacent to and downstream of the stator for rotation about an axis coaxial with the hub axis of the stator. As the rotor 41 is rotated, its lobes 72 successively move into and out of positions obstructing the flow of the fluid jets through the ports of the stator 40, to produce a pressure pulse signal that is transmitted upstream in the circulating mud.
When the rotor 41 is rotated in relation to the stator 40 so as to momentarily present the greatest flow obstruction to the circulating mud stream, the resulting acoustic signal will be at its maximum amplitude. As the rotor 41 continues to rotate, the amplitude of the acoustic signal produced by the modulator 32 will decrease from its maximum to its minimum value as the rotor moves to a position in which it presents the least obstruction to the mud flow. Further rotor rotation will cause a corresponding increase in signal amplitude as the rotor again approaches its next maximum flow obstruction position.
Those skilled in the art will recognize that rotation of the modulator rotor 41 will produce an acoustic output signal having a cyclic waveform with successively alternating positive and negative peaks referenced about a mean pressure level. Continuous rotation of the rotor 41 will produce a typical alternating or cyclic signal at a designated frequency which will have a determinable phase relationship in relation to some other alternating signal, such as a selected reference signal generated in the circuitry of the signal detector 36. By momentarily advancing, retarding, stopping or reversing the rotation of the rotor 41 in response to output from the encoder 28, the rotor can be selectively shifted to a different position vis-a-vis the stator 40 than it would have occupied had it continued to rotate without change. This selective shifting causes the phase of the acoustic signal to shift relative to the phase of the reference signal. Such controlled phase shifting of the signal generated by the modulator 32 acts to transmit downhole measurement information by way of the mud column to the well surface for detection by the signal detector 36. A shift in phase at a particular instance signifies a binary bit " 1" (or "0") and absence of a shift signifies a binary bit "0" (or "1"). Other signal modulation techniques are usable, and selection of the specific encoding, modulation and decoding schemes to be employed in connection with the operation of the modulator 32 are matters of choice, detailed discussion of which is unnecessary to an understanding of the present invention.
As shown in FIG. 2, both the stator 40 and the rotor 41 are mounted within a tubular housing 42 which is force-fitted within a portion of a drill collar 43 by means of enlarged annular portions 44 and 45 of the housing 42 which contact the inner surface of the drill collar 43. A plurality of "O"-rings 46 and 47 provide sealing engagement between the collar 43 and the housing 42.
The stator 40 is mounted by way of threaded connections 50 (see also FIG. 4b) to an end of a supporting structure 51 centrally located within the housing 42 and locked in place by a set screw 56. The space between the end of the threaded portion of the stator 40 and an adjacent shoulder of the supporting structure 51 is filled with a plurality of "O"-rings 55. The supporting structure 51 is maintained in spaced relationship to the inner walls of the housing 42 by means of a front standoff or spider 52. The standoff 52 is secured to the supporting structure 51 by way of a plurality of hex bolts 53 (only one of which is shown) and, in turn, secured to the housing 42 by a plurality of hex bolts 54 (only one of which is shown). The front standoff 52 is provided with a plurality of spaced ports to permit the passage of drilling fluid in the annular space formed between the supporting structure 51 and the inner walls of the housing 42.
The rotor 41 is mounted for rotation on a shaft 60 of the motor 35 (FIG. 1) which drives the rotor 41. The rotor 41 has a rotor bushing 59 (FIG. 2) keyed near the end of the shaft 60 and forced into abutment with a shoulder 61 of the shaft 60 by a bushing 62 also keyed to the end of the shaft 60. The bushing 62 is forced against the rotor bushing 59 by means of a hex nut 63 threaded to the free end of the shaft 60. An inspection port 58 is provided for examining the stator and rotor lobes 71, 72 to measure rotor-stator spacing and to detect wear.
The shaft 60 is supported within a bearing housing 65 for rotation about a bearing structure 66. The bearing housing 65 is supported in spaced relationship to the inner walls of the housing 42 by way of rear standoff or spider 67 secured to the bearing housing by way of hex bolts 68 and, in turn, secured to the housing 42 by way of hex bolts 69.
As shown in FIGS. 2 and 3, drilling fluid flows into the top of the housing 42 in the direction indicated by arrows 70 (FIG. 2) through the annular space between the external wall of the supporting structure 51 and the inner walls of the housing 42 and flows through ports of the stator 40 and the rotor 41. The fluid flow continues past the rear standoff 67 and on to the drill bit 22 (FIG. 1). The shaft 60 drives the rotor 41 to interrupt the fluid jets passing through the ports of the stator 40 to generate a coded acoustic signal that travels upstream.
In accordance with the invention, the rotor 41 is positioned downstream of the stator 40 and its lobes 72 are configured to provide fluid dynamic forces in response to the mud flow which drive the rotor 41 to an open position relative to the stator 40 whenever the rotor 41 is not being driven by the motor 35. More specifically, the relative geometry and placement of the stator 40 and the rotor 41 establishes fluid dynamic biasing of the rotor 41 into an orientation in which the lobes 72 of the rotor 41 provide the least obstruction to fluid flowing through the ports of the stator 40.
FIGS. 3a-5c show thefeatures of a first embodiment of modulator 32 that exhibits such "stable open" behavior. FIG. 6 identifies dimensions useful in understanding these features.
The general relationship between the stator 40 and the rotor 41 of the modulator 32 is shown in FIG. 3a. As indicated by the arrows, drilling mud flows through the housing 42 in the downhole direction and rotation of the rotor 41 generates an acoustic signal that is transmitted uphole. In contrast to prior art modulators which usually position the rotor upstream of the stator, the rotor of the modulator 32 is located downstream of the stator.
As shown, both the stator 40 and the rotor 41 are provided with a plurality of radially extending lobes 71, 72 circumferentially spaced in a symmetrical fashion about coaxial central hubs. The lobes constitute wedge-like projections radiating from the hub, each lobe being defined by a top (upstream surface), a base (downstream surface), opposite radially-extending sides (surfaces extending outwardly from the hub that join the top and the base), and an end (surface furthest from and concentric with the hub that abuts the inner walls of the housing). All lobes 71 of the stator 40 are identically constructed and all lobes 72 of the rotor 41 are identically constructed. The same number of lobes is used for the stator and the rotor, this number being conveniently selected as six. Selection of a different number is possible, but will change the characteristics of the generated signal.
For more rigidity, either one or both of the stator 40 and rotor 41 may optionally be provided with a rim that circumscribes the ends of its lobes. The stator 40 may also, alternatively, be formed integrally with the housing 42. This is a choice based on manufacturing convenience.
The ports between adjacent lobes on each of the stator and the rotor are defined by the periphery of the hub and the facing sides of adjacent lobes. It is considered advantageous, though not essential, for the respective lobes and intervening ports to be dimensioned so that they are approximately the same size.
The six lobes 71 of the stator 40 (FIGS. 3a, 3b, 4a and 4b) are evenly distributed about the stator hub. The tops and bases of the stator lobes 71 are parallel to each other and perpendicular to the hub axis. The sides of the lobes 71 are generally radial with respect to the hub axis, with opposite sides of each lobe being angled at 30° and like sides of adjacent lobes being angled at 60° relative to the hub axis (FIG. 4a). The internal threads 50 provided on the inside of the stator hub (see FIG. 4b), in addition to connecting the stator 40 to the supporting structure 51 as described previously, provide means for adjusting the amplitude of the generated acoustic signal by varying the spacing between the bases of the stator lobes 71 and the tops of the rotor lobes 72. Stator lobes 71 are formed with the outer width W1 and area of the top of the lobe being equal to the outer width W2 and area of the base of the lobe (FIG. 6). Stator ports are formed to have equal inlet and outlet openings, with the inner and outer widths P1, P3 of the inlet openings being the same as the respective inner and outer widths P2, P4 of the outlet openings.
The rotor lobes 72 (FIGS. 3a, 3b and 5a-5c) are evenly distributed about the rotor hub so that radial lines drawn from the hub axis through centers of lobes 72 make angles of 60° with each other and angles of 30° with lines drawn from the hub axis through the centers of adjacent rotor ports (see FIG. 5a). Like those of the stator 40, the lobes 72 of the rotor 41 have parallel tops and bases which are perpendicular to the hub axis. The sides of the lobes 72, however, are outwardly tapered in the direction of fluid flow ("positive" taper). Thus, the outside width W4 (see FIG. 6) and area of the base (trailing face) of each rotor lobe 72 is greater than the corresponding outside width W3 and area of its top (leading face). FIG. 5c illustrates a preferred positive uniform taper of 12° for the sides of the lobes 72. Other tapers of 8° to 30° are also suitable.
As shown in FIG. 5a, the edges 74 and 75 of each rotor lobe 72 (formed where the sides meet the top) are angled at 27°, as are the edges 76 and 77 (formed where the sides meet the base). The tops of the rotor lobes 72 underlap the bases of the stator lobes 71, with the outside width W3 (FIG. 6) and area of the top of each rotor lobe 72 being less than the corresponding outside width W2 and area of the base of each stator lobe 71. The rotor ports are configured in a complementary way, so that the inside width P5, outside width P7 and area of the inlet opening of each rotor port are greater than the corresponding inside width P2, outside width P4 and area of the outlet opening of each stator port (see FIG. 6). Since the rotor ports are formed by the spaces between the rotor lobes 72, the sides of the ports are inwardly tapered in the downstream direction.
As shown in FIGS. 5a and 5b, each rotor lobe 72 has a bore 80 to receive the machine screws 57 (FIG. 2) which serve to fasten the lobes 72 to the rotor bushing 59.
The relative dimensioning of stator and rotor lobes 71, 72, as described, causes the flowing mud to exert fluid dynamic forces on the rotor which bias the modulator 32 into a stable open position. When the modulator 32 is in a nonequilibrium state as shown in FIG. 3b, forces are generated that act on the geometry of the modulator to cause high pressure to be applied to one side of the rotor lobes 72 and low pressure to be applied to the other side. These forces urge the rotor lobes 72 into positions directly below the stator lobes 71, thereby aligning stator and rotor ports to provide the greatest passageway for flow of fluid through the modulator 32.
Example stator and rotator dimensions for a modulator, configured as shown in FIGS. 3a-5c, that exhibits stable open performance are give below. Thses dimensions give an underlap between rotor and stator of 1/8" and gave satisfactory performance at a rotor-stator spacing of 1/16". Dimensions are identified with reference to FIG. 6.
______________________________________ Stator 40 Number of Lobes = 6 Outside Diameter = 41/2" Depth = 5/8" Width W1 = 15/16" Width W2 = 15/16" Thickness = 1" Hub Diameter = 21/4" Port Spacing P1 = 5/8" P2 = 5/8" P3 = 15/16" P4 = 15/16" Rotor 41 Number of Lobes = 6 Outside Diameter = 4 15/32" Depth = 19/32" Width W3 = 13/16" Width W4 = 11/8" Thickness = 5/8" Hub Diameter = 21/4" Taper = 12° Port Spacing P5 = 5/8" P6 = 3/8" P7 = 1" P8 = 11/16"______________________________________
It is pointed out that stable open performance is achieved only for the fluid flow direction shown in FIG. 3a. For fluid flow in the opposite direction, modulator 32 will exhibit the stable closed performance of prior art devices. For a freely rotatable shaft 60 (not driven and not prevented from rotating), modulator 32 will thus act in the manner of a check valve, opening in response to fluid flow in one direction and closing in response to fluid flow in the other direction.
Other embodiments of stable open modulators 32 can be constructed following the same principles applied above.
In general, the stator should be located upstream of the rotor. Stator lobes should preferably have straight (untapered) radially-extending sides and be dimensioned so that lobes and intervening ports have approximately the same size. The rotor thickness (FIG. 6) should prefrably be equal to or less than the thickness of the stator. The sides of the rotor lobes should be outwardly tapered in the downstream direction, with a positive taper preferably of 8° to 30°. Underlap should be provided between the top of the rotor lobes and the base of the stator lobes (i.e. the area of the top of the rotor lobes should be smaller than the area of the base of the stator lobes). The amount of underlap needed will depend on the rotor thickness and taper. The thinner the rotor, the less underlap will be required. Rotor-stator spacing should not be too small. Suitable spacing can be determined empirically. Smaller spacings give stronger signals; larger spacings give better stable open performance.
A second embodiment of the modulator 32, constructed in accordance with the foregoing criteria, comprises a stator 85 and a rotor 86 as illustrated in FIGS. 7a and 7b. The stator 85 has five lobes 87 evenly spaced about the periphery of a central stator hub. Example stastor and rotor dimensions for a stable open modulator, configured as shown in FIGS. 7a and 7b for operation with a rotor-stator spacing of 3/32", are given below:
______________________________________ Stator 85 Number of Lobes = 5 Outside Diameter = 43/8" Depth = 3/4" Width W1 = 1 13/32" Width W2 = 1 13/32" Thickness = 11/4" Hub Diameter = 2 13/16" Port Spacing P1 = 13/16" P2 = 13/16" P3 = 1 9/32" P4 = 1 9/32" Rotor 86 Number of Lobes = 5 Outside Diameter = 4 11/32" Depth = 3/4" Width W3 = 1 15/32" Width W4 = 17/8" Thickness = 13/32" Hub Diameter = 2 13/16" Taper = 30° Port Spacing P5 = 15/16" P6 = 17/32" P7 = 1 3/16" P8 = 3/4"______________________________________
Radial lines drawn through the centers of adjacent lobes 87 make angles of 72° with each other. The opposite sides of each lobe 87 are angled at 36° and the facing sides of adjacent lobes 87 are also angled at 36°. The stator is thus symmetrical, with the size of its lobes being the same as the size of its ports.
The rotor 86 is located downstream of the stator 85 and likewise has five lobes 88 evenly spaced about a central hub. The sides of the lobes 88 are outwardly tapered in the downstream direction with a positive taper of 30°. The outside width W3 of each rotor top is slightly greater than the outside width W2 of each stator lobe base (see end view FIG. 7b). Underlap is provided between the stator lobes 87 and the rotor lobes 88 by providing a greater angle of convergence for the top edges of the sides of the rotor lobes 88 than for the bottom edges of the sides of the stator lobes 87. As shown in FIG. 7a, the lower edges 89 of the sides of each rotor lobe 85 are angled at 52° and radiate outwardly from a point on the center axis of the rotor hub. The upper edges 90 and 91 of the sides of each rotor lobe 86, also angled at 52°, radiate from a point along the lobe centerline displaced from the hub axis. Consequently, the rotor lobe top has a smaller surface area than that of the base of the stator lobe 85. Although the underlap at the adjacent edges of the ends of the rotor and stator lobes is slightly negative (W2-W3=-1/16" in the example given above), the underlap increases rapidly with lobe depth toward the hub.
FIG. 8 illustrates another embodiment of the present invention that comprises a stator 100 positioned upstream of a rotor 101. The stator 100 has six lobes and is similar to the stator 40, previously described with reference to FIGS. 4a and 4b. The sizes of the stator lobes 102 and intervening stator ports are the same, with the widths W1, W2, P3 and P4 all being equal (see FIG. 6). The rotor 101 is designed so that the outside width W4 of the base of each lobe 103 is equal to the outside width P8 of the outlet of each port. The relationship between stator 100 and rotor 101 dimensions is such that W1=W2=W4=P3=P4=P8. This configuration, wherein stator port inlet and outlet openings and rotor port outlet openings have the same sizes, minimizes interference of the rotor taper with the fluid flow when the modulator is in its open position. This has the advantage of reduced wear and erosion of the rotor lobes 103.
To improve the acoustic signal, rotor thickness can be reduced by milling the top of the rotor. This, however, reduces the underlap between the tops of the rotor lobes 103 and the bases of the stator lobes 102. To assure stable open performance, a region 104 of increased taper is provided by cuts made on an inside part (adjacent the rotor hub 105) of the upstream edges of the sides of the lobes 103. These partial cuts 104 assist the tapered sides to establish the fluid dynamic forces that provide the stable open characteristic of the modulator 32.
FIG. 9 shows a modification of the partial cut construction of the rotor 101 of FIG. 8. The rotor 106 of FIG. 9 differs from the rotor 101 of FIG. 8 in that the outside widths W2, W4 and P4, P8 are not equal. The sides of each rotor lobe 107 each have a positive taper of approximately 12° and each lobe 107 is provided with partial cuts 108 of increased taper similar to the cuts 104 of rotor 101.
Further modifications to the foregoing embodiments can be made to provide a modulator that not only exhibits the desirable stable open characteristic, but will also exhibit a fluid flow induced agitation to dislodge debris caught between the rotor and the stator. Such a modification is illustrated in FIGS. 10a and 10b in which a modulator 32 comprises a stator 110 and a rotor 113 mounted within a housing 42. The stator 110 is like the six-lobed stator 40 previously described. The sides of its lobes 111 are untapered and are generally radial with respect to the stator hub axis. The sides of the lobes 111 of the rotor 113, however, although including a central outwardly tapered region similar to that of previously described embodiments, also have leading and trailing untapered regions 115, 116 which are parallel to the sides of the stator lobes 111 (see unwrapped view of FIG. 10b.) The outer width W3 (FIG. 6) of the top of the rotor lobe 114 that abuts the leading untapered region 115 is less than the outer width W2 of the base of the stator lobe 111, thus providing underlap. The outer width W4 of the base of the rotor lobe 114 that abuts the trailing untapered region 116 is approximately the same as the outer width W3 of the top. The trailing untapered region 116 of each rotor lobe side is formed by undercutting the tapered region across the full depth of the rotor lobe 114. The edges between the rotor lobe top and the leading regions 115 of the rotor lobe sides are preferably sharp in order to assert a cutting action on debris lodged in the gap between the stator and the rotor.
The configuration of FIGS. 10a and 10b generates fluid dynamic forces in response to the drilling fluid through direct impact and vortex separation that act on the rotor 113 to urge the modulator into a stable open position. However, the restoring forces in the azimuthal direction are proportional to the angular displacement, with the result that a periodic motion in the nature of aerodynamic flutter is set up when the rotor is not driven by the shaft. The amplitude and frequency of the flutter depend on the fluid flow rate, the modulator configuration and the shaft inertia. This flutter causes the rotor lobes 114 to oscillate between partially closed and fully open positions, also generating an acoustic signal whose frequency depends upon the flutter rate. Since flutter rate is a function of flow rate, the modulator construction of FIGS. 10a and 10b can be employed for flow rate monitoring, with the frequency of the generated signal being monitored in a known way, such as by conventional frequency analyzing circuitry incorporated into the signal detector 36 (FIG. 1).
While particular embodiments of the present invention have been shown and described by way of example, it will be apparent to those skilled in the art to which the invention relates that further changes and modifications may be made without departing from the invention and its broader aspects and, therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the spirit and scope of this invention. | An improved acoustic signal generator has rotor and stator elements, each having a plurality of radially-extending lobes and intervening ports relatively positioned and configured to establish fluid dynamic forces that bias the generator into an open position, thereby imparting a "stable open" characteristic to the generator. The rotor is located downstream of the stator, and rotor lobes are outwardly tapered in the downstream direction and have underlap relative to the upstream stator lobes. The invention is especially suited for use in oil industry MWD operations to communicate downhole measurement data to a well surface during drilling. In one embodiment, undercuts on the rotor lobes impart a flutter action which clears debris. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority to Japanese Patent Application No. 2005-098439, filed on Mar. 30, 2005, the contents of which are hereby incorporated by reference into the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a technique for forming print data utilized by an ink jet printer. The ink jet printer of the present specification includes all devices for printing onto a print medium by means of discharging ink (printers, copiers, fax machines, multifunctional products, etc.).
2. Description of the Related Art
Ink jet printers print onto a print medium by means of discharging ink The manner in which printing is performed by an ink jet printer will be described with reference to FIG. 18 . An ink jet printer 151 has an ink jet head 152 that moves with respect to a print medium 150 . In FIG. 18 , the ink jet head 152 moves in a Y direction with respect to the print medium 150 . The ink jet head 152 passes a front side of the print medium 150 . The ink jet head 152 has a plurality of nozzles 153 ˜ 157 . The nozzles 153 ˜ 157 are aligned in an X direction that is orthogonal to the Y direction. The nozzles 153 ˜ 157 can discharge ink droplets in the direction perpendicular to the page.
The ink droplets are discharged from the nozzles 153 ˜ 157 while the ink jet head 152 is moving with respect to the print medium 150 . One dot is formed on the print medium 150 by discharging one or a plurality of ink droplets from one nozzle. In FIG. 18 , 35 dots have been formed on the print medium 150 . The dots aligned in the Y direction have been formed by one nozzle. For example, a dot line D 1 has been formed by continuously discharging ink droplets from the nozzle 153 . Similarly, a dot line D 2 has been formed by the nozzle 154 , a dot line D 3 has been formed by the nozzle 155 , a dot line D 4 has been formed by the nozzle 156 , and a dot line D 5 has been formed by the nozzle 157 .
The nozzles 153 ˜ 157 might not be equidistant in the X direction. In the example of FIG. 18 , the nozzle 155 is slightly displaced toward the right. In this case, the dot line D 3 is formed slightly displaced toward the right The dot line D 2 and the dot line D 3 barely overlap, and there is a large overlap of the dot line D 3 and the dot line D 4 . In this case, ink density between the dot line D 2 and the dot line D 3 is much less than in other portions. The region in which the ink density is smaller extends continuously in the Y direction. Further, the ink density between the dot line D 3 and the dot line D 4 is much greater than in other portions. The region in which the ink density is greater extends continuously in the Y direction. When the region in which the ink density is smaller or greater extends continuously in the Y direction, a user can perceive a striped pattern that extends in the Y direction. Printing results are thus unsatisfactory.
The technique set forth in Japanese Patent Application Publication No. 2004/345167 will be described with reference to FIG. 19 . An ink jet head 202 of an ink jet printer 201 has a plurality of nozzle units 203 ˜ 207 . The nozzle unit 203 has a pair of nozzles 203 a and 203 b that are aligned in a direction (a Y direction) in which the ink jet head 202 moves with respect to a print medium 200 . The other nozzle units 204 ˜ 207 each have a configuration similar to the configuration of the nozzle unit 203 . That is, the nozzle units 204 ˜ 207 have nozzles 204 a ˜ 207 a and nozzles 204 b ˜ 207 b . The nozzles 203 a ˜ 207 a and nozzles 203 b ˜ 207 b can discharge the same color ink.
The nozzle unit 203 can form one dot on the print medium by discharging ink droplets from either of the nozzles 203 a and 203 b . The other nozzle units 204 ˜ 207 can also form one dot on the print medium by discharging ink droplets from either of the nozzles.
With the technique of FIG. 19 , an external device (for example, a PC) connected with the ink jet printer 201 selects one nozzle at random from the nozzles of the nozzle unit which corresponds to the position at which the dot is to be formed.
For example, if the position at which a dot is to be formed is P 11 , one nozzle (the nozzle 203 a or the nozzle 203 b ) is selected at random from the nozzle unit 203 that corresponds to P 11 . In the case where the external device has selected the nozzle 203 a , the external device creates information including the combination of P 11 and the nozzle 203 a.
As another example, if the position at which a dot is to be formed is P 12 , one nozzle is selected at random out of the nozzles 203 a and 203 b . In the case where the external device has selected the nozzle 203 b , the external device creates information including the combination of P 12 and the nozzle 203 b.
As another example, if the position at which a dot is to be formed is P 21 , one nozzle (the nozzle 204 a or the nozzle 204 b ) is selected at random from the nozzle unit 204 that corresponds to P 21 . In the case where the external device has selected the nozzle 204 b , the external device creates information including the combination of P 21 and the nozzle 204 b.
The external device creates data that includes a plurality of combinations of position and nozzle. Below, this data will be termed print data. The external device outputs the print data to the ink jet printer 201 . The ink jet printer 201 discharges ink from the nozzles based on the print data. For example, in the case where print data has been obtained having the combination of P 11 and the nozzle 203 a , the ink jet printer 201 discharges ink from the nozzle 203 a toward P 11 . As another example, in the case where print data has been obtained having the combination of P 12 and the nozzle 203 b , the ink jet printer 201 discharges ink from the nozzle 203 b toward P 12 . As another example, in the case where print data has been obtained having the combination of P 21 and the nozzle 204 b , the ink jet printer 201 discharges ink from the nozzle 204 b toward P 21 .
In FIG. 19 , hatching has been applied to the dots formed by the nozzles 203 a ˜ 207 a Hatching has not been applied to the dots formed by the nozzles 203 b ˜ 207 b.
In the nozzle line D 3 of FIG. 19 , the dots formed by the nozzle 205 a are displaced toward the right. The dots formed by the nozzle 205 b are not displaced. The dots of the other nozzle lines D 1 , D 2 , D 4 , and D 5 are also not displaced.
With this technique, if the nozzle 205 a is not aligned equidistantly in the X direction, the dot line D 3 will not be formed only by the nozzle 205 a , but will instead be formed by both the nozzle 205 a and the nozzle 205 b . As a result, some dots in the dot line D 3 are not displaced. With this technique, it may be possible to prevent in which the ink density is much greater or smaller from continuing across a wide range. Better printing results can be obtained with this technique than with the conventional technique described using FIG. 18 .
BRIEF SUMMARY OF THE INVENTION
In the conventional technique described using FIG. 19 , one nozzle is selected at random from among the plurality of nozzles for the position where the dot is to be formed. In this case, there is a possibility that the same nozzle will be selected continuously for a large number of positions continuously aligned along the Y direction. With this technique, therefore, it is not possible to completely eliminate the phenomenon wherein regions in which the ink density is much greater or smaller continue across a wide range There is a possibility that satisfactory printing results cannot be obtained.
The present invention has been created taking the above conditions into consideration. The present invention teaches a technique that allows better printing results to be obtained than the conventional technique.
The present invention relates to a technique for creating print data utilized by an ink jet printer. The print data creating technique of the present invention will be described using FIG. 1 .
In the present invention, print data is created that is utilized by an ink jet printer 301 provided with the following conditions.
(1) The ink jet printer 301 has an ink jet head 302 that moves along a predetermined direction (a Y direction in FIG. 1 ) with respect to a print medium 300 .
(2) The ink jet head 302 has a plurality of nozzle units 303 ˜ 307 .
(3) The nozzle units 303 ˜ 307 each have at least two nozzles aligned in the aforementioned predetermined direction. For example, the nozzle unit 303 has nozzles 303 a and 303 b . The other nozzle units 304 ˜ 307 each have at least two nozzles 304 a ˜ 307 a and 304 b ˜ 307 b.
(4) The nozzles 303 a ˜ 307 a and 303 b ˜ 307 b can discharge the same color ink.
(5) Each nozzle unit 303 ˜ 307 can create a dot on the print medium 300 by discharging ink from one nozzle (for example 303 a ) selected out of the nozzles (for example, 303 a and 303 b ) of the nozzle unit (for example, 303 ).
A computer program product for creating print data is taught in the present invention. This computer program product includes instructions for ordering a computer to perform a reading step and a print data creating step.
In the reading step, image data including a plurality of first combinations is read. Each of the first combinations includes a position and information hereafter termed dot information) concerning whether a dot is to be formed at the position. For example, 35 positions P 11 , P 12 , P 13 , etc. are shown in FIG. 1 . In the case of FIG. 1 , the image data including the 35 first combinations are read in the reading step. Further, in this example, dots are to be formed at all positions except for P 13 .
In the print data creating step, print data is created by creating a second combination for each position at which the dot is to be formed. In the example of FIG. 1 , the second combinations are created for the positions P 11 , P 12 , etc. Since P 13 is a position at which a dot is not to be formed, a second combination is not created for P 13 . Each of the second combinations includes the position at which the dot is to be formed, and one nozzle randomly selected from the nozzles of the nozzle unit corresponding to the position. For example, the second combination for P 11 is a combination including P 11 and one nozzle ( 303 a or 303 b ) randomly selected from the nozzles 303 a and 303 b of the nozzle unit 303 corresponding to P 11 . Further, the second combination for P 21 is a combination including P 21 and one nozzle ( 304 a or 304 b ) randomly selected from the nozzles 304 a and 304 b of the nozzle unit 304 corresponding to P 21 .
Moreover, in the print data creating step, it is prohibited to select the same nozzle for more than a predetermined number of positions continuously aligned along the predetermined direction (the Y direction). For example, if the predetermined number is two, the same nozzle cannot be selected for three or more positions aligned continuously along the Y direction. In this case, for example, the same nozzle (for example 303 a ) cannot be selected for P 14 , P 15 , and P 16 .
The print data created by the present invention is utilized by the ink jet printer 301 . When the ink jet printer 301 obtains, for example, the second combination of P 11 and the nozzle 303 a , the ink jet printer 301 causes ink to be discharged from the nozzle 303 a towards P 11 , and a dot is thus formed. In FIG. 1 ( c ), 34 dots formed by the ink jet printer 301 are shown. A dot is not formed at the position corresponding to P 13 . This is because P 13 is not a position where a dot is to be formed in this example.
In FIG. 1 ( c ), hatching has been applied to the dots formed by the nozzles 303 a 307 a Hatching has not been applied to dots formed by the nozzles 303 b ˜ 307 b.
Dots formed by the nozzle 305 a are displaced toward the right in a nozzle line D 3 . The dots formed by the nozzle 305 b are not displaced. The dots of the other nozzle lines D 1 , D 2 , D 4 , and D 5 are also not displaced
With this technique, if the nozzle 305 a is not aligned equidistantly in the X direction, the dot line D 3 will be formed by both the nozzle 305 a and the nozzle 305 b . As a result, displacement of all of the dots in the dot line D 3 is prevented. Moreover, in the print data creating step, the same nozzle cannot be selected for more than a predetermined number of positions aligned continuously along the Y direction. As a result dots cannot be formed by the same nozzle for more than the predetermined number of positions aligned continuously along the Y direction. With this technique, it is possible to completely eliminate the phenomenon wherein regions in which the ink density is much greater or smaller continue across a wide range. With the present invention, it is possible to create print data that allows better printing results than the conventional technique.
The content of FIG. 1 and the description based thereon is an example, and a scope of the present invention is not restricted based on FIG. 1 or the above content. The scope of the present invention is determined objectively based on the teachings of the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a figure for describing the content of the present invention. FIG. 1 ( a ) shows a plan view of a portion of an ink jet head. FIG. 1 ( b ) shows positions on printing paper FIG. 1 ( c ) shows an example of a dot pattern formed on the printing paper.
FIG. 2 is a simple view of a printing system of an embodiment.
FIG. 3 is a simple plan view of an ink jet head.
FIG. 4 is an enlarged view of a part of the ink jet head.
FIG. 5 is a view in the V direction of FIG. 3 . FIG. 5 is a figure for describing how ink is discharged from two nozzle lines.
FIG. 6 shows three dots with differing sizes.
FIG. 7 shows a block view of a PC and a printer.
FIG. 8 shows a one row data storage.
FIG. 9 shows count value storages.
FIG. 10 shows buffer areas.
FIG. 11 shows functions realized by the PC.
FIG. 12 shows a flowchart of printing processes executed by the PC.
FIG. 13 shows an example of image data
FIG. 14 shows a flowchart of a print data creating process.
FIG. 15 shows the flowchart of the print data creating process (continued from FIG. 14 ).
FIG. 16 shows the buffer areas in which selected nozzle information has been written.
FIG. 17 shows a satisfactory dot pattern, and two types of unsatisfactory dot pattern.
FIG. 18 shows a figure for describing the conventional technique.
FIG. 19 shows a figure for describing the conventional technique.
DETAILED DESCRIPTION OF THE INVENTION
Embodiment
An embodiment of the present invention will be described with reference to figures. FIG. 2 is a simple view of a printing system 10 of the present embodiment. The printing system 10 has a PC 20 and an ink jet printer 30 . Below, the ink jet printer 30 may be simply referred to as ‘printer 30 ’. The PC 20 and the printer 30 are connected so as to be capable of communication via a communication cable 50 .
The PC 20 has a keyboard 62 a , a mouse 62 b , a display 64 , etc. A user can utilize the keyboard 62 a and the mouse 62 b to command the PC 20 to print content displayed on the display 64 . In this case, the PC 20 creates print data, and outputs the print data that has been created to the printer 30 .
The printer 30 inputs the print data that was output from the PC 20 . The printer 30 has an ink jet head 32 (shown in FIG. 3 ) capable of discharging ink. The printer 30 discharges ink from the ink jet head 32 towards printing paper 12 (shown in FIG. 3 ) in accordance with the content of the print data. Letters or images are thus printed on the printing paper 12 based on the content of the print data.
FIG. 3 is a plan view of the ink jet head 32 . The printer 30 has a transferring device 104 (shown in FIG. 7 ) for transporting the printing paper 12 in the direction of the arrow YP. That is, the ink jet head 32 moves in the direction of the arrow Y with respect to the printing paper 12 . The printing paper 12 passes a back side of the ink jet head 32 perpendicular to the plane of FIG. 3 .
The ink jet head 32 has two nozzle lines 34 a and 34 b . The nozzle lines 34 a and 34 b includes a plurality of nozzles 34 . In FIG. 3 , not all of the nozzles 34 have numbers applied thereto. The nozzle lines 34 a and 34 b extend in an X direction. The X direction is a direction perpendicular to the Y direction. The length of the X direction of the nozzle lines 34 a and 34 b is approximately the same as the width in the X direction of the printing paper 12 . The nozzles 34 can discharge ink of the same color (black, for example) in the direction perpendicular to the plane of FIG. 3 .
The ink jet head 32 discharges ink while the printing paper 12 is being transported. A hatched region 12 a of the printing paper 12 is a region that has been printed by the ink jet head 32 . A region 12 b of the printing paper 12 that has not been hatched is a region that has not yet been printed by the ink jet head 32 .
In the present embodiment, the ink jet head 32 is fixed to a printer main body (not shown). That is, the printer 30 is a line type printer.
FIG. 4 is an enlarged view of a part of the ink jet head 32 . In the present embodiment, a pair of nozzles aligned in the Y direction will be termed a nozzle unit. Five nozzle units 34 - 1 ˜ 34 - 5 are shown in FIG. 4 . In fact, more nozzle units are formed in the ink jet head 32 . The nozzle units 34 - 1 ˜ 34 - 5 are offset in the X direction.
The nozzle unit 34 - 1 has a pair of nozzles 34 a - 1 and 34 b - 1 aligned in the Y direction. Similarly, the other nozzle units 34 - 2 ˜ 34 - 5 each also have a pair of nozzles ( 34 a - 2 ˜ 34 a - 5 , 34 b - 2 ˜ 34 b - 5 ) aligned in the Y direction. Two adjacent nozzle units (for example, 34 - 1 and 34 - 2 ) are separated by a predetermined pitch P.
FIG. 5 is a view of the ink jet head 32 in the V direction of FIG. 3 . The nozzles (for example 34 a - 1 ) of the nozzle line 34 a discharge ink in an oblique direction towards the nozzle line 34 b . The nozzles (for example 34 b - 1 ) of the nozzle line 34 b discharge ink in a vertical direction If the pair of nozzles (for example, 34 a - 1 and 34 b - 1 ) of one nozzle unit (for example, 34 - 1 ) discharge ink with the same timing, the ink adheres to the same position. Each of the nozzle units (for example, 34 - 1 ) can form one dot by discharging ink from either nozzle (for example, 34 a - 1 or 34 b - 1 ).
One nozzle unit (for example, 34 - 1 ) forms one dot line (for example, D 1 in FIG. 1 ). One dot line includes a plurality of dots aligned in the Y direction.
Further, the ink jet printer 30 can vary the quantity of ink for forming one dot. A large dot is formed when the ink quantity is large. A small dot is formed when the ink quantity is small. A medium dot is formed when the ink quantity is medium. FIG. 6 shows three dots with differing sizes. Each nozzle can form large dots, medium dots, and small dots. As a result, the printer 30 of the present embodiment can describe four gradations (large dot, medium dot, small dot, and no dot).
FIG. 7 shows a block view of the PC 20 and the printer 30 . First, the configuration of the PC 20 will be described.
The PC 20 has a CPU 60 , an inputting device 62 , the display 64 , an interface (IF) 66 , a RAM 68 , a ROM 84 , a hard disc 86 , etc. Each of the devices 60 , 62 , etc. are connected so as to be capable of communication by a bus line 92 .
The CPU 60 reads and executes a printer driver 88 stored in the hard disc 86 .
The inputting device 62 includes the keyboard 62 a and the mouse 62 b shown in FIG. 2 . The user can input information utilizing the inputting device 62 . For example, the user can input information for causing the printer 30 to print content displayed by the display 64 .
The display 64 can display information created by various applications.
The IF 66 is connected with an IF 102 of the printer 30 . The IF 66 outputs the print data to the printer 30 .
The RAM 68 has a work area 70 , a one row data storage 72 , a pixel data storage 74 , a first count value storage 76 a , a second count value storage 76 b , a first buffer area 80 a , a second buffer area 80 b , etc.
The work area 70 is a storage utilized when the printer driver 88 is being executed.
The storages 72 , 74 , 76 a , 76 b , 80 a , and 80 b are storages utilized in a print data creating process (to be described).
FIG. 8 shows the one row data storage 72 . The one row data storage 72 has a plurality of cells 72 - 1 ˜ 72 - n (n being a positive integer). The one row data storage 72 stores gradation values of one row's worth of data (one row data) included in image data. Each cell can store any of the values 0, 1, 2, 3. The number of cells corresponds to the resolution of the printer 30 in the X direction (see FIG. 3 , etc.). That is, the number of cells is the same as the number of nozzle units. One cell 72 - n corresponds to one nozzle unit 34 - n . For example, the cell 72 - 1 corresponds to the nozzle unit 34 - 1 . As another example, the cell 72 - 5 corresponds to the nozzle unit 34 - 5 . The manner in which the one row data storage 72 is utilized will be described in detail later.
The pixel data storage 74 shown in FIG. 7 stores data for one cell (pixel) included in the one row data. The manner in which the pixel data storage 74 is utilized wilt be described in detail later.
FIG. 9 shows the first count value storage 76 a and the second count value storage 76 b . The first count value storage 76 a has a plurality of cells 76 a - 1 ˜ 76 a - n . The number of cells of the first count value storage 76 a corresponds to the resolution of the printer 30 in the X direction. The cell 76 a - n corresponds to the nozzle 34 a - n . The first count value storage 76 a stores a count value for each of the nozzles 34 a - 1 ˜ 34 a - n included in the nozzle line 34 a . The cell 76 a - n stores a count value of the corresponding nozzle 34 a - n . The count value will be described in detail later. Each cell of the first count value storage 76 a can store any of the values 0, 1, 2.
The second count value storage 76 b has a plurality of cells 76 b - 1 ˜ 76 b - n . The number of cells of the second count value storage 76 b corresponds to the resolution of the printer 30 in the X direction. The cell 76 b - n corresponds to the nozzle 34 b - n . The second count value storage 76 b stores a count value for each of the nozzles 34 b - 1 ˜ 34 b - n included in the nozzle line 34 b (see FIG. 4 , etc.). The cell 76 b - n stores a count value of the corresponding nozzle 34 b - n . Each cell of the second count value storage 76 b can store any of the values 0, 1, 2.
FIG. 10 shows the first buffer area 80 a and the second buffer area 80 b . The first buffer area 80 a has a plurality of cells 80 a - 1 ˜ 80 a - n . The number of cells of the first buffer area 80 a corresponds to the resolution of the printer 30 in the X direction. The cell 80 a - n corresponds to the nozzle 34 a - n . Each cell of the first buffer area 80 a can store any of the values 0, 1, 2, 3.
The second buffer area 80 b has a plurality of cells 80 b - 1 ˜ 80 b - n . The number of cells of the second buffer area 80 b corresponds to the resolution of the printer 30 in the X direction. The cell 80 b - n corresponds to the nozzle 34 b - n . Each cell of the second buffer area 80 b can store any of the values 0, 1, 2, 3.
Although this will be described in detail later, the content of the first row data is sorted into the first buffer area 80 a or the second buffer area 80 b.
The ROM 84 of FIG. 7 stores programs for controlling the CPU 60 .
The hard disc 86 stores the printer driver 88 . The user installs media included as an auxiliary component of the printer 30 on the PC 20 . A program causing the PC 20 to execute processes (to be described: see FIGS. 12 , 14 , 15 ) is stored in the media. When this program has been installed on the PC 20 , the printer driver 88 can function. The processes to be described are executed by the printer driver 88 . The hard disc 86 also stores image data 90 . The user can input information to the inputting device 62 so that the image data 90 is printed by the printer 30 .
The PC 20 realizes various functions by means of the above devices 60 ˜ 86 . FIG. 11 shows an example of functions realized by the PC 20 . The PC 20 has a reading device 120 , a selected nozzle information creating device (a print data creating device) 122 , a counter 124 , and an outputting device 126 .
The reading device 120 reads the image data 90 . The reading device 120 functions when the processes of FIG. 14 and FIG. 15 (to be described) are to be executed. The reading device 120 is realized by the functioning of the CPU 60 , the one row data storage 72 , etc.
The selected nozzle information creating device 122 creates selected nozzle information (print data). The selected nozzle information creating device 122 functions when the processes of FIG. 14 and FIG. 15 (to be described) are to be executed. Else selected nozzle information creating device 122 is realized by the functioning of the CPU 60 , the RAM 68 , the ROM 84 , the printer driver 88 , etc.
The counter 124 stores count values of nozzle units 34 , etc. The counter 124 functions when the process of FIG. 14 and FIG. 15 (to be described) are to be executed. The counter 124 is realized by the functioning of the CPU 60 , the count value storages 76 a and 76 b , etc.
The outputting device 126 outputs the selected nozzle information (the print data) that has been created to the printer 30 . The outputting device 126 functions when the processes of FIG. 14 and FIG. 15 (to be described) are to be executed. The outputting device 126 is realized by the functioning of the CPU 60 , the IF 66 , etc.
Next, the configuration of the printer 30 will be described.
The printer 30 has a CPU 100 , the IF 102 , the transferring device 104 , a RAM 106 , the ink jet head 32 , etc. The devices 100 , 102 , etc. are connected so as to be capable of communication by a bus line 112 .
The CPU 100 controls the transferring device 104 and the ink jet head 32 based on commands from the PC 20 .
The IF 102 is connected with the IF 66 of the PC 20 . The IF 102 inputs print data sent from the PC 20 .
The transferring device 104 moves the printing paper 12 (see FIG. 3 ) in the direction of the arrow YP.
The ink jet head 32 prints the printing paper 12 by discharging ink.
The RAM 106 has a work area 108 for operating the CPU 100 .
In the present embodiment, the hardware configuration of the ink jet printer 30 is explained in an extremely simple manner. The configuration of the ink jet printer 30 is taught in, for example, U.S. patent application Ser. No. 11/281,463 and 11/285,291. The contents of U.S. Ser. No. 11/281,463 and U.S. Ser. No. 11/285,291 may be incorporated by reference into the present application.
Next, the processes executed by the PC 20 will be described with reference to the flowchart of FIG. 12 . FIG. 12 shows a flowchart showing the processes executed by the PC 20 . The processes of FIG. 12 are executed by the CPU 60 (see FIG. 7 ) utilizing the printer driver 88 .
The user can use the inputting device 62 (see FIG. 7 ) to command the image data 90 being stored in the hard disc 86 to be printed. In this case, the CPU 60 activates the printer driver 88 , and executes a rasterizing process (S 801 ).
The image data 90 prior to the execution of the rasterizing process is displayed in a vector format. In the rasterizing process, the image data 90 in the vector format is converted to data in a bit mapped format. The image data 90 is converted to data that conforms with the resolution of the printer 30 . The image data 90 in the bit mapped format contains information for a plurality of pixels. One pixel is represented by data having the combination of the position (coordinate on the printing paper) and the gradation at that position In the image data 90 in the bit mapped format, one pixel is represented by 256 gradations (8 bits) or 6553 gradations (16 bits). The image data 90 after the rasterizing process is stored in the work area 70 of the RAM 68 .
Next, the CPU 60 executes a color adjustment process (S 802 ). In the color adjustment process, the colors for the image data 90 are corrected. Further, ROB data is converted into CMYK data. The image data 90 after the color adjustment process is stored in the work area 70 of the RAM 68 . The image data 90 prior to the color adjustment process is erased from the RAM 68 .
The CPU 60 executes a halftone process (S 803 ). As described above, with the image data 90 after the rasterizing process, one pixel is represented by 256 gradations or 6553 gradations. By contrast, the printer 30 of the present embodiment can only represent four gradations (large dot, medium dot, small dot, and no dot) for one pixel (i.e. for one position). In the halftone process, the image data 90 in the bit mapped format is converted into data having four gradations for one pixel. The error diffusion method or the dither method is utilized in the halftone process. Since these methods are known, they will not be described in detail here. The image data 90 after the halftone process is stored in the work area 70 of the RAM 68 . The image data 90 prior to the halftone process is erased from the RAM 68 .
FIG. 13 shows an example of the image data 90 after the halftone process. The image data 90 has a plurality of pixels C 1 ˜C 5 etc. The number of pixels aligned in the X direction is the same as the resolution of the printer 30 in the X direction. That is, the number of pixels aligned in the X direction is the same as the number of nozzle units of the ink jet head 32 . The X direction is a direction orthogonal to the direction in which the printing paper 12 is transported. The number of pixels aligned in the Y direction is the same as the resolution of the printer 30 in the Y direction. The Y direction is the direction in which the printing paper 12 is transported. X and Y in FIG. 13 correspond to X and Y in FIG. 3 , etc.
Below, the position of one pixel of the image data 90 is represented as a two dimensional coordinate. For example, the position of the pixel C 1 is represented as (1,1). The position of the pixel C 2 is represented as (2,1).
Each pixel stores one out of the gradation values 0, 1, 2, 3. The gradation value 0 corresponds to ‘no dot.’ The gradation value 1 corresponds to ‘small dot.’ The gradation value 2 corresponds to ‘medium dot.’ The gradation value 3 corresponds to ‘large dot.’
The pixel C 1 has a gradation value 0. As a result, the pixel C 1 is data having a combination of (1,1) and the gradation value 0. With the pixel C 1 , no dot is to be formed at the coordinate (1,1) of the printing paper 12 . Further, the pixel C 2 is data having a combination of (2,1) and the gradation value 1. With the pixel C 2 , a small dot is to be formed at the coordinate (2,1) of the printing paper 12 .
Below, the plurality of pixels aligned in the X direction of the image data 90 is termed one row data. In FIG. 13 , five row's worth of one row data is shown.
When the CPU 60 has finished the halftone process, the CPU 60 executes the print data creating process (S 804 ). In the process of S 804 , print data that includes selected nozzle information is created.
FIGS. 14 and 15 show a flowchart of the print data creating process. The CPU 60 initializes the count value storages 76 a and 76 b (S 1001 ). In S 1001 , 0 is written into all of the cells 76 a - 1 ˜ 76 a - n (see FIG. 9 ) in the first count value storage 76 a . Further, 0 is written into all of the cells 76 b - 1 ˜ 76 b - n (see FIG. 9 ) in the second count value storage 76 b.
Next, the CPU 60 initializes the buffer areas 80 a and 80 b of the RAM 68 (S 1002 ). In S 1002 , 0 is written into all of the cells 80 a - 1 ˜ 80 a - n (see FIG. 10 ) in the first buffer area 80 a . Further, 0 is written into all of the cells 80 b - 1 ˜ 80 b - n (see FIG. 10 ) in the second buffer area 80 b.
Next, the CPU 60 reads the one row data (S 1003 ) of the image data 90 (being stored in the work area 70 of the RAM 68 ) after the halftone process (S 803 ). When the process of S 1003 is performed at the first time, a first row of one row data (C 1 ˜C 5 , etc. of FIG. 13 ) is read.
The one row data that has been read is written into the one row data storage 72 of the RAM 68 (see FIG. 7 ). The one row data storage 72 of FIG. 8 stores the first row of the one row data of the image data 90 of FIG. 13 . The one row data storage 72 stores the one row data in a state that maintains the sequence of the cells of the image data 90 . For example, the first row of the one row data of FIG. 13 has the gradation values aligned in the sequence, from left, 0, 1, 3, 1, 3. In this case, the one row data storage 72 also stores the gradation values in this sequence. In FIG. 8 , also, these are aligned in the sequence, from left, 0, 1, 3, 1, 3.
In the process of S 1003 , only one row's worth of the one row data is read. A plurality of row's worth of one row data is not read. When the following processes have been completed for one row's worth of the one row data, the next one row data is read. For example, when the processes have been completed for the first row of the one row data, the second row of the one row data is read. In S 1003 , the one row data is read in the sequence of alignment in the Y direction of the image data 90 .
Next, the CPU 60 reads the gradation value of one pixel (cell) from the one row data in the one row data storage 72 (S 1004 ). The gradation value that has been read is stored in the pixel data storage 74 of the RAM 68 .
One pixel is read in the process of S 1004 . A plurality of pixels is not read. When the following processes have been completed for one pixel, the next pixel is read. In S 1004 , the pixels are read in the sequence of alignment in the X direction of the one row data. For example, when the processes have been completed for the cell 72 - 1 of FIG. 8 , the cell 72 - 2 is then read. When the processes have been completed for the cell 72 - 2 , the cell 72 - 3 is then read.
The CPU determines whether the gradation value stored in the pixel data storage 74 is 0 (S 1005 ). If the gradation value is 0 (YES in S 1005 ), 0 is written (S 1006 ) in the count value storages 76 a and 76 b that correspond to the pixel read in S 1004 . For example, if the cell 72 - 1 of FIG. 8 is read in S 1004 , YES is determined in S 1005 . The cell 72 - 1 corresponds to the cells 76 a - 1 and 76 b - 1 of FIG. 9 . In S 1006 , 0 is written in both the cells 76 a - 1 and 76 b - 1 .
In S 1006 , nothing is written in the buffer areas 80 a and 80 b . The buffer areas 80 a and 80 b are initialized in S 1002 . As a result, the cells of the buffer areas 80 a and 80 b that correspond to the pixel read in S 1004 remain at 0. For example if the cell 72 - 1 of FIG. 8 is read in S 1004 , 80 a - 1 and 80 b - 1 of FIG. 10 remain at 0.
When S 1006 ends, the CPU 60 determines whether all the processes have been completed for all the pixels stored in the one row data storage 72 (S 1050 ). In the case where NO is determined, the process returns to S 1004 , and the CPU 60 reads the next pixel. For example, if the process for the cell 72 - 1 of FIG. 8 has been completed, the cell 72 - 2 is read.
However, if NO was determined in S 1005 , the process proceeds to S 1011 of FIG. 15 . For example, in the case where the cell 72 - 2 of FIG. 8 has been read in S 1004 , the gradation value of the cell 72 - 2 is 1, and consequently NO is determined in S 1005 . In this case, the processes after S 1011 are executed.
In S 1011 of FIG. 15 , the CPU 60 determines whether 2 is stored in the cell of the first count value storage 76 a that corresponds to the pixel read in S 1004 . That is, in the case where the cell 72 - n of FIG. 8 has been read in S 1004 , the value of the cell 76 a - n of FIG. 9 is checked in S 1011 . For example, if the cell 72 - 2 of FIG. 8 has been read in S 1004 , the value of the cell 76 a - 2 of FIG. 9 is checked in S 1011 .
If YES was determined in S 1011 , the CPU 60 writes the gradation value of the pixel read in S 1004 into the cell of the second buffer area 80 b that corresponds to this pixel (S 1012 ). That is, in the case where the gradation value of the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes that graduation value into the cell 80 b - n of FIG. 10 in S 1012 . For example, in the case where the cell 72 - 2 (gradation value 3) of FIG. 8 has been read in S 1004 , 1 is written into the cell 80 b - 2 of FIG. 10 in S 1012 .
When S 1012 has been completed, the process proceeds to S 1013 . The CPU 60 writes 0 in the cell of the first count value storage 76 a that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 0 in the cell 76 a - n of FIG. 9 in S 1013 . Further, the CPU 60 writes I in the cell of the second count value storage 76 b that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 1 in the cell 76 a - n of FIG. 9 in S 1013 .
When S 1013 has been completed, the process proceeds to S 1050 (see FIG. 14 ).
If NO was determined in S 1011 , the process proceeds to S 1014 . The CPU 60 determines whether 2 is stored in the cell of the second count value storage 76 b corresponding to the pixel read in S 1004 . That is, in the case where the cell 72 - n of FIG. 8 has been read in S 1004 , the value of the cell 76 b - n of FIG. 9 is checked in S 1014 .
If YES was determined, the CPU 60 writes the gradation value of the pixel read in S 1004 into the cell of the first buffer area 80 a that corresponds to this pixel (S 1015 ). That is, in the case where the gradation value of the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes that graduation value into the cell 80 a - n of FIG. 10 in S 1015 .
When S 1015 has been completed, the process proceeds to S 1016 . The CPU 60 writes 1 in the cell of the first count value storage 76 a that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 1 in the cell 76 a - n of FIG. 9 in S 1016 . Further, the CPU 60 writes 0 in the cell of the second count value storage 76 b that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 0 in the cell 76 b - n of FIG. 9 in S 1016 .
When S 1016 has been completed, the process proceeds to S 1050 (see FIG. 14 ).
If NO was determined in S 1014 , the CPU 60 randomly obtains either 1 or 2 (S 1021 ). The random number 1 or 2 is created in the work area 70 of the RAM 68 .
The CPU 60 checks whether the random number obtained in S 1021 is 1 (S 1022 ). If NO is determined (if the random number is 2), the CPU 60 writes the gradation value of the pixel read in S 1004 into the cell of the second buffer area 80 b that corresponds to this pixel (S 1031 ). That is, in the case where the gradation value of the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes that graduation value into the cell 80 b - n of FIG. 10 in S 1031 .
When S 1031 has been completed, the process proceeds to S 1032 . The CPU 60 writes 0 in the cell of the first count value storage 76 a that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 0 in the cell 76 a - n of FIG, 9 in S 1032 . Further, the CPU 60 adds 1 to the value of the cell of the second count value storage 76 b that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 adds 1 to the value of the cell 76 b - n of FIG. 9 in S 1032 . For example, if the value in the cell 76 b - n was 0, the value of the cell 76 b - n becomes 1. As another example, if the value in the cell 76 b - n was 1, the value of the cell 76 b - n becomes 2. Moreover, if the value in the cell 76 b - n was 2, YES was determined in S 1014 , and consequently the process would not have proceeded to S 1032 .
When S 1032 has been completed, the process proceeds to S 1050 (see FIG. 14 ).
If YES was determined in S 1022 (if the random number was 1), the CPU 60 writes the gradation value of the pixel read in S 1004 into the cell of the first buffer area 80 a that corresponds to his pixel (S 1041 ). That is, in the case where the gradation value of the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes that graduation value into the cell 80 a - n of FIG. 10 in S 1041 .
When S 1041 has been completed, the process proceeds to S 1042 . The CPU 60 adds 1 to the value of the cell of the first count value storage 76 a that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 adds 1 to the value of the cell 76 a - n of FIG. 9 in S 1042 . For example, if the value in the cell 76 a - n was 0, the value of the cell 76 a - n becomes 1. As another example, if the value in the cell 76 a - n was 1, the value of the cell 76 a - n becomes 2. Moreover, if the value in the cell 76 a - n was 2 , YES was determined in S 1011 , and consequently the process would not have proceeded to S 1042 . Further, the CPU 60 writes 0 in the cell of the second count value storage 76 b that corresponds to the pixel read in S 1004 . That is, if the cell 72 - n of FIG. 8 has been read in S 1004 , the CPU 60 writes 0 in the cell 76 b - n of FIG. 9 in S 1042 .
When S 1042 has been completed, the process proceeds to S 1050 (see FIG. 14 ).
In S 1050 of FIG. 14 , the CPU 60 determines whether the processes have been executed for all the pixels of the one row data. In the case where NO is determined, the process returns to S 1004 , and the next pixel is read.
In the case where YES is determined, the process proceeds to S 1051 . In S 1051 , the CPU 60 outputs the contents of the buffer areas 80 a and 80 b to the printer 30 . At the point when S 1051 is executed, the gradation values of all the pixels of the one row data have been sorted into either of the buffer areas 80 a and 80 b.
In the present embodiment, the content stored in the buffer areas 80 a and 80 b is termed the print data. FIG. 16 shows the print data corresponding to the one row data of FIG. 8 . Since the gradation value of the cell 72 - 1 of FIG. 8 is 0, the cells 80 a - 1 and 80 b - 1 of FIG. 16 both store 0. Further, the gradation value of the cell 72 - 2 of FIG. 8 is 1. The gradation value 1 of the cell 72 - 2 is sorted into either of the cells 80 a - 2 and 80 b - 2 . In the example of FIG. 16 , 1 is stored in the cell 80 a - 2 and 0 is stored in the cell 80 b - 2 . Further, the gradation value of the cell 72 - 3 of FIG. 8 is 3, the gradation value of the cell 72 - 4 is 1, and the gradation value of the cell 72 - 5 is 3. This information is also sorted into either of the buffer areas 80 a and 80 b . That is, in the example of FIG. 16 , the cell 80 b - 3 stores 3, the cell 80 b - 4 stores 1 , and the cell 80 a - 5 stores 3.
In S 1051 , the CPU 60 outputs one row's worth of the print data (the contents stored in the buffer areas 80 a and 80 b ) to the printer 30 . The manner in which the print data is utilized by the printer 30 will be described later.
After S 1051 has been completed, the CPU 60 determines whether the processes have been completed for all the one row data included in the image data 90 (S 1052 ). If NO is determined in S 1052 , the process returns to S 1002 and the processes for the next one row data are executed.
If YES is determined in S 1052 , the print data creating process ends.
Next, the process for executing the printer 30 will be described. The print data output from the PC 20 in the process of S 1051 is input to the printer 30 . The CPU 100 of the printer 30 controls the ink jet head 32 and the transferring device 104 (see FIG. 7 ) based on the input print data
The CPU 100 causes ink to be discharged from the nozzles 34 a - n in accordance with the content of the cells 80 a - n of FIG. 16 . For example, since the gradation value of the cell 80 a - 1 of FIG. 16 is 0, the CPU 100 does not cause ink to be discharged from the nozzle 34 a - 1 . As another example, since the gradation value of the cell 80 a - 2 is 1, the CPU 100 causes ink to be discharged from the nozzle 34 a - 2 . Here, a quantity of ink is discharged for forming a small dot. As another example, since the gradation value of the cell 80 a - 2 is 3, the CPU 100 causes ink to be discharged from the nozzle 34 a - 5 . Here, a quantity of ink is discharged for forming a large dot. Further, the CPU 100 causes ink to be discharged from the nozzles 34 b - n in accordance with the content of the cells 80 b - n of FIG. 16 . For example, since the gradation value of the cell 80 b - 1 of FIG. 16 is 0, the CPU 100 does not cause ink to be discharged from the nozzle 34 b - 1 . As another example, since the gradation value of the cell 80 b - 3 is 3, the CPU 100 causes ink to be discharged from the nozzle 34 b - 3 . Here, a quantity of ink is discharged for forming a large dot.
Moreover, the CPU 100 causes ink to be discharged from the nozzles simultaneously For example, in the example of FIG. 16 , ink is discharged simultaneously from the nozzles 34 a - 2 , 34 b - 3 , 34 b - 4 , and 34 a - 5 . As a result, a plurality of dots aligned in the X direction are formed simultaneously on the printing paper 12 .
The CPU 100 forms the dots based on one row's worth of print data, then drives the transferring device 104 so as to transport the printing paper 12 . The printing paper 12 is transported by a distance corresponding to the resolution of the printer 30 in the Y direction. When the CPU 100 transports the printing paper 12 , the CPU 100 waits for the next row's worth of print data to be output from the PC 20 . The CPU 100 repeatedly executes the process of forming dots based on one row's worth of print data and the process of transporting the printing paper 12 . An image corresponding to the image data 90 is thus printed on the entire range of the printing paper 12 .
As described above, the CPU 100 discharges ink from the nozzles based on the information in the cells of the print data. In the example of FIG. 16 , the gradation value of both the cell 80 a - 1 and the cell 80 b - 1 is 0, and therefore ink is discharged from neither the nozzle 34 a - 1 nor the nozzle 34 b - 1 . That is, in the case of this one row's worth of print data, neither of the nozzles for discharging ink from the nozzle unit 34 - 1 has been selected by the PC 20 .
However, the gradation value of the cell 80 a - 2 of FIG. 16 is 1, and consequently ink is discharged from the nozzle 34 a - 2 , and is not discharged from the nozzle 34 b - 2 . That is, the nozzle 34 a - 2 of the nozzle unit 34 - 2 has been selected by the PC 20 . Further, the gradation value of the cell 80 b - 3 of FIG. 16 is 3, and consequently ink is discharged from the nozzle 34 b - 3 , and is not discharged from the nozzle 34 a - 3 . That is, the nozzle 34 b - 3 of the nozzle unit 34 - 3 has been selected by the PC 20 .
The print data includes a plurality of combinations of position where the dot is to be formed, one nozzle selected from the nozzles of the nozzle unit corresponding to that position, and the ink quantity to be discharged from that nozzle. For example, in the example of FIG. 16 , when 1 is stored in the cell 80 a - 2 , this signifies the combination ‘X˜2’, ‘the nozzle 34 a - 2 ’ and ‘ink quantity for forming a small dot.’ It might seem that position in the Y direction is not stored in this information. However, the position of the image data 90 in the Y direction is retained in the sequence in which the print data is sent. The PC 20 creates print data that is mapped to positions in the Y direction by creating this print data in the sequence of the Y direction.
In the present embodiment, the combination of position, selected nozzle, and ink quantity included in the print data is also termed the selected nozzle information. That is, the print data includes a plurality of items of selected nozzle information.
The PC 20 basically selects one nozzle at random utilizing a random number (see S 1021 ˜S 1042 of FIG. 15 ). That is, the PC 20 randomly selects one nozzle from the nozzles of one nozzle unit, thus creating the selected nozzle information.
However, the PC 20 counts the number of times that the same nozzle of each nozzle unit has formed dots. For example, in the case where the nozzle 34 a - 1 has formed a dot when 0 is stored in the cell 76 a - 1 of the first count value storage 76 a, 1 is written in the cell 76 a - 1 (S 1042 ). Further, in the case where the nozzle 34 a - 1 has formed a dot when 1 is stored in the cell 76 a - 1 of the first count value storage 76 a, 2 is written in the cell 76 a - 1 (S 1042 ). Random selection is prohibited when 2 is being stored in the cell 76 a - 1 , and instead the nozzle 34 b - 1 must be selected (S 1012 ). In this case, the dot is formed by the nozzle 34 b - 1 . The nozzle 34 a - 1 is thus prevented from forming three consecutive dots.
The PC 20 prohibits the same nozzle from being selected for more than two positions continuously aligned in the Y direction. As a result, dots are prevented from being formed by the same nozzle at more than two consecutive positions in the Y direction. With the present embodiment, even when nozzles are not aligned equidistantly in the X direction, it is possible to completely eliminate the phenomenon wherein regions in which the ink density is much greater or smaller continue across a wide range in the Y direction. As a result, better printing results can be obtained than the conventional technique.
Furthermore, if dots are formed by the same nozzle at consecutive positions in the Y direction, the following problem may occur.
Dots 140 of FIG. 17 are aligned in the sequence of a large dot 140 a , a large dot 140 b , and a small dot 140 c . If these dots are formed by the same nozzle, dots 141 or 142 may be formed. With the dots 141 , a small dot 141 c is larger than the small dot 140 c . With the dots 142 , a small dot 142 c is smaller than the small dot 140 c.
When dots are formed by the same nozzle at consecutive positions in the Y direction, dots with the intended size might not be obtained. With the present embodiment, dots are prevented from being formed by the same nozzle at more than two consecutive positions in the Y direction, As a result, the above type of problem does not readily occur. Satisfactory printing results can therefore be obtained
Variants of the above embodiment are given below.
(1) The technique of the above representative embodiment can also be utilized by a serial type ink jet printer.
(2) The nozzles of the nozzle line 34 a may also discharge ink in a vertical direction (see FIG. 5 ). In this case, the timing at which ink is discharged from the nozzles of the nozzle line 34 a may vary from the timing at which ink is discharged from the nozzles of the nozzle line 34 b . The nozzle line 34 a and the nozzle line 34 b can thus form dots at the same positions.
(3) The number of nozzles in one nozzle unit is not limited to two. The number can be changed to three or more.
(4) In the above representative embodiment, the maximum number of times the same nozzle can be selected consecutively was two times. However, the maximum number of times can be changed to three or more. Of course, the maximum number of times the same nozzle can be selected consecutively is a number smaller than the resolution (the number of dots that can be formed in the Y direction) of the printer 30 in the Y direction. Further, the maximum number may be one when the number of nozzles in one nozzle unit is more than three.
It is preferred that the maximum number of times the same nozzle can be selected consecutively is a small number For example, it is preferred that this number is set to be less than 10 times. The maximum number of times may equally well be set based on the resolution (dpi (dots per inch)) in the Y direction.
(5) The maximum number of times the same nozzle can be selected consecutively need not be fixed at two times. For example, the maximum number may be set as two times in the case of processing one item of image data, and may be set as a number other Man two times in the case of processing a different item of image data. Further, the maximum number of times may be changed to a number other than two while one item of image data is being processed.
(6) In the above representative embodiment, a case was described in which the ink jet printer 30 utilizes only one color of ink. However, the technique of the above representative embodiment can also be utilized by an ink jet printer utilizing a plurality of colors of ink. For example, an ink jet printer utilizing four colors of ink has four ink jet heads. In this case, the PC 20 creates the image data shown in FIG. 13 for each of the colors.
(7) Furthermore, in the above representative embodiment, the PC 20 creates the print data. However, the printer 30 may equally well create the print data. In this case, the reading device 120 , the selected nozzle information creating device 122 , and the counter 124 of FIG. 11 are mounted in the printer 30 . In this case, the following type of variant can be obtained.
For example, the printer 30 may have a scanner function, and may be able to print an image that has been scanned. In this case, the printer 30 creates print data from bit mapped data obtained from the scanned image, and executes a printing operation based on the print data that has been created. | This specification discloses a computer program product for creating print data utilized by an ink jet printer. The ink jet printer comprises an ink jet head moving in a predetermined direction with respect to a print medium. The computer program product includes instructions for ordering a computer to perform a reading step of reading image data that includes a plurality of first combinations. Each first combination comprises a position and information concerning whether a dot is to be formed at the position. The computer program product includes instructions for ordering the computer to further perform a print data creating step of creating the print data by creating a second combination for each position at which the dot is to be formed. Each second combination comprises the position at which the dot is to be formed and one nozzle randomly selected from the nozzles of the nozzle unit which corresponds to the position. In the print data creating step, the same nozzle cannot be selected for more than a predetermined number of positions continuously aligned along the predetermined direction. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method and apparatus for flushing the cooling system of an internal combustion engine.
2. Description of the Prior Art
Periodic backflushing of the cooling system of internal combustion engines is necessary to flush away accumulated sediment and deposits such as rust and scale. The accumulation of such material in the cooling system clogs components such as the radiator core, thermostat and heater valve, and interferes with efficient operation of the system, adversely affects the engine operating temperature and causes premature engine wear and failure.
The typical motor vehicle cooling system includes a radiator, engine block and heater. A do-it-yourself motorist usually flushes the cooling system by simply removing the radiator cap, draining the coolant from a low point in the system, and forcing water into the radiator with a garden hose. This is largely ineffective since it does not reversely circulate water through the engine block or the heater, nor does the water pass through the thermostat, which would be closed because of the relatively low temperature of the flushing water.
Commerical backflushing of cooling systems is effective to reversely circulate flushing liquid and thereby dislodge accumulated deposits, but it is a significant maintenance expense and requires a trip to a garage or other repair facility.
An increasing number of motorists are beginning to backflush their own cooling systems and various devices have been made available to reach this market. However, no one device provides all of the basic features needed. Some are not portable, many are too costly, and most are too complicated or cumbersome to use. Ideally, a backflushing system should be easily installable and readily available for the periodic use necessary to keep a cooling system in proper operating condition.
One system of the prior art employs a "T" fitting which is permanently installed in the heater hose between the engine block and the heater. The third leg of the "T" is capped when the fitting is not being used for backflushing. For backflushing the cap is removed and a garden hose is attached to force water through the cooling system. However, the water is forced out the two legs of the "T" in opposite directions, most going into and out of the radiator via the most convenient path or path of least resistance. Because most engines must be run during backflushing, the usual water pump bucks or resists the intended backflush water circulation. Thus, there is little if any flushing action on the heater, hoses, engine block, or water pump, the backflushing being essentially confined to the radiator. Insofar as is known, most other systems are not permanently installed as a part of the cooling system. Consequently, for periodic backflushing of the cooling system, it is necessary to disconnect hoses and locate and reinstall the system components required for such backflushing.
SUMMARY OF THE INVENTION
According to the present invention, a backflush coupling and method is provided which is adapted to quickly and easily flush the cooling system of an internal combustion engine. The preferred method comprises cutting of the upper heater hose extending between the engine block and the heater, and installing male and female connector halves of a backflush coupling into the cut ends. The second or lower heater hose, connecting the heater to the water pump could also be used, if desired, since the coupling can be readily installed into the heater hose for flushing flow in either direction. A union fitting provides a convenient threadably interconnection between the connector halves so that coolant can flow through the installed backflush coupling during normal operation of the engine. Lock means are provided to secure the interconnection against any unintentional or inadvertent separation.
Periodic flushing of the cooling system is easily accomplished by simply unlocking the locking means, rotating the union sleeve to separate the male and female connector halves, placing the male connector half in a convenient position to act as a drain, and connecting a garden hose or the like to the female connector half. Water or any suitable liquid under pressure from a suitable source is then circulated in a backflush direction through the engine block, past the water pump, upwardly through the radiator and out the radiator cap, in those instances where it has been opened or removed. Water also circulates past the water pump and through the heater for discharge to drain through the male connector half. This method affords a fairly thorough backflushing through all of the major components of the cooling system. If desired, the garden hose can then be connected to the male connector half of the coupling to circulate fluid into the conduits leading from that connector half. This added flushing provides additional cleaning of the cooling system.
The connector halves include stepped or two diameter portions so that they are adapted to fit within at least two different sizes of radiator hose. Moreover, one of the connector halves includes a resilient element overlying one or more pressure relief openings, the element being forced away from the openings at a predetermined pressure to allow liquid to pass through the openings and thereby signal an over-pressure condition in the cooling system. This liquid leakage is permitted in one position of a reversible stop element, but in another position the stop element effects a positive seal of the pressure relief openings and prevents any leakage, even at high system internal pressures.
In one embodiment a portion or portions of the coupling is made transparent to enable examination of the character and rate of flow of the coolant during either normal or backflush operation of the cooling system. If desired, a ramp and ball indicator means may be temporarily installed during flushing with the backflush coupling to provide a more positive indication of the rate of flow of the coolant. In yet another embodiment an aspirator is temporarily incorporated during flushing operations to the coupling to introduce air and thereby provide a more turbulent flushing action for improved purging.
Other objects and features of the invention will become apparent from consideration of the following description taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the present backflush coupling installed in the cooling system of a typical internal combustion engine;
FIG. 2 is a perspective view of the present backflush coupling;
FIG. 3 is an enlarged view taken along the line 3--3 of FIG. 2;
FIG. 4 is a view taken along the line 4--4 of FIG. 3;
FIG. 5 is a view taken along the line 5--5 of FIG. 3;
FIG. 6 is an enlarged detail view taken in the area denoted by the numeral "6" in FIG. 3;
FIG. 7 is a view similar to FIG. 3, but illustrating the stop element in a reversed position, wherein it bears against the resilient sealing element to disable the excess pressure leakage function;
FIG. 8 is an enlarged detail view taken in the area denoted by the numeral "8" in FIG. 7;
FIG. 9 is a view similar to FIG. 3, but illustrating a garden hose attached to another embodiment of a female connector half, and in which an aspirator is included for use during backflushing;
FIG. 10 is a view of yet another embodiment of the invention in which a ramp and ball indictor means is incorporated in the male connector half of the backflush coupling;
FIG. 11 is a view taken along the line 11--11 of FIG. 10; and
FIG. 12 is a longitudinal cross sectional view of a back check device that may be incorporated in the female connector half of FIG. 10 during a backflush operation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, and particularly to FIGS. 1-6, there is illustrated a backflush coupling 10 for use in conjunction with the cooling system of an internal combustion engine, the cooling system comprising, generally, a radiator 12, an inlet hose 14, a thermostat 16, an engine block 18, a bottom or outlet hose 20 from the radiator 12, a water pump 22, a heater valve 24, a heater inlet hose 26, a heater 28, and a heater outlet or return hose 30.
A preferred procedure is backflushing the cooling system is to first add a suitable flushing cleaner or chemical composition by pouring it into the radiator cap opening. The radiator cap 32 is replaced and the engine is operated until the coolant temperature has risen sufficiently to open the thermostat 16 for circulation of the coolant and cleaner through the radiator, and also to open the heater valve 24 to enable circulation of the coolant and cleaner through the heater 28 and through the balance of the cooling system conduits. Any of various cooling system flushing agents or chemicals are commercially available for this purpose. After a prescribed interval, the engine is then stopped, cap 32 is removed, and the radiator drain valve 34 is opened to drain the system. Depending upon the radiator design, the valve 34 is then closed and the system is ready for back flushing. In some cooling system designs it may be more advantageous to leave the radiator cap 32 in place while flushing the system, as will be apparent to those skilled in the art.
Normal flow of engine coolant through an automotive cooling system is from the water pump 22 to the engine block 18. Once in the engine block, the coolant can take two paths, one through the heater valve 24, then to the heater inlet hose 26, through the heater 28, and back through the heater outlet hose 30 to the water pump 22. The other path is through the thermostat 16, the radiator inlet hose 14, the radiator 12, and back to the water pump 22 through the radiator outlet hose 20.
It is an object of the present invention to facilitate backflushing so that it can be done simply and quickly by relatively inexperienced motorists. For this reason, the backflushing coupling 10 preferably is installed in the most readily accessible portion of the cooling system, that is, in the upper heater inlet hose 26 which is normally located above the engine in plain view. The heater outlet hose 30 is usually accessible and the coupling 10 could also be installed and used in this conduit if desired.
Using a sharp knife or single edge razor blade, the hose 26 is slit transversely and the backflushing coupling 10 inserted into the cut ends so that it forms a permanent coolant circuit during normal operation of the cooling system.
The internal diameter of the hose 26 often varies from one engine to the next and the coupling 10 is made to fit within hoses of various sizes. More particularly, the coupling 10 comprises, generally, a male connector half 36 having an elongated, cylindrical hollow body 38 characterized by an outer extremity 40 having an inner tapered step 42 of a diameter adapted to be press fitted into the cut end of the section of hose 26 leading to the heater 28. The male connector outer extremity 40 also includes an outer tapered step 44 having a lesser outer diameter, compared to the tapered step 42, so that it is insertable within a heater inlet hose 26 of lesser internal diameter.
The tapered steps 42 and 44 are each characterized by a succession of longitudinally spaced apart circumferential barb flanges adapted to relatively easily slide into the hose, but configured to resist being pulled out of the hose, as will be apparent.
The inner extremity of the male connector body 38 is reduced in diameter and provided with male threads 46 adapted to be threadably engaged by the female end of a garden hose 48. As will be seen, the male connector half 36 preferably serves as the drain line during the backflushing operation and can be used to drain onto a driveway or the like, or the garden hose 48 can be attached to it to allow drainage to a gutter, sink drain or the like.
The backflush coupling 10 also comprises a female connector half 50 having an elongated, cylindrical hollow body 52 provided at its outer extremity with an inner tapered step 54 and an outer tapered step 56 identical in construction and configuration to the steps 42 and 44 of the male connector half 36. The inner tapered step 54 is forcibly inserted into the section of the heater hose 26 which extends to the heater valve 24.
Although not shown, usual hose clamps are disposed about the ends of the hose 26 adjacent the tapered steps 42 and 54 to securely hold the coupling 10 within the cut ends of the hose 26.
The inner extremity of the hollow body of the female connector half 50 includes an annular flange 58 adjacent a lesser diameter end portion.
As best seen in FIG. 6, the annular flange 58 includes a front seating surface 62 and a rear seating surface 64. An annular sealing means or O-ring 66 is disposed upon the front seating surface. In addition, for a purpose which will become apparent, one or more radially extending passages 60 extend from the interior or bore of the female connector body 52 to the outer circumferential surface of the end portion beneath the O-ring 66, the passages 60 normally being closed and sealed off by the O-ring 66. Also, the rear seating surface 64 is provided with one or more radially extending grooves 70 which, as will be seen, are adapted to allow air to pass to the area in which the O-ring 66 is located.
The female connector half 50 also includes a cylindrical union nut or sleeve 72 having an annular wall 74 at one extremity for seating against the rear seating surface 64. The opposite extremity of the union sleeve 72 is provided with female theads 76 adapted to engage upon the male threads 46 of the male connector half 36 to secure the coupling 10 together. The union sleeve 72 renders the connection of the mating portions of the coupling 10 comparatively easy since only relative rotation of the sleeve 72 is necessary to effect the connection.
A fluid tight seal is provided by an annular washer 78 bearing on one side against the end of the male connector half 36, and at the other side against an annular stop washer 80 whose opposite face bears against the end of the female connector half 50 and against the O-ring 66.
Rotation of the union sleeve 72 in one direction compresses the O-ring 66 and the washer 78 to establish a fluid tight connection whereby the coupling 10 may serve as a conduit for coolant in the normal operation of the cooling system. The union sleeve 72 is rotatable in an opposite direction to enable separation of the connector halves 36 and 50 to apply flushing liquid to the cooling system for backflushing, as will be seen. Clearance spaces are defined between the union sleeve 72 and the adjacent portions of washer 80, flange 58 and body 52.
In the coupled state illustrated in FIG. 3, the dimensions of the components are carefully selected so that upon attainment of a predetermined excessive pressure in the cooling system, such as above approximately 20 pounds per square inch, the excessive pressure, acting through the passages 60, will tend to circumferentially outwardly expand the O-ring 66 away from the passages 60 and allow flushing liquid to flow past the O-ring and through the clearance spaces provided between the flange 58 and the confronting portions of the union sleeve 72 and the female connector 50. The escape of such fluid will generally be apparent upon any periodic inspection of the engine coolant system and, in any event, would be noticed as a collection of coolant on the floor or driveway or as a wet condition around the immediate area of the coupling. Over pressurization of the cooling system is a hazardous condition in that it tends to cause failure of hoses and hose connections and adversely affects or destroys other cooling system components.
In the event that the motorist elected to sacrifice the over pressurization feature and did not wish to have coolant escape under any conditions, the stop washer 80 can be reversed in position to accomplish this. In the position of the stop washer 80 illustrated in FIG. 3, the rear face of the washer is flat, while the opposite face includes a central shallow bore defining an axially extending annular face 82. On disassembly of the coupling 10, the washer 80 can be reversed in position so that the annular face 82 bears against the O-ring 66, whereupon forcible tightening of the union sleeve 72 on reassembly will exert sufficient compressive force upon the O-ring 66 that it cannot be circumferentially moved away from the passage 60 despite any over pressure condition in the cooling system. This stop leak position of the washer 80 is illustrated in FIGS. 7 and 8.
One or more passages 83, FIG. 3, are preferably provided in the male connector half 36, leading from the interior bore of the body 38 to the annular seat for an O-ring 86. The O-ring 86 acts in a manner similar to the operation of the O-ring 66 previously described, but is useful in signaling over pressure conditions when a source of pressure, such as a garden hose is attached by a suitable adaptor to the male connector half 36, rather than the female connector half 50. Further, if desired, O-rings 86 and 66 can be selected such that each releases fluid at a different pressure, thereby affording an indication of operation of the system between two predetermined pressures.
It is important that the coupling 10 remain coupled despite engine vibration, road shocks and the like, and a lock sleeve 84 is provided for this purpose. The lock sleeve 84 is cylindrical and of an internal diameter to closely slidably fit over the cylindrical outer surface of the male connector body 38, as best seen in FIGS. 3 and 4. The groove for the O-ring 86 is located adjacent the threads 46 to normally underlie the sleeve 84, providing frictional constraint to prevent inadvertent separation of the sleeve 84 from the male connector half 36 when the coupling 10 is decoupled. The sleeve 84 would be moved from its overlying relation to the O-ring 86 whenever it was desired to enable the O-ring 86 to lift off its seat to signal an over pressure condition.
The lock sleeve is characterized by an axially extending locking tab 88 at one edge, as seen in FIG. 2, and by a cutaway portion or tab slot 90 in its opposite edge adjacent the tab 88. The tab 88 is adapted to slidably enter and fit within any one of a plurality of axially extending, equally circumferentially spaced tab seats 92.
The tab slot 90 is adapted to slidably receive a generally rectangular lock element 94 projecting radially outwardly of and integral with the male connector half body 38.
In order to securely lock the coupling 10 together, the mating halves 36 and 50 are fitted together and the union sleeve 72 is tightened with hand pressure, which is usually sufficient to effect a good fluid tight seal against the O-ring 66 and the washer 78, the lock sleeve 84 at this time having been moved to the left such that the lock element 94 is received within the tab slot 90. This locates the locking tab 88 out of the way of the rotating sleeve 72. Next the lock sleeve 84 is axially slid to the right to locate the locking tab 88 within the closest one of the tab seats 92. The union sleeve 72 is then rotated or advanced a partial turn to align the lock element 94 with a shallower tab slot 96 adjacent the deeper tab slot 90. Leftward movement of the lock sleeve 84 will now locate the lock element 94 within the tab slot 96, but without complete disengagement of the locking tab 88 from the tab seat 92. Consequently, relative rotation between the connector halves 36 and 50 is impossible without deliberate axial movement of the lock sleeve 84 to disengage the lock element 94 from the tab slot 96. Further, seal 86 offers significant resistance to movement of sleeve 84 and this precludes inadvertent rotation of sleeve 84 even with slots 90 and 96 disengaged from the locking element 94, thus tending to maintain the coupling halves joined together. The sealing washer 78 also tends to prevent relative rotation of the connector halves.
In the permanent or in-line position of the coupling 10 illustrated in FIG. 2, it may be desirable to determine the condition and flow rate of the coolant through the cooling system. In that event, one or more of the components of the coupling 10 can be made of transparent material so that the motorist can determine if the coolant is characterized by a suspension of rust particles, for example, and also can determine the rate of flow by gauging the speed of passage of entrained bubbles or the like.
From the foregoing it will be apparent that in the installed position of the coupling 10 there is no adverse affect on the normal operation of the engine cooling system. However, the coupling can be readily decoupled to perform the periodic backflushing which is so important to the proper maintenance of the engine cooling system. As previously indicated, this can be done by appropriately positioning the lock sleeve 84 to enable relative rotation and separation of the connector halves 36 and 50. Next, as schematically indicated in FIG. 1, the male end of a garden hose 98 is threaded into the female connector half 50 and water or suitable liquid under pressure from a suitable source 100, such as the water supply system of a household, is directed through any of many commercially available one way anti-siphon or check valves 101 to the heater inlet hose section leading to the heater valve 24. At this time the stop washer 80 is preferably in the position illustrated in FIG. 3 so that over pressurization of the cooling system by the source 100 can be immediately detected by noting any leakage of flushing water past the O-ring 66. If leakage occurs, it will appear adjacent the annular wall 74, and the degree of leakage will give some indication of the amount of over pressurization. Also, the degree of leakage may be used as a visual aid in adjusting the fluid flow at the source such that an adequate inlet pressure is applied through the hose 98 upon the cooling system.
During the backflushing operation water under pressure will pass through the engine block, through the water pump 22 and upwardly through the radiator 12, the radiator cap 32 preferably being removed to enable drainage of some of the flushing liquid through the radiator cap opening. Other flushing liquid back flows through the heater outlet hose 30, through the heater 28, and out of the male connector half 36 to any suitable drain, or through the garden hose 48 if the hose 48 is being used for drainage. In most instances it is desirable to have the engine running during the backflushing operation, although this is not always essential. As will be seen, it is advisable in some cooling systems to leave the radiator cap 32 in position for a portion of the backflushing operation.
It is advantageous to create a turbulent flow of coolant fluid through the cooling system during the backflushing operation and for this purpose air can be aspirated into the flushing liquid flow by employing an aspirator 102, as best seen in FIG. 9. The aspirator includes an axially extending portion of circular transverse cross section which diminishes in diameter in a downstream direction. The upstream end of the aspirator includes an annular flange 104. In using the aspirator 102, O-ring 66 is removed, the stop washer 80 is removed, and the flange 104 of the aspirator 102 is placed in the same position previously occupied by the washer 80. Water flowing through the aspirator 102 produces a low pressure area adjacent the plurality of passages 60, drawing in or aspirating air from around the flange 58 and through radially directed passages 114 which may be provided in the sleeve 72 adjacent the flange 58, as seen in FIG. 9. This air mixes with the water at the tip of aspirator 102 and passes into the cooling system.
The back check 106 of FIG. 12 is made of elastomeric material and is pinched closed at its down stream end. The pinched end opens under the pressure of the flushing liquid, but closes if any reverse flow of the flushing liquid were to occur. The back check 106 thus serves as a check valve to supplement operation of the check valve 101. In normal use of the cooling system, back check 106 would be removed, as would be the aspirator 102 described previously.
With reference to FIGS. 10 and 11, an embodiment of the coupling is illustrated which utilizes transparent material for the male connector half 36a and the lock sleeve 84. In addition, the internal bore of the connector half 36a is provided with an inclined portion or ramp 108 which defines an internal coolant passage of progressively smaller size in a downstream direction, assuming normal operation and coolant flow. The downstream end of the ramp 108 includes a stop 110 which limits the downstream movement of a ball 112 located on the ramp 108. The rate of flow of the coolant moves the ball 112 further up the ramp, thereby giving an indication of the rate of flow of the coolant, and thus affording a check on the proper operation of the water pump 22, or on the existence of possible blockages in the system. The ball 112 would normally be removed during usual operation of the cooling system to reduce resistence to coolant flow.
When backflushing is completed, the coupling is simply recoupled and any good grade of antifreeze or other coolant is added to the cooling system with fresh water.
From the foregoing it will be apparent that the coupling 10 is relatively economical to manufacture and simple for the average motorist to install and use. Backflushing is easily accomplished by attachment of the householder's garden hose, following which the coupling can be reconnected to remain with the vehicle in position for immediate use during periodic maintenance. It is a particular feature of the coupling 10 that the backflushing liquid flow is uni-directional at any given time. Usually it is quite sufficient and thorough to introduce source liquid only into the female connector half. However, it could be introduced into the male connector half. Also, if desired, the coupling 10 could be incorporated instead in the lower or outlet heater hose 30. Backflushing in this situation would be achieved by installing the female connector half 50 in the slit end of the portion of the heater hose 30 leading to the heater 28.
Transparent components can be utilized to provide an indication of the condition and flow rate of the engine coolant. Moreover, during either backflushing or normal use, the coupling can be employed to provide an indication of coolant system over pressurization. The lock sleeve also provides assurance against accidental loosening and separation of the coupling 10 during normal engine operation, and gives a visual indication of its locked condition. The union connection greatly facilitates connection and disconnection of the coupling connector halves in that no rotation of the connector halves within their respective hose ends is necessary. Air aspiration is readily available by incorporating a separate aspirator within the coupling, and a relatively minor modification of the internal configuration of one of the connector halves permits incorporation of a fluid flow indicator.
The cooling system described and illustrated in the drawings is typical but variations in cooling systems, engines and radiators may require some deviations from the procedure recommended. In some cases backflushing should be done with the engine running, in some cases not. This is also true with respect to whether or not the radiator cap should be removed, and whether or not the radiator drain valve should be left open. Also, in many situations it is not necessary to use a check valve between the liquid source and the cooling system. However, if potable water is used as the source liquid, always use a suitable check valve 101. Otherwise, it would be possible during backflushing to contaminate the water supply. These individual differences do not, however, alter the basic operation of the present coupler and method.
Further, although the preferred embodiment of the coupling includes tapered steps or hose barbs to facilitate insertion of the coupling into the cut ends of a radiator hose, it is contemplated that other end fittings could be used, so long as the end result is installation of the coupling in fluid communication with the heater hose. Thus, an auto manufacturer could install one of the connector halves, preferably the female connector, integral with the engine, heater valve, or water pump, or threadably connected thereto. The heater hose would then be clamped to the other connector half.
It should also be noted that the present coupling is useful in an emergency to mend a heater hose. The hose on opposite side of the failure would be cut and clamped to the connector halves, not only providing a hose repair, but also providing a future backflushing capability, as needed.
Various modifications and changes may be made with regard to the foregoing detailed description without departing from the spirit of the invention. | A backflush coupling and method for flushing the cooling system of an internal combustion engine. The preferred method comprises cutting the coolant discharge hose which extends from the engine to a heater and installing the male and female connector halves of a backflush coupling into the cut ends. The installed backflush coupling constitutes a conduit for normal coolant flow. The coupling is disconnectable for attachment of a flushing hose to the female connector half, the male connector serving as a drain. A union sleeve facilities assembly and disassembly of the coupling connector halves. The coupling is adapted to fit within heater hoses of different sizes, and certain embodiments signal over pressurization of the cooling system, reveal condition of the coolant and indicate general rate of flow, and provide for air induction for mixture with the flushing liquid. A locking device prevents inadvertent separation of the coupling connector halves. | 5 |
[0001] This application claims benefit of Provisional Application Ser. No. 61/970,562, filed Mar. 26, 2014, entitled “Linear Impact Switch”, the entire disclosure of which is incorporated herein by this reference.
FIELD OF THE INVENTION
[0002] The invention relates to a switch that is actuated by an impact or pressure on its surface, wherein the switch may be oriented generally vertically so that an impact that occurs in a generally horizontal direction will activate the switch. The switch may be installed, for example, on a barrier, wall, or fence, so that an object moving generally horizontally against the generally vertical switch will activate the switch. An especially-preferred application is installation of the switch on or near a barrier or guard-rail near a road, path, or equipment, so that an avalanche, falling rock, or mud-slide will fall or roll against the switch to activate the switch to signal that the event has occurred.
SUMMARY
[0003] The invention comprises switch system apparatus, and/or methods of using apparatus, that provide a contact closure, when pressure-activated at any of multiple locations over substantial distances and surface areas. One or more switch units are provided that may extend along a significant distance to signal an event that may happen at any location along said distance, the event comprising or relating to an object impacting/pressing one or more of the switch units to signal the event.
[0004] Preferred switch units are positioned with their impact faces in a generally vertical orientation to receive generally horizontal forces. An especially-preferred embodiment and/or method comprises triggering an alarm in a falling rock or slide area, wherein the switch units are placed beside a road, path, fence, retaining wall, or other perimeter. For example, certain embodiments of the invention may be installed on standard 10 ft. long concrete “jersey-barriers” used as a barricade against falling, sliding, or rolling debris, for example, to limit or prevent the debris from entering a roadway. By using certain embodiments of the invented switch system on one or preferably a line of said barriers, travelers, officials, and/or highway agencies may be made aware of the movement of debris against and even over the barrier(s). This way, the travelers may be alerted to slow down and/or the officials/agencies may be alerted that remediation of the situation is needed or that subsequent, additional falling, sliding, or rolling of debris may be imminent.
[0005] Instead of providing a single point of contact for activation of the switch, certain embodiments of the invention provide many, and preferably practically limitless, contact points along the length and/or width of each switch unit. Relay technology may be integrated into certain embodiments of the switch system to adapt the system to detect an event at any, or substantially any, locations along long sections of adjacent barriers or other elongated structures, for example, along many feet, yards, or even miles of said barriers/structures. Typically the switch system will be installed along sections of road where falls or slides are known to happen or are anticipated in the future.
[0006] The contact closure system of each switch unit comprises multiple, elongated, parallel or generally parallel, electrically conductive components that normally are spaced apart so that they are not in contact, resulting in the switch normally being open. An impact and/or pressure pushes an outer component of said conductive components inward to contact an inner component of said conductive components. Said contact of the inner and outer components closes the switch, hence allowing current to flow to signal the impact/pressure that typically equates to an undesirable or dangerous event.
[0007] In certain embodiments, the two elongated, conductive components may comprise an elongated rod, bar, channel, tube, or other member (“rod” hereafter) and an elongated plate, wherein the rod is the inner or “rearward” component and the plate is the outer or “forward” component. Upon impact/pressure on one or more regions of the plate, the plate will move inward or “rearward” to contact the rod, closing the switch. In preferred embodiments, the inward or rearward movement is flexing of the plate or at least a portion of the plate, but other ways and means of moving are envisioned, for example, sliding or pivoting. More than one rod may be provided in various locations inside the switch unit to ensure that the moving/flexing plate will contact one or more rods. One or more plates or plate portions may be provided in a switch unit, but a single continuous plate is preferred for each switch unit, so that sealing against the environment is enhanced, and so that impact/pressure against nearly any region of the single plate will move/flex the plate to an extent that part of the plate contacts the rod(s).
[0008] Contact between the conductive components serves as the switch that energizes a relay. The output of the relay circuit (also “relay”) provides the signal of event detection. The electrical resistance of the materials used in the switch will determine the possible length/dimensions of the elongated conductive components, and the distance a switch unit will function using a single relay. Switch units may be manufactured at fixed lengths, for example, several feet long, but multiple switch units may be aligned, for example, end-to-end along a span, and electrically connected by junctions and using multiple relay circuits, in order to extend the distance that the system operates. The longer the span, the more relay circuits may be needed, but, with the switch units wired in parallel, any contact point within any individual switch unit will generate the closure and signal the impact/pressure event. Said signal may be sent wired to a local controller, which may activate a warning beacon or audio alarm near the impact zone, and/or wirelessly using existing cellular or satellite technology to inform those who wish to monitor such events. Thus, the control room of the emergency management personnel may be remote from the event causing the signal.
[0009] The distance (or “span”) which is monitored by the switch system for impact/pressure events may correspond approximately to the total length of the multiple switch units. The vertical height range being monitored will correspond approximately to the width of each switch unit. If all the switch units are the same width and are all installed at about the same level above the ground/road, then the vertical height range being monitored will be the same, or substantially the same, all along the span.
[0010] In certain embodiments, the conductive plate or other outer conductive component is somewhat flexible and resilient, so that the impact/pressure pushing it inward to close the switch does so without permanently denting, scarring, or closing the switch. This way, after the rock or other cause of the alarm has been removed, the outer conductive component of the switch unit initiating the alarm will return to be at or very near its original position, and hence the switch unit will return to a switch-open condition. The unit would be visually and/or electrically/electronically inspected for the return to the switch-open condition and for damage that might cause an inadvertent/accidental switch-closure and alarm signal. Alternatively, because the preferred switch units are modular in design, for disconnection from each other and easy replacement of individual units, a damaged unit may be easily replaced if there is a question about its condition or future performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a front view of one embodiment of an invented switch unit, wherein wires extending from one end of the unit (top of sheet) are for connection to another switch unit via relay and/or junction apparatus, and wires extending from the other end (bottom of sheet) are for connection to the illustrated controller.
[0012] FIG. 2 is a side isometric view of the unit of FIG. 1 .
[0013] FIG. 3 is a side (edge) view of the unit of FIG. 1 , without any wiring extending from either end of the unit.
[0014] FIG. 4 is a cross-sectional side view of the unit of FIG. 1 , viewed along the line 4 - 4 in FIG. 1 .
[0015] FIG. 4 a is a detail of the region of the unit surrounded by dashed lines in FIG. 4 .
[0016] FIG. 5 is a cross-sectional end view of the unit of FIG. 1 , viewed along the line 5 - 5 in FIG. 1 .
[0017] FIG. 6 is a cross-sectional end view of the unit of FIG. 1 , viewed along the line 6 - 6 in FIG. 4 and also generally along the line 6 - 6 in FIG. 1 .
[0018] FIG. 7 is a front view of a portion of a switch system according to one embodiment, with junction and relay apparatus connecting two switch units.
[0019] FIG. 8 is a side view of another embodiment of switch system, schematically showing multiple switch units electrically connected via relay and/or junction apparatus, and to a controller, to form a switch system spanning a long distance along a road, path, fence or barrier system.
[0020] FIG. 9 is a wiring schematic of two switch units electrically connected together and adapted for connection to additional switch units, to form a switch system spanning a long distance along a road, path, fence or barrier system.
[0021] FIG. 10 is a front isometric view of a single switch unit installed on a side of a single barrier, so that the unit is generally vertical on one side of the barrier.
[0022] FIG. 11 is a front isometric view of one embodiment of a multiple-unit switch system on a line of barriers, with relay and/or junction equipment between the switch units.
[0023] FIG. 12 is an end view of one embodiment of a switch unit/system on a barrier, wherein rock/debris has fallen (or is falling) against the barrier, but has not impacted the switch unit, so that the switch is still open.
[0024] FIG. 12 a is a detail of the impact region of FIG. 12 , wherein the rock/debris has impacted and depressed the front face of the switch unit so that a portion of the front face contacts the inner rod and closes the switch.
[0025] FIG. 13 is a front isometric view of another embodiment of a multiple-unit switch system on a line of barriers, including embodiments of relay and/or junction equipment in dashed lines inside the housings of the switch units.
[0026] FIG. 14 is a front view of an alternative switch unit with two conductive inner rods extending longitudinally through the inside of the switch unit and spaced from the single conductive cover of the unit, wherein wires extending from one end of the unit (top of sheet) are for connection to another switch unit via relay and/or junction apparatus, and wires extend from the other end (bottom of sheet) for connection to a controller.
[0027] FIG. 15 is a front view of one embodiment of a switch unit electrically connected to relay and junction equipment (top of sheet) and having wires extending (bottom of sheet) for connection to another switch, wherein the illustrated switch unit and relay-and-junction apparatus are at the far-end of a switch system opposite a controller.
DETAILED DESCRIPTION
[0028] Referring to the Figures, there are shown several, but not the only, embodiments of the invented switch unit, switch system, and/or unit/system installation and use.
[0029] FIGS. 1-6 illustrate one embodiment of a switch unit 100 that may be called a “linear impact switch” due to the switch being elongated and adapted to receive an impact at many places, and preferably substantially all along its length and its width, to close its switch. The switch unit 100 is preferably longer (up and down in FIG. 1 ) than it is wide (left and right in FIG. 1 ), and much longer and wider than it is thick (into the paper in FIG. 1 ).
[0030] The switch unit ( 100 ) may be described as having a housing in which certain conductive element(s) and wiring are held. As best seen in FIGS. 2-6 , the housing preferably comprises a rear panel ( 1 ) and a front cover ( 3 ), and endcaps ( 4 ), but may comprise other or additional housing portions in certain embodiments. The switch unit 100 is adapted in dimensions, construction, and materials, so that an impact on its cover ( 3 ) will move at least a portion of the cover ( 3 ) inward to close the switch mechanism of the unit ( 100 ). Preferably, cover ( 3 ) comprises front face ( 103 ) that moves inward by flexing inward to close the switch mechanism of the unit. The impact may hit/pressure any, or nearly any, part of the front face 103 , but the housing or other elements of the unit 100 may be rigid enough near the ends or side edges so that an impact at or very close to the ends or the side edges may not allow the front face 103 to flex sufficiently to close the switch. For example, it is desired that an impact at any point along 80 percent or greater (for example, 80-95 percent) or preferably along 90 percent or greater (for example, 90-95 percent) of the length, will cause flexing of the front face 103 sufficient to close the switch. Also, for example, it is desired than an impact at any point along 80 percent or greater (for example, 80-95 percent) or preferably 90 percent or greater (for example 90-95 percent) of the width, will cause flexing of the front face 103 sufficient to close the switch.
[0031] The construction of the switch unit 100 is preferably such that it is much longer than it is wide, as illustrated in FIGS. 2 and 10 , 11 , and 13 , so that a single unit 100 senses an impact/pressure along a significant distance. The width will typically relate/correspond generally to the height range above the ground or road at which, or over which, the user wants to sense the impact/pressure. For example, the unit 100 length may be 2-10 feet long, so it extends along the ground/road about 2-10 feet, while the unit 100 may be 0.5 feet wide and mounted with its bottom edge about 2 feet off the ground, so it will sense an impact/pressure from something that approaches the unit 100 in the range of about 2-2.5 feet above said ground/road. Or, as a further example, a unit 100 that is 2 feet wide and mounted with its bottom edge about 1 foot off the ground will sense an impact/pressure from something that approaches the unit 100 in the range of about 1-3 feet above said ground/road. Or, a unit 100 may be installed so that it is above the ground at any level where an object is expected to approach, for example, a 8 inch-wide unit 100 installed about 3 feet above the ground/road on a guard-rail or fence-rail at the level of the rail.
[0032] The rear panel ( 1 ) is preferably non-conductive and may be mounted to the barrier, wall, or fence, for example, by concrete fasteners ( 114 ) or other fasteners. A conductive rod ( 5 ), or other elongated conductive member (also “inner conductive member”), spans the length of the unit and is held in place by non-conductive stand-offs ( 2 ), as best seen in FIGS. 1 , 4 and 6 . The rod has a dual purpose by acting as one of the contacts of the switch of the switch unit ( 100 ) as well as a conduit for holding wiring inside the interior passage of the rod ( 5 ) along at least part of the length of the switch unit ( 100 ). The rod ( 5 ) is portrayed in the figures as a hollow cylinder, but rods having other outer and/or inner shapes may be used in certain embodiments.
[0033] The cover plate ( 3 ) is placed on the front of the switch unit ( 100 ) and connected to the rear panel ( 1 ). Cover plate ( 3 ) comprises said front face ( 103 ) that is generally parallel to, but distanced from, the rear panel ( 1 ) to provide the interior space ( 107 ) where the rod ( 5 ) and wiring is placed, with a gap ( 11 ) between the rear surface ( 109 ) of the front face ( 103 ) and the front surface ( 111 ) of the rod ( 5 ). As best seen in FIGS. 5 and 6 , in addition to the front face ( 103 ), the cover plate 3 also comprises sidewalls ( 105 ) that are generally perpendicular to the front face ( 103 ), and flanges ( 113 ) that are connected to the rear panel ( 1 ), for example, by friction-fit metal channels (CH) extending all along the length of the unit ( 100 ). Preferably gaskets, weather-stripping, or other moisture-seal means (not shown), are placed between the flanges ( 113 ) and the rear panel ( 1 ) to prevent moisture intrusion into the interior space ( 107 ).
[0034] The shape of the preferred cover ( 3 ) ensures it remains at a fixed distance from the rod ( 5 ) when no impact or pressure is applied by an object against the front face ( 103 ). As best seen in FIGS. 4 a , 5 and 6 , this maintains the air gap ( 11 ) (an empty space except that it is filled by air) between the front surface ( 111 ) of the rod ( 5 ) and the rear surface ( 109 ) of the front face ( 103 ) preferably over the entire length of the switch unit ( 100 ). When an impact event pushes the front face ( 103 ) toward the rod ( 5 ), the rear surface ( 109 ) contacts the rod ( 5 ), that is, closing the air gap ( 11 ) (reducing it to zero gap) in at least one location along the length of the switch unit ( 100 ). Thus, the impact brings the cover ( 103 ) into physical and electrical contact with the rod ( 5 ), activating the switch. Non-conductive end caps ( 4 ) help hold the rod ( 5 ) in place, and the preferred rigidity of the rod ( 5 ) also keeps the rod ( 5 ) in place relative to the end caps ( 4 ), and the rear panel ( 1 ), so that the rod ( 5 ) may be considered immovable or substantially immovable inside the interior space ( 107 ).
[0035] Therefore, rod ( 5 ) and cover ( 3 ) make up the switch that is used to energize the relay (R), for relaying a signal to a controller (CT, see FIGS. 1 , 1 , 8 , 9 , 11 , and 13 ) and transmission of the alarm/notification to a beacon, sign, or control/monitoring room (not shown). As best shown by the top end of FIG. 1 and the bottom end of FIG. 15 , and FIGS. 4 , 4 a , and 5 , wires (W 1 ) (via connections C 1 , C 1 ′ and terminal blocks TB 1 ) electrically connect the rods ( 5 ) of the switch units, and wires (W 3 ) (via connections C, C′ and terminal blocks TB 3 ) electrically connect the covers ( 3 ) of the switch units. As best seen in FIGS. 1 , 7 and 15 , wire (W 2 ) (also called “ground/common” wire) which extends all the way through each switch unit by passing through the hollow space of the rod(s) and is connected to the wire (W 2 ) of the adjacent switch units via terminal block (TB 2 ), is connected (via terminal block TB 2 and W 4 ) to the negative side of a low-voltage power supply (for example, battery B), and ground to the controller (CR). The positive side of the low-voltage supply (B) is connected by wire (W 5 ) to one end of the coil of the relay (R). The other end of the coil of the relay (R) is electrically connected to the cover ( 3 ), for example, via wire (W 6 ), terminal block (TB 3 ), wire (W 3 ), and connection point (C). Therefore, when the cover ( 3 ) is impacted with enough force to be pressed against the rod ( 5 ), contact is made which energizes the relay (R). The output of the relay (R) is electrically connected to wire (W 2 ) via wire (W 7 ) and terminal block (TB 2 ), providing the feedback necessary to detect the event. It will be understood that the wires described and shown will be electrically-conductive, for example, copper. Conventional battery(ies) B, relays (R), and terminal blocks (TB 1 , TB 2 , and TB 3 ), and housing and wiring for these components may be used, and one of average skill in the electrical arts will be able to assembly and the wire the units ( 100 ) into a switch system ( 300 ) after viewing this disclosure and the drawings. Also, after viewing this disclosure, one of average skill in the electrical and/or control arts will be able to operatively connect the switch system ( 300 ) by wire or wireless communication to a light, beacon, alarm, and/or control/monitoring room.
[0036] The switch units ( 100 ) are preferably manufactured at fixed lengths, and, since electrical resistance in the wires is much lower than in the materials of the rod ( 5 ) and cover front face ( 103 ), greater distances can be attained with a switch system ( 300 ) that comprises multiple switch units ( 100 ) and one or more relays (R), rather than just a single switch unit ( 100 ). The electrical resistance of the materials used will determine the distance that the system will function using a single relay circuit. As best seen in FIGS. 7-9 , 11 , 13 , and 15 , the units ( 100 ) can be operatively connected into a system ( 300 ) by electric connection of the multiple switch units via relay circuits ( 200 ) or by junctions ( 200 ′), as will be understood from this description and the drawings. Thus, switch system ( 300 ) includes multiple switch units ( 100 ) (also “modules”) operatively connected by relays ( 200 ), providing the junction function and also the relay function, and also by junctions ( 200 ′) that provide junction function but not relay function. The longer the span, the more relays ( 200 ) will be integrated.
[0037] In FIGS. 1 , 7 , and 8 , 9 , 11 , 13 , the call-out number “ 100 ” is used to denote the switch unit that is closest to the controller, for example, at the far left of the “string” of switch units in FIGS. 11 and 13 , wherein typically wires (W 1 , W 2 , and W 3 ) extend from one end to another switch unit 100 ′ via a relay ( 200 ) or junction ( 200 ′), but typically only wires (W 2 ) and (W 3 ) extend from the other end of the switch unit 100 to, via a junction ( 200 ′) (see FIG. 8 ), connect to the controller (CR). Call-out number “ 100 prime” ( 100 ′) is used to denote a switch unit anywhere in the middle of the “string”, which connects via relays ( 200 ) or junctions ( 200 ′) to two other switch units, that is, one at each end of the switch unit 100 ′ (see FIGS. 7 , 8 , and 9 , 11 , and 13 ). Call-out number “ 100 double prime” ( 100 ″) is used to denote the switch unit at the far-end of the “string” of switch units, that is, at the end opposite from the controller CR, as shown in FIG. 15 . It may be noted that the relay ( 200 ) in FIG. 15 is at the end of the switch system and, while it comprises relay equipment and terminal blocks for connection of wires, it does not comprise wiring to another switch unit. In this description and the drawings, the call-out “ 100 ” is used generally, that is, to represent any switch unit in a system ( 300 ), unless the context of the writing or drawings is pointing out a particular position in the “string” of units.
[0038] In certain embodiments, multiple of the switch units ( 100 ) are close enough to each other, and/or the impacting object is so large, that a single event/object (a single rock, a single mud-slide, a single tree, etc), will impact multiple of the units ( 100 ). In certain embodiments, a single event/object will impact only one of the units ( 100 ). Since the units ( 100 ) are wired in parallel, as shown in FIG. 9 , a contact point within any individual unit ( 100 ) will generate the switch closure, and, hence, the alarm signal.
[0039] The length of each switch unit ( 100 ) is preferably parallel to the length of the barrier or other object onto which the unit is mounted and which extends along a horizontal distance. Each unit ( 100 ) may be considered generally flat and generally planar, for example called a “switch plate”, due to its much greater length and width compared to its thickness. For example, the front of the unit ( 100 ) is substantially a plate and the rear is substantially a plate, and the thickness in-between (the sides and the ends) are small in comparison to these front and rear plates. For example, in certain embodiments, the front and rear plates are each at least 8, at least 24, at least 40, or at least 120 times greater in length than the thickness of the unit ( 100 ) and preferably at least 2, at least 3, at least 6, or at least 10 times greater in width than the thickness of the unit ( 100 ). Thus, the switch unit may be said to have a central plane (CP, into the paper, in FIG. 2 ) through the unit ( 100 ) that is generally or exactly parallel to both of the front face and the rear plate, wherein the orientation of the central plane is representative of the orientation of the front face and the unit as a whole. In certain embodiments, the unit ( 100 ) is mounted and used in a generally vertical position, that is, wherein the central plane of the unit, and the front face of the unit is generally vertical. “Generally vertical”, in this mounting and use context, means nearer vertical than horizontal, specifically within less than 45 degrees of vertical. Thus, preferably at least the front face ( 103 ), and preferably both the front face and the central plane (CP), are within 44 degrees or less of vertical, in other words exactly vertical or slanted rearward away from the likely impact source up to and including 44 degrees (more preferably up to and including 40 degrees, 30 degrees, 20 degrees or 10 degrees) or slanted forward toward the likely impact source up to and including 44 degrees (more preferably up to and including 40 degrees, 30 degrees, 20 degrees or 10 degrees).
[0040] Certain, but not the only, examples of installation are shown in FIG. 10-13 . One or more switch units ( 100 ), and preferably an entire system ( 300 ) comprising multiple units ( 100 ) with multiple relays ( 200 ) and typically also multiple junctions ( 200 ′), are provided on conventional road-side barrier(s) 13 . As shown in FIG. 11 , the relay ( 200 ) and junction ( 200 ′) apparatus may be provided in separate, water-proof housings between the switch units, for example, wherein the relay ( 200 ) and junctions ( 200 ′) alternate and the final (farthest from the controller) apparatus is a relay ( 200 ) as shown in FIG. 15 . Alternatively, as shown in FIG. 13 the relay ( 200 ) and junction ( 200 ′) apparatus (in dashed lines) may be provided inside the switch units, that is, inside the housing in the interior space ( 107 ) of each switch unit, for example, wherein the relay ( 200 ) and junctions ( 200 ′) are provided in alternate units and the final (farthest from the controller) relay ( 200 ) apparatus would be housed inside the final unit 100 ″ rather than being in a separate housing as it is shown in FIG. 15 . Therefore, for example, the final switch unit 100 ″ might have both a junction ( 200 ′) in the interior space 107 at one end (bottom end of FIG. 15 , to connect with another switch unit 100 ′) and a relay ( 200 ) in the interior space 107 at the other, outer end (top of FIG. 15 ).
[0041] System installations, such as shown in FIGS. 10-13 , may be particularly beneficial for avalanche, falling rock, and mud-slide warning systems, for example. In such installations, the portion of the side of the barrier 13 onto which the unit(s) ( 100 ) is/are mounted slants rearward about 5 degrees from vertical, and the front face of the unit, and also its central plane (CP) are orientated at about that same orientation (that is, slanted rearward about 5 degrees). In other words, the unit ( 100 ) slants slightly rearward from vertical (rearward being away from the impact source, or the rocks) but is still generally vertical and is facing the likely location of the fall/slide, and so will be impacted by rocks or other debris (D) that falls or rolls to the barrier as long as the rock/debris reaches as high as some part of the unit ( 100 ). See the detail in FIG. 12 a , wherein the rock/debris impacts/presses against only a lower region of the unit ( 100 ), and not directly in front of the rod ( 5 ), but the pressure on the front face depresses/flexes a substantial portion of the front face to an extent that a higher-up portion of the front face also flexes inward to contact the rod ( 5 ) in order to close the switch. Thus, the rock/debris (D) closes at least one switch in the switch unit ( 300 ), but may impact and close the switches of multiple switch units ( 100 ).
[0042] Preferably, the materials of cover ( 3 ) are selected so that wherever the impact location (I) is on the cover ( 3 ) of a switch unit ( 100 ), the switch will close by closing gap ( 11 ), to signal the presence of the rock/debris (D). The materials and construction of the switch unit may be selected for a particular range of impacts, that is, to close the gap ( 11 ) upon impact by a particular object weight to match the expected problematic object movement. For example, the switch unit may be designed to move to a switch-closed position upon a pressure of greater than 50 pounds per square inch, or greater than 100 pounds per square inch, or greater than 200 pounds per square inch.
[0043] The signal, from one or more switches of the system ( 300 ) closing, may be sent wired to a local controller (CR) which may activate a warning beacon or audio alarm near the impact zone, or wirelessly using existing cellular or satellite technology to inform those who wish to monitor such events. Thus, the control room of the emergency management personnel may be remote from the event causing the signal. Adaptations may be made in the system ( 300 ), and/or its controller/control room, to activate the warning beacon or audio alarm or wireless signal when the switch closure initially happens, even if the switch closure is of short duration. Alternatively, adaptations may be made in the system ( 300 ), and/or its controller/control room, to activate the warning beacon or audio alarm or wireless signal only when the switch closure continues for a certain amount of time, for example, for more than 5 seconds, more than 10 seconds, more than 30 seconds, or more than 1 minute. This may adapt the system to account for “false alarms”, for example, caused by animals, pranksters, or other temporary or accidental circumstances. Alternatively, the materials of the cover ( 3 ) may be chosen so that a substantial force, such as a rock, tree, or mud slide, is required to close the switch, but an animal or other moderate force will not close the switch.
[0044] In certain embodiments, the air gap ( 11 ) when “open” (for example, no debris against and no flexing of the cover ( 3 )) is approximately 3/16 to 5/16 inches. Or, for other embodiments and/or other materials of construction, the open gap is in the range of 1/16-1 inch, 1/16 inch to 2 inches. In certain embodiments, the dimensions of each switch unit ( 100 ) are in the ranges of 24 to 118 inches long, 6 to 10 inches wide, and 1 to 3 inches thick, for example. Or, for other embodiments and/or other materials of construction, the dimensions of each switch unit are in the ranges of 24 to 140 inches long, 6 to 36 inches wide, and 1 to 5 inches thick, for example. Other dimensions may be used in certain switches for certain applications.
[0045] If more vertical area is desired to be monitored, switch units may be provided that are wider, so they extend a greater vertical distance. For example, units may be provided that have more than one inner conductive components. For example, unit 400 in FIG. 13 has two conducting rods that are spaced apart across the width of the unit and that are electrically connected by wire (W 8 ). However, by doubling the conductive material in the switch, the distance one relay circuit will cover is reduced by half. Dimensions for a multiple-rod unit, such as the two-rod ( 5 ) unit ( 400 ), may be, for example, 24 to 120 inches long, 14 to 20 inches wide, and 1 to 3 inches thick.
[0046] The materials used for the cover ( 3 ) may be galvanized sheet metal, and the materials used for the rod ( 5 ) may be galvanized steel, for example, or other durable and conductive materials. In certain embodiments, the conductive plate or other outer conductive component is at least somewhat flexible and resilient, so that the impact/pressure pushing it inward to close the switch does so without permanently denting, scarring, or closing the switch. This way, after the rock or other cause of the alarm has been removed, the cover of the switch unit initiating the alarm would return to its original, switch-open condition, by resiliently moving away from the rod ( 5 ) or other inner conductive component(s). Thus, the cover ( 3 ) preferably is made/formed of a material and/or thickness that allows the cover front face ( 103 ) to flex inward upon impact to be concave, and then (when the debris/object is removed) to resiliently return to its normal outward position, for example, as a planar plate generally or exactly parallel to the rear panel, as explained elsewhere in this document.
[0047] After clearing of the impacting objects, the unit would be visually and/or electrically/electronically inspected for the return to the switch-open condition and for damage that might cause a continued, inadvertent, or accidental switch-closure and alarm signal. Alternatively, because the preferred switch units are modular in design, for disconnection from each other and easy replacement of individual units, a damaged unit may be easily replaced if there is a question about its condition or future performance.
[0048] Certain embodiments may comprise, consist essentially of, or consist of the following elements:
a linear switch system for signaling the impact of an object against the system, the switch system comprising at least one switch unit comprising (or consisting essentially of, or consisting of):
a non-conductive rear panel; a conductive front cover that is generally parallel to the rear panel and spaced from the rear panel to provide an interior space between the front cover and the rear panel; an elongated conductive inner member secured inside the interior space parallel to, but spaced from, the front cover when the switch unit is in a switch-closed position; wherein the switch unit is placed in a generally vertical position, and the front cover is sufficiently flexible so that, upon impact from an object moving in a generally horizontal direction, at least a portion of the front cover will move horizontally inward to contact the conductive inner member to be in a switch-closed position; wherein the front cover and inner member are wired to produce, when the unit is in the switch-closed position, a signal to an alarm or control station indicating that the impact has occurred. In some embodiments, a relay may be added and electrically connected to said front cover and said inner member to relay the signal to said alarm or control station. In certain embodiments, the front cover may be a plate with sidewalls protruding rearward for connection (by flanges, brackets, gaskets, or other fastening structure) to the rear panel or other rear members. The front cover may be elongated and the inner member may be an elongated tubular member extending along the entire or substantially the entire length of the front cover. The rear panel may be planar but may be other shapes in certain embodiments.
[0055] In certain embodiments, the switch unit may consist essentially or, or consist of, the rear panel, the inner member mounted inside the interior space in the unit, the front cover, endcaps or endplates or adaptations in the front cover to close and waterproof the ends, and wiring and circuitry to accomplish the signaling and/or relaying of the signal upon the switch closing. The interior space between the rear panel, front cover, and the endcaps, may be empty except for said inner member (one or more), mounting means for the inner member(s), wiring and air/gasses. Certain embodiments of the switch system may comprise at least four switch units, at least ten switch units, at least 20 switch units, at least 50 switch units, in each case, with sufficient junction and relay apparatus as needed for effective transmission of the signal(s). For example, certain embodiments provide junctions/terminals for wiring between all the switch units, and, additionally, relay circuitry for every two switch units.
[0056] Certain embodiments are methods of using linear impact switches and/or systems, according to any of the disclosure in this document or the figures. Certain methods comprise signaling an event along a road wherein the method comprises (or consists essentially of, or consists of):
providing a road-side barrier having a generally vertical side; providing a switch system comprising a switch unit comprising:
a rear panel mounted to said barrier; a conductive front face that is spaced from the rear panel to provide an interior space between the front face and the rear panel; an elongated conductive inner member secured inside the interior space parallel to, but spaced from, the front cover when the switch unit is in a switch-closed position; and wherein at least a portion of the front cover is moveable rearward relative to the inner member, and the switch unit is wired so that, when said at least a portion of the front cover is pushed inward to be in a switch-closed position contacting the conductive inner member, an electrical signal is produced; and
the method further comprising:
mounting the switch unit on the barrier so that the front cover is generally vertical so that, upon an object moving in a generally horizontal direction and impacting the generally vertical front cover, the front cover will flex inward to the switch-closed position; and sending said electrical signal to an alarm or control station to communicate that the impact has occurred. At least a portion of the front cover may be moveable rearward relative to the inner member by flexing toward the inner member. Said at least a portion of the front cover may in some embodiments resiliently return to the switch-open position when the object impacting the front cover is removed. Alternatively, substantially all or all of the front cover may be moveable rearward toward the conductive inner member, to close the switch. And, substantially all or all of the front cover may be moveable forward away from conductive inner member, to open the switch again after the impacting object is removed, for example. The rearward movement and the forward movement may be flexibility and resilience in some embodiments. The method may also include providing multiple of switch units and multiple relay circuits electrically connected to the conductive front cover and inner member to relay the electrical signal to an alarm or control station.
[0066] Although this disclosed technology has been described above with reference to particular means, materials, and embodiments, it is to be understood that the disclosed technology is not limited to these disclosed particulars, but extends instead to all equivalents within the scope of the following claims. | A linear impact switch provides a contact closure, when pressure-activated at any of multiple locations over substantial distances and surface areas. Preferred switch units are positioned with their impact faces in a generally vertical orientation to receive generally horizontal forces. The switch units may be used to trigger an alarm in a falling rock or slide area, wherein the switch units are placed beside a road, path, or other perimeter, for example, on a barrier, fence, retaining wall, or other structure. The switch units may be simple and durable, using a conductive outer (or forward) member and a conductive inner (or rearward) member, whereby the impact/pressure forces the outer/forward member to make contact with the inner/rearward member, thereby closing the switch to send or relay a signal notifying drivers or authorities of the event that caused the signal, even though the event may be in an isolated or seldom-inspected region. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method and device for picture signal enhancement, as well as to a display apparatus comprising such a picture signal enhancement device.
2. Description of the Related Art
European Patent Application No. EP-A-0,747,855, corresponding to U.S. Pat. No. 5,581,370, discloses a method of improving the contrast in a natural scene image. A relevant histogram of the image is derived from a selected subset of local histograms representing regions of the image. The signal describing the histogram is operated on with a filter having the characteristic of weakening strong peaks and valleys in the function, but not effecting flat portions of the signal. The filtered histogram signal is used for controlling the TRC mapping in a device at which the image is to be printed. To assure optimum selection of local histograms, regions including the black point and white point of an image are determined and added to the subset of local histograms representing regions of the image.
European Patent Application No. EP-A-0,833,501, corresponding to U.S. Pat. No. 6,078,686, discloses an image enhancement circuit in which an enhanced luminance signal is output by independently equalizing histograms for sub-images divided on the basis of the mean value of the received luminance signal. A local contrast defined as a difference between the value of an input sample with respect to the enhanced luminance signal and each value obtained by low-pass filtering the samples in a predetermined-sized window including the input sample, and the input sample value is adaptively weighted according to a detected local contrast, so that a changed luminance signal is output.
In the field of picture improvement, histogram modification algorithms are contrast/detail enhancement algorithms based on the luminance level distribution over a whole picture (or the whole relevant part of it). Because the measurement is made globally and does not take into account textures or color components, histogram modification algorithms can be less optimized in special texture or color regions. Typical local histogram modification algorithms, based on local measurement, are usually not suitable for picture improvement because they lead to continuity artifacts. A common version of such a typical local histogram modification algorithm is first to decompose the picture in simple spatial blocks, either orthogonal ones or corresponding to the limits of objects in the picture, and then to apply the same algorithm for each block, but only taking into account the histogram distribution of the given block. A major problem in this kind of algorithm is formed by the “blocking” artifacts.
Another more elaborate version is to first decompose the picture in different zones depending on their color/texture properties, and then apply different algorithms for the different zones to optimize individually each color/structure block. A major problem in this kind of algorithm is the continuity problem due to the switching of one algorithm to another and the artifacts due to the fact that the detection can never be perfect.
SUMMARY OF THE INVENTION
It is, inter alia, an object of the invention to provide an improved picture signal enhancement.
In a method of picture signal enhancement in accordance with a primary aspect of the invention, a picture signal is subjected to a histogram-based picture signal modification based on a luminance level distribution over a whole picture or a first part of the picture, and the histogram-based picture signal modification is locally adjusted in dependence on locally measured picture signal properties other than contrast and brightness, the locally measured picture signal properties relating to second parts of the picture that are each substantially smaller than the whole picture or the first part of the picture, the second parts being within the whole picture or the first part of the picture. Preferably, the second parts are individual pixels. While the second parts for which picture signal properties are measured and for which the histogram-based picture signal modification is locally adjusted, are each substantially smaller than the whole picture or the first part of the picture, it might very well turn out that (substantially) identical local adjustments are made for a substantial part of the whole picture or the first part, for example, if skin tone turns out to occupy such a substantial part.
These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 shows a basic block diagram of a first embodiment of a display apparatus comprising a picture signal enhancement device according to the invention;
FIG. 2 shows two parameters as a function of the luminance;
FIG. 3 shows a skin-tone to histogram correction for different parameter settings;
FIG. 4 shows part of the block diagram of FIG. 1 in more detail;
FIG. 5 illustrates the skin-tone detection domain in YUV;
FIG. 6 illustrates the skin-tone detection domain in UV for Y>256;
FIG. 7 illustrates the skin-tone detection domain in Vref 1 , Vref 2 for Y>256; and
FIG. 8 illustrates the correction factor depending on the position in the skin-tone detection domain.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The solution proposed by the present invention is a slight local modulation of the original histogram modification, where the local modulation parameter is defined by the local color or texture characteristics. A basic block diagram of the solution is shown in FIG. 1 .
In the local color/texture detection block 1 , different measurements of YUV are done for each pixel to determine whether the pixel belongs to an area with particular color or textures characteristics, to obtain a correction factor cor-fac that will be explained in detail below. The luminance signal Y is also applied to a histogram modification block 3 to obtain a value delta_y. The correction factor cor_fac and the histogram value delta_y are applied to a local color/texture correction block 5 to produce a value local_delta_y. A UV histogram correction block 7 produces output values Yout, Uout and Vout in response to the input UV signals, the correction factor cor_fac, and the value local_delta_y.
For each detection type, a correction factor cor_fac is defined with the values:
0 if the pixel is outside or at the limits of the corresponding detection domain, and Max value at the center of the corresponding detection domain.
The value of the correction factor cor_fac increases continuously as the pixel moves from the limits of the detection domain to the center of the detection domain. A clipping can be done so that the Max value is assigned to a more or less large zone around the center of the detection domain.
Herein, the detection domain depends on what one wants to detect. Basically, properties are defined that identify the domain. For instance, for skin tone, one wants the YUV point inside a kind of truncated simple geometric form within the YUV domain. The idea is that the correction factor cor_fac gives a slight modulation on the original histogram modification. The original histogram modification is optimal for most signal conditions, for most (80%) colors or textures. Only in some limited cases, like skin tone, grass, etc., it is desired to have a slightly different histogram modification. The detection domain limits the areas where your original histogram modification needs to be slightly adjusted. Compared to the whole YUV domain, it has to be relatively small. Otherwise, it just means that your original histogram modification is not designed properly, since it is then not suitable for most conditions.
A typical value for Max value of the correction factor cor_fac is chosen depending on the effect wanted at the center of the detection domain. One will generally choose one of the values 4, 8, 16 or 32 to allow easy computations. Then the choice is determined by:
The sensitivity required in the steps of histogram, as what one wants to avoid is to see ugly steps of the histogram in the corrected domain. For skin tone, it is preferable to be on the safe side, because one has to deal with relatively flat luminance domains and because the human eye is very sensitive in skin tone. In most cases, a value above 32 (64) is useless, considering that differential gains introduced in the histogram are never so big that one would need 64 steps in the modulation effect; and The maximum modulation that is wanted. 4 or 8 look risky, but they can be chosen if the modulation effect should not be too large. Then it is a question of normalizing the gain of the function Fy mentioned below.
The functions:
local_delta — y=Fy (cor_fac,delta — y )
local_delta — u=Fu (cor_fac,delta — y,U,Y )
local_delta — v=Fv (cor_fac,delta — y,V,Y )
are all functions for which it holds that the absolute value of the difference between local_delta_x and delta-x (with x=y, u, v) is monotonously rising with the parameter cor_fac, with the condition:
local_delta_y=delta_y for cor_fac=0
local_delta_u=delta_u for cor_fac=0
local_delta_v=delta_v for cor_fac=0
with delta_y, delta_u and delta-v equal to what one gets in the original histogram algorithm.
The advantages of this solution are that:
The whole picture, including special color or texture regions still globally benefit from the global histogram modification algorithm;
Histogram modification algorithms can be roughly optimized globally, the correction factor will do the final fine adjustment. There is no need to develop different histogram algorithms for each color/texture type;
The correction algorithms are rather independent from the global histogram modification algorithms;
The local correction allows dedicated improvements for special color or textures regions without continuity problems;
The precision of the detection domain becomes less critical because the correction factor is reduced to 0 at the limits of the domain; and
The system is rather flexible. It can be reduced to its minimum, for instance with a color detector based on UV only and a correction factor which only switches off the color compensation in the UV histogram correction block. The system can be easily extended with a new additional detection domain.
The idea is as follows: in an original histogram modification, look at the Y level distribution and calculate a delta_Y. If only a correction on Y is applied, one usually gets a saturation problem. So, it is necessary to compensate by a delta_U and delta_V. A 100% correction can be chosen for, in which case delta_U=(delta_Y/Y)*U and delta_V=(delta_Y/Y)*V. It is also possible to compensate for 50% or to compensate only when delta_Y>0, which would be preferred in a dynamic contrast algorithm.
At the moment that the delta_Y is corrected locally, it is also necessary to use local_delta_y for the correction of U and V: if a 100% correction is desired, delta_U=(local_delta_y/Y)*U and delta_V=(local_delta_y/Y)*V. Basically this can be written as
delta — U=Fu (local_delta — y,U,Y ) and
delta — V=Fv (local_delta — y,V,Y ).
In the last formula, the correction factor has disappeared. It means that the same type of U, V compensation (100%, 50% or only for delta_Y>0) is made inside and outside the correction domain. Actually, situations could exist where it is not desired to have the same kind of compensation inside and outside the correction domain. That is why the following formulation is preferred:
delta — U=Fu (cor_fac,delta — y,U,Y ) and
delta — V=Fv (cor_fac,delta — y,V,Y )
In a practical embodiment, delta_U and delta_V are the same as local_delta_u and local_delta_v.
The formulas look actually much more complicated that it is in practice. First of all, Fu and Fv will almost always be the same, and basically in most cases:
Fu (cor_fac,delta — y,U,Y )= Fu 1(delta — y,U,Y )
for correction_factor=0
Fu2(delta_y,U,Y)
for correction_factor>0
local-delta- u=U out− U
local-delta- v=V out− V
The following examples for Fy, Fu and Fv can be given:
Example 1
For skin tone, suppose that cor-fac=32 at the center of the skin domain and that it is desired to have the all the skins lighter than what the original histogram gives:
Fy (cor_fac,delta — y )=delta — Y *(32+cor_fac)/32 for delta_Y>0
Fy (cor_fac,delta — y )=delta — Y *(32−cor_fac)/32 for delta_Y<0
Fu (cor_fac,delta — y,U,Y )= U *(delta — Y *(32+cor_fac)/32) Y for delta_Y<0 and
Fu (cor_fac,delta — y,U,Y )= U *(delta — Y *(32−cor_fac)/32)/ Y for delta_Y<0
Same for Fv.
In that case, for typical skin tone, one gets:
local_delta — Y= 2*delta — Y< for delta_Y<0 and
local_delta_Y=0 for delta_Y<0.
This means the skin is just made lighter. The U, V compensation is 100%.
Example 2
Suppose a domain where it is not desired to change the histogram itself, but rather to do the U, V compensation differently. In the rest of the picture, one has a 100% compensation, but in that specific domain, it is just nut desired to desaturate when delta_Y<0. In that case one would choose:
Fy (cor_fac,delta — y )=delta — y
Fu (cor_fac,delta — y,U,Y )= U *(delta — y *(32+cor_fac)/32)/ Y , for delta_y>0, and
Fu (cor_fac,delta — y,U,Y )=0 for delta_Y<=0
Same for Fv.
The important thing in Fy, Fu and Fv is the continuity of the function.
The system is especially suitable for special color and textures. It has been applied with success to improve the performance of histogram algorithms in skin tone regions. The weak points of the prior art global histogram algorithm considered were that darker skins were made too dark, and white spots on bright faces tended to be worsened. In that case, the correction factor determines the amount of correction depending on the position in the skin domain. It is equal to 0 at the limits of the domain and to 32 at the center of the skin domain.
The output of the local color/texture correction block 1 is:
LocalDelta — y =(Local_pos_gain( Y )*max(0,Delta — y +max(Delta — Y ,delta — yo )+Local_neg_gain( Y )*min(0,Delta — y +min(Delta — Y ,−delta — yo )−4*Delta — y )*cor_fac/128+Delta — y
where
delta_yo is given a small positive value;
Local_pos_gain(Y) and Local_neg_gain(Y) are as shown in FIG. 2 ;
LocalDelta_u=Delta_u; and
Local_Delta_v=Delta_v
This simple algorithm helps substantially to reduce the problems of the histogram algorithm in skin tones, without creating new artifacts, nor affecting the rest of the picture. A similar concept can be applied to improve the histogram performance in other color areas, like green. The system can also be applied to textures. The input of the local measurement consists then of the YUV of the current pixel and the YUV of the neighboring pixels.
Histogram modification algorithms are contrast/detail enhancement algorithms based on the luminance level distribution measured over the whole picture. Because the measurement is made globally and does not take into account textures or color components, histogram modification algorithms can be less optimized in special texture or color regions. In particular, skin tones, which are very critical for the human eye, can be degraded by histogram algorithms. Common cases are too much black-stretch in a dark skin or too much white stretch in an already very bright skin. (Herein, dark skins and bright skins are defined by the luminance level of the skin tone; they do not refer to any racial skin differences.) Therefore, there is a need to couple locally skin tone to the histogram correction.
The basic block diagram of the skin tone/histogram algorithm is again as shown in FIG. 1 . The local color/texture measurement block 1 now performs a skin-tone detection. The local color/texture correction block 5 now performs a histo-skin correction.
Basic criteria for the development of the algorithm are:
The coupling needs to remain simple. At the end of the original modification algorithm, a correction factor, coming from the skin tone detector allows a slight modulation of delta_y to local_delta_y;
This allows developing a coupling algorithm that is rather independent from the histogram modification algorithm chosen; and
Different histogram algorithms are likely to go wrong in a different way in skin tone regions. 6 parameters are introduced to allow any kind of situation to be corrected. They change the gain of the histogram modification locally or add an offset to get skins darker or brighter. Different corrections can be done for dark and bright skins. The parameters are fully described below. One could also eventually couple these parameters to the skin tone angle chosen in the skin tone correction color algorithm.
The skin tone detection is very close to the one in the color algorithm block. The parameter cor_fac determines the amount of correction depending on the position in the skin domain. At the center of the skin domain, cor_fac is at maximum at a value of 32. At the limit of the skin domain, for continuity reasons, it must be equal to 0.
6 parameters allow an adjustment of the coupling skin tone-histogram:
1. max_dark_skin defines the maximum level of luminance corresponding to dark skins. max_dark_skin can be adjusted from 0 to 31 (corresponds to the index in the LUT for a given Y level).
2. min_bright_skin defines the minimum level of luminance corresponding to bright skins. min_bright_skin can be adjusted from 0 to 31 (corresponds to the index in the LUT for a given Y level). For a proper working of the algorithm, min_bright_skin should be chosen equal or higher than max_dark_skin.
3. dark_pos_gain defines the type of skin tone-histogram correction for dark skins if dark skins are boosted (delta_y>0). It can be adjusted from 0 to 4 with:
LocalDelta_y = ( dark_pos _gain - 2 ) * cor_fac * Delta_y 64 + Delta_y for Delta_y > 0 and index ( Y ) < max_dark _skin
4. dark_neg_gain defines the type of skin tone-histogram correction for dark skins if dark skins are black-stretched (delta_y<0). It can be adjusted from 0 to 4 with:
LocalDelta_y = ( dark_neg _gain - 2 ) * correction_factor * Delta_y 64 + Delta_y for delta_y < 0 and index ( Y ) < max_dark _skin .
5. bright_pos_gain defines the type of skin tone-histogram correction for bright skins if bright skins are boosted (delta_y>0). It can be adjusted from 0 to 4 with:
LocalDelta_y = ( bright_pos _gain - 2 ) * correction_factor * Delta_y 64 + Delta_y for Delta_y > 0 and index ( Y ) > min_bright _skin .
6. bright_neg_gain defines the type of skin tone-histogram correction for bright skins if bright skin levels are reduced (delta_y<0). It can be adjusted from 0 to 4 with:
LocalDelta_y = ( bright_neg _gain - 2 ) * correction_factor * Delta_y 64 + Delta_y for Delta_y < 0 and index ( Y ) > min_bright _skin .
Continuity of the Formula Around Delta_y=0
These formulas are, however, not always suitable for delta_y around 0. For instance, the situation dark_pos_gain=4 and dark_neg_gain=0 means less black-stretch of dark skins and more boosting of dark skins. This can also be interpreted simply as Dark skins should be lighter. This leads to a new formula for abs(Delta_y)≦delta_yo:
LocalDelta_y = Delta_y + cor_fac 64 * ( ( dark_pos _gain - dark_neg _gain ) * delta_yo 2 + cor_fac 64 * ( ( dark_pos _gain + dark_neg _gain ) 2 - 2 ) * Delta_y )
A general formula for the whole delta_y range is:
LocalDelta — y =(dark_pos_gain*max(0,Delta — y +max(Delta — y ,delta — yo )+dark_neg_gain*min(0,Delta — y +min(Delta — Y ,−delta — yo )−4*Delta — y )*cor_fac/128+Delta — y
A similar formula is derived for bright skins around delta_y=0. In the algorithm, the value delta_yo was chosen equal to 5.
FIG. 3 shows Localdelta_y as function of delta_y, in the center of the skin domain (i.e., at cor_fac=32) for different combinations of dark_pos_gain and dark_neg_gain.
In this way, we get the possibility to reduce or increase the effect of histogram in dark skins, and to make dark skins lighter or darker. Similar possibilities are implemented for bright skins.
Transition Between Max_Dark_Skin and Min_Bright_Skin.
The choice of max_dark_skin and min_bright_skin allows to make different corrections on the histogram in low luminance and bright luminance regions. Normally, min_bright_skin is chosen higher than max_dark_skin. A smooth transition from dark parameters to bright parameters is made.
We then get general formulas over the whole luminance range:
Local_Delta
_Y
=
(
Local_pos
_gain
-
2
)
*
cor_fac
*
delta_y
64
+
delta_y
for
Delta_y
>
0
with
Local_pos
_gain
=
dark_pos
_gain
for
index
(
Y
)
≤
max_dark
_skin
Local_pos
_gain
=
dark_pos
_gain
+
(
bright_pos
_gain
-
dark_pos
_gain
)
4
for
max_dark
_skin
<
index
(
Y
)
≤
max_dark
_skin
+
min_bright
_skin
-
max_dark
_skin
)
4
Local_pos
_gain
=
dark_pos
_gain
+
(
bright_pos
_gain
-
dark_pos
_gain
)
2
for
max_dark
_skin
+
(
min_bright
_skin
-
max_dark
_skin
)
4
<
index
(
Y
)
≤
max_dark
_skin
+
(
min_bright
_skin
-
max_dark
_skin
)
2
Local_pos
_gain
=
bright_pos
_gain
+
(
dark_pos
_gain
-
bright_pos
_gain
)
2
for
max_dark
_skin
+
(
min_bright
_skin
-
max_dark
_skin
)
2
<
index
(
Y
)
≤
max_dark
_skin
+
3
*
(
min_bright
_skin
-
max_dark
_skin
)
4
Local_pos
_gain
=
bright_pos
_gain
+
(
dark_pos
_gain
-
bright_pos
_gain
)
4
for
max_dark
_skin
+
3
*
(
min_bright
_skin
-
max_dark
_skin
)
4
<
index
(
Y
)
≤
min_bright
_skin
Local_pos
_gain
=
bright_pos
_gain
for
index
(
Y
)
≥
min_bright
_skin
.
In the same way, dark_neg_gain and bright_neg_gain are combined to compute Local_neg_gain. Then Localdelta_Y is computed using the general formula:
LocalDelta — y =(Local_pos_gain*max(0,Delta — y +max(Delta — Y ,delta — yo )+Local_neg_gain*min(0,Delta — y +min(Delta — Y ,−delta — yo )−4*Delta — y )*cor_fac/128+Delta — y
The algorithm allows a modulation of the histogram modification effects in skin tone. Especially, when the dynamic contrast algorithm is used, it provides significant improvement in near-to-black skins and near-to-white skins.
The basics of the histogram are very simple. Care is only taken to provide the required continuity from dark to bright domain and from delta_y<0 to delta_y>0. The gain parameters were chosen, considering the already existing parameters for UV histogram compensation.
Histogram modification algorithms are optimized taking into account a large number of pictures. Often, compromises are made so that the algorithm performs properly in critical material, such as skin tone. The local coupling skin-tone to histogram could thus allow improving the histogram modification algorithm for the whole picture, without degrading the skin tones. The main limitation of the algorithm is actually the precision of the skin tone domain. Sometimes, the most correction would be required just within the limits of the skin tone domain. But, for continuity reasons, to avoid affecting non-skin areas, the correction has to be 0 at the limit of the skin domain. The correction proposed manages to improve most pictures.
FIG. 4 shows a detailed embodiment of the histo-skin correction block 5 , and how the skin detector 1 controls this block 5 . It is just an implementation of the above formulae indicating how the parameters dark_pos_gain, bright_pos_gain, dark_neg_gain, bright_neg_gain, min_bright_skin, max_dark_skin, and index are used to obtain local_delta_y from the correction factor cor_fac and delta_y.
In an embodiment of the skin tone detection block 1 , the correction factor cor_fac is derived from YUV as follows. Two axes are defined:
V ref1=4* U+ 3* V
V ref2=2.5* V− 2* U −min( Y, 256)−256
At Y constant, the skin tone is a parallelogram defined by abs(Vref 1 )<min (Y, 256) and abs(Vref 2 )<min (Y, 256). The formulas, of course, depend on the YUV format, the original format of which is 9 bits. The important thing is that it will always look like a parallelogram in a constant Y plane.
The correction factor at Y constant is a pyramid, more details of which will be set out below.
For applications other than skin tone, the goal is to keep to a simple geometric form in no more than 3 or 4 dimensions. The trick is to define good Vref 1 and Vref 2 axes. Basically, it is desired to find axes where the detection domain looks like a parallelogram so that the correction factor cor_fac is easy to express as a pyramid. If there are more than 4 dimensions, one has to deal with more continuity conditions and, in most of the cases, it means really trying to isolate a very small portion, very specific portion of the signal conditions. The detection must remain quite small compared to the whole domain, but still it must be relevant.
Experiments show that skin tones are concentrated in YUV as shown in FIG. 5 . Skin tones concentrate along an axis defined by 4*U+3*V=Vref 1 . Along Vref 1 =0, we get the highest concentration of typical skin tones, independently from Y.
Vref 1 >0 corresponds to more reddish skins.
Vref 1 <0 corresponds to mote yellowish skins.
It we look in the UV domain alone, we find that the skin tone area is getting smaller and smaller when Y decreases. Furthermore, the center of the area is moving towards smaller UV values when Y is decreased.
At Y constant, the skin domain can be represented as a parallelogram defined by:
| V ref1|<MaxSkinToneVariation
| V ref2|<MaxSaturationVariation
with V ref2=2.5* V− 2* U −min( Y, 256)
MaxSkinToneVariation=min( Y, 256)
MaxSaturationVariation=min( Y, 256)
FIGS. 6 and 7 show the skin tone domain in UV and Vref 1 , Vref 2 for Y>256. The detection angles defined by Vref 1 , Vref 2 and the limits defined by MaxSkinToneVariation, MaxSaturationVariation are a result of a compromise to include as much as possible skin tones in the domain and exclude as much as possible real yellow or red tones. Skin tones at (Vref 1 , Vref 2 )=(0,0) will be the most corrected in percentage to the histogram correction wanted specifically in skin tones. The further we go from the center of the domain, the lesser correction will be done.
The pyramid of FIG. 8 defines the amount of correction (scaled to 256). It is defined by the following algorithm, in which local_y, local_u, and local_v are the local YUV values:
Skin V Ref1=3*local — v+ 4*local — u
maximum skin correction SkinCorrMax=min(local — y, 256)
Skin V Ref2=5*local — v/ 2−2*local — u− 256
SkinDistance=min(max(2*abs(Skin V Ref1),2*abs(Skin V Ref2)),SkinCorrMax
cor_fac=min(32,64*(SkinCorrMax−SkinDistance)/max(SkinCorrMax,8))
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word “comprising” does not exclude the presence of elements or steps other than those listed in a claim. The word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements. The invention can be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In the device claim enumerating several means, several of these means can be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. | In a method of picture signal enhancement, a picture signal is subjected ( 3, 7 ) to a histogram-based picture signal modification based on a luminance level distribution over a whole picture or a first part of the picture, and the histogram-based picture signal modification is locally adjusted ( 5 ) in dependence on locally measured picture signal properties other than contrast and brightness, the locally measured picture signal relating to second parts of the picture that are each substantially smaller than the whole picture or the first part of the picture, the second parts being within the whole picture or the first part of the picture. Preferably, the second parts are individual pixels. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/205,283, filed Aug. 8, 2011, which is a continuation of U.S. application Ser. No. 10/845844 filed May 14, 2004, now issued as U.S. Pat. No. 7,993,387 on Aug. 9, 2011, the contents of each is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to stents having welded portions and atraumatic looped ends. The present invention also relates to such stents having their welded portions electro-chemically polished to reduce their profile and/or having a suture loop threaded at one or both extremities and/or being manufactured with a wire having a radiopaque core, and/or being fully or partially covered with a polymer such as silicone.
BACKGROUND OF THE INVENTION
[0003] Stents made from interconnecting, often braiding, elongate wires may be made less traumatic, i.e., atraumatic, by closing the loose wire ends at the ends of the stents. The loose wire ends have typically been closed by mechanical means, such as by clamps, for example clamped microtubes, or by welding. Such mechanical means, however, provide regions of high profile as compared to the other regions of the stents, see e.g., U.S. Pat. No. 6,083,257. The high profile regions are undesirable, often leading to deployment concerns, including higher deployment forces.
[0004] Electropolishing or electro-chemical polishing of laser cut nitinol stents to improve surface finishes has been previously mentioned, see e.g. U.S. Pat. No. 6,325,825 B1 and U.S. Patent Application Publication No. 2003/0024534 A1. Further, electro-polishing or electrochemical polishing services are available, see e.g. from Admedes Schuessler GmbH. Such polishing, however, has not been attempted to alleviate the above-discussed deployment concerns.
[0005] The present invention provides a stent made from elongate wires in a closed-end design while avoiding the disadvantages of the prior art. More particularly, the present invention is directed to certain advantageous closed-end stent loop designs having reduced profiles to lower deployment forces and ease deployment of the stent.
SUMMARY OF THE INVENTION
[0006] In one aspect of the present invention is a method for making an implantable stent. The method comprises the steps of (i) providing a plurality of elongate stent wires; (ii) forming the wires into a hollow tubular structure having opposed first and second open ends; (iii) terminating the wires at the second end; (iv) aligning the wires at the second end into a plurality of mated adjacent wires to define a plurality of abutting regions; (v) welding the mated adjacent wires to one and the other at the abutting regions to define a plurality of welds; and, optionally, (vi) chemically or electro-chemically removing a portion of the welding material from the plurality of welds. Desirably, the mated adjacent wires are substantially parallel to one and the other at the abutting regions.
[0007] In this aspect of the present invention, the step of welding may include the step of providing an inert gas proximal to the weld areas. Further, the step of welding includes laser welding, electron beam welding, resistance welding, tungsten inert gas welding, metal inert gas welding, and combinations thereof.
[0008] Desirably, the step of forming the tubular structure comprises braiding the wires, winding the wires, knitting the wires, and combinations thereof, preferably braiding the wires. The material of the wires and the material of the welds may be the same type of material.
[0009] Further, the stent wire may include a radiopaque material.
[0010] The step of chemically or electro-chemically removing the portion of the welding material may include chemical polishing or etching, chemical deburring, electrochemical polishing or etching, jet-electropolishing and combinations thereof. The step of electro-chemically removing the portion of the welding material further includes the step of providing an electrolyte, where the electrolyte is selected from the group consisting of NaClO 3 electrolyte, NaNO 3 electrolyte, NaCl electrolyte, Na 2 Cr 2 O 7 electrolyte, HOCH 2 CH 2 OH electrolyte, and combinations thereof.
[0011] In further detail, the step of electro-chemically removing the portion of the welding material may further include the step of (i) providing an electrolyte; (ii) placing a cathode into the electrolyte; (iii) placing a portion of the stent having the welding material into the electrolyte; (iv) providing an electrical voltage or current so that the cathode is negatively charged and the stent portion is positively charged; and (v) partially dissolving the portion of the stent exposed to the electrolyte.
[0012] In another aspect of the present invention, the method of making the stent may further include the steps of (i) extending at least one of the mated stent wires to provide an extended stent wire; (ii) looping the extended stent wire so the extended end abuts a proximal pair of stent wires; and (iii) welding extended and looped wire to the proximal pair of wires. Desirably, the step of looping includes forming the wire into an arch with equilateral sides, having an apex, but not having other sharp bends. Desirably, the step of looping includes forming the wire into an equilateral arch having one vertex having similar curvatures on either side of the one vertex, where the equilateral arch does not contain a second vertex having dissimilar curvatures on either side of the second vertex.
[0013] In another aspect of the present invention, the method of making the stent may further include the steps of (i) extending at least one of the mated stent wires past the abutting regions to provide an extended stent wire; and (ii) looping the extended stent wire at its extended end to form a coil thereat. A plurality of extended wires may also be formed into one coil or pig tail.
[0014] Desirably, the elongate wires comprise biocompatible materials selected from the group consisting of nitinol, stainless steel, cobalt-based alloy such as Elgiloy, platinum, gold, titanium, tantalum, niobium, and combinations thereof, preferably nitinol. The elongate wires may be composite wires for improved radiopacity, such as having an inner core of tantalum, gold, platinum, iridium or combination of thereof and an outer layer or member of nitinol.
[0015] In another aspect of the present invention, an implantable stent is provided. The stent of this aspect of the present invention may include a plurality of wires arranged to form a hollow tubular structure having a tubular wall to define an interior surface and an exterior surface and having opposed open first and second ends, where the wires terminate at the second open end ends and adjacently abutting wires are welded at the second open end with a welding material to provide welds, and further where at least a portion of the welded material has been removed to reduce the profile of the welds. Desirably, the portion of welded material has been removed by chemical or electro-chemical polishing. Preferably, at least 25 to 50% by weight of the stent material at or around the weld location has been removed. The reduced profile of the welds are from about 5 to about 50 linear percent of a diameter of the stent wires.
[0016] The stent includes wires made from biocompatible materials, such as nitinol, stainless steel, cobalt-based alloy such as Elgiloy, platinum, gold, titanium, tantalum, niobium, and combinations thereof. The weld material and the wire material may also be the same, for example nitinol. Further, the elongate wires have an inner core of tantalum gold, platinum, iridium or combination of thereof and an outer member of nitinol.
[0017] In another aspect of the present invention, at least one some of the adjacently abutting stent wires are extended past the welds and looped into an arch with equilateral sides having an apex, but not having other sharp bends, or in other words at least some of the adjacently abutting stent wires are extended past the welds and looped into an arch with equilateral sides having one vertex having similar curvatures on either side of the one vertex, where the arch design does not contain a second vertex having dissimilar curvatures on either side of the second vertex. Alternatively, at least some of the adjacently abutting stent wires are extended past the welds and looped to form a coil thereat in the shape of a pig tail. Still alternatively, at least some of the adjacently abutting stent wires are extended past the welds and looped to form one coil thereat.
[0018] The stent wires may be coated, for example coated with silicone. Further, the stent may be fully or partially covered with a polymeric covering, such as silicone, in order to prevent tissue or tumor ingrowth.
[0019] The stent may further include a hollow tubular graft disposed over the interior or the exterior surface. The graft may be a polymeric material, for example, a polyester, a polypropylene, a polyethylene, a polyurethane, a polynaphthalene, a polytetrafluoroethylene, an expanded polytetrafluoroethylene, a silicone, and combinations thereof.
[0020] Desirably, the stent is a braided stent.
[0021] The stent may further include a polymeric ring disposed over the exterior surface at the second open end. Additionally, the stent may further include a suture secured to one of the open ends. Such suture or sutures are useful for positioning, repositioning, and/or removing the stent. The suture can be a metallic, polymeric or textile suture loop threaded through the stent loops at one or both extremities of the stent. The suture loop may include a protruding part to help facilitate the capture or grabbing of the stent end.
[0022] In another aspect of the present invention, an implantable stent includes a plurality of wires arranged to form a hollow tubular structure having a tubular wall to define an interior surface and an exterior surface and having opposed open first and second ends, where the wires terminate at the second open end ends and adjacently abutting wires are welded at the second open end with a welding material to provide welds, and further where at least a portion of the welded material has been removed by chemical or electrochemical polishing to reduce the profile of the welds.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 is a perspective view of a hollow, tubular stent according to the present invention.
[0024] FIG. 2 is an expanded view of a wall portion of the stent of FIG. 1 taken along the 2 - 2 axis showing a plurality of stent wires.
[0025] FIG. 3 depicts a braided stent with a closed-end loop design having a plurality of welds at the closed end according to the present invention.
[0026] FIG. 4 is an expanded view of a weld of FIG. 3 .
[0027] FIG. 5 depicts a weld adjoining two stent wires according to the present invention.
[0028] FIG. 5A depicts a weld adjoining two stent wires having an insulator or photoresist on selected stent wire portions according to the present invention.
[0029] FIG. 6 is a cross-sectional view of the adjoining stent wires of FIG. 5 taken along the 6 - 6 axis.
[0030] FIG. 7 is a cross-sectional view of the welded stent wires of FIG. 5 taken along the 7 - 7 axis.
[0031] FIG. 8 is a cross-sectional view of the welded stent wires of FIG. 7 after chemical or electrochemical polishing.
[0032] FIG. 9 is a schematic depiction of an electro-chemical polishing cell according to the present invention.
[0033] FIGS. 10-14 depict an arch with equilateral sides and an apex in a closed-end loop design according to the present invention.
[0034] FIG. 15 depicts another embodiment according to the present invention of a closed-end loop design of the present invention having a plurality of coils at the closed end.
[0035] FIG. 16 depicts yet another embodiment according to the present invention of a closed-end loop design of the present invention having one coil or pigtail at the closed end.
[0036] FIGS. 17-18 depict yet another embodiment according to the present invention of a closed-end design having a band disposed over the stent wires at the closed end.
[0037] FIG. 19 depicts a mandrel having shaped pins for forming the closed loops of FIGS. 10-14 .
[0038] FIG. 20 depicts a stent having a covering of silicone according to the present invention.
[0039] FIG. 21 is a cross-sectional view if the stent of FIG. 20 showing an outer covering of silicone about the stent.
[0040] FIG. 22 is a cross-sectional view if the stent of FIG. 20 showing an inner covering of silicone about the stent.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0041] The present invention overcomes the deficiencies of the prior art by providing, among other things, low profile stent welds that reduce stent deployment forces. FIG. 1 depicts stent 10 of the present invention. Stent 10 is a hollow tubular structure having opposed open ends 12 , 14 and having a tubular wall 16 therebetween. A portion of the tubular wall 16 is depicted in FIG. 2 as having a plurality of elongate wires 18 formed into the tubular wall 16 . The elongate wires 18 traverse the length of the stent 10 in a direction traverse to the longitudinal length of the stent 10 . The elongate wires 18 may be formed into the tubular wall 16 by braiding the wires 18 , winding the wires 18 , knitting the wires 18 , and combinations. Preferably, the wires 18 are braided to form the tubular wall 16 .
[0042] A welded stent 10 ′ according to the present invention is depicted in FIG. 3 . The elongate wires 18 terminating at open end 12 are mated and adjacently mated wires are secured to one and the other by welds 20 . The joining of three adjacently mated wires 18 and the welding thereat is depicted in further detailed in FIG. 4 . The positioning of adjacently mated wires to form closed-loop end designs, excluding the closed-end arch loop design of the present invention which is described below, is further described in U.S. Application No. 60/472,929, filed May 23, 2003, which represents U.S. application Ser. No. 10/852,495 and which published as US 2005/0049682 A1, the contents of which are incorporated herein by reference. The weld 20 may be a low profile weld, i.e., a weld with a reduced welding zone as compared to stent welds of the prior art. The stent 10 ′ depicted in FIG. 3 includes 24 wires 18 of nitinol or nitinol-containing material. The wires are relatively thin at a diameter of about 0.011 inches. The number of wires and the diameters of the wires, which may be the same or different, depicted in FIG. 3 are not limiting, and other numbers of wires and other wire diameters may suitably be used.
[0043] A pair of adjacently welded wires according to the present invention is depicted in FIGS. 5-8 . Weld 24 securably joins adjacently mated stent wires 22 . As compared to the prior art, the weld 24 of the present invention has a significant reduction in the amount of welding material in weld 24 . Desirably, weld 24 has at least about 25% or less welding material than prior art welds, for example from about 25% to about 50% less welding material. Alternatively, the weld 24 desirably has a profile, i.e., a depth d 3 and/or a width d 4 , that is less than the diameter, d 1 , of the wire 22 . Yet alternatively, or in addition to, the welds 24 of the present invention have a profile of about 150 microns or less, preferably from about 50 microns to about 150 microns. Yet alternatively, or in addition to, the weld 24 ′ of the present invention and portions of the stent wires 22 ′ proximal to the welds 24 ′ have a reduced profile where the profile of weld 24 ′ is lower than the profile of weld 24 and where the diameter, d 2 , of the proximal stent portions 22 ′ is less than the diameter, d 1 , of stent wire portions 22 . The mass and volume of the weld 24 ′ and/or stent portions 22 ′ is suitably reduced by chemical or electrochemical polishing. Reduced profile welds 24 , 24 ′ of the present invention overcome the difficulty of constraining the stent 10 , 10 ′ on a delivery device (not shown) by removing excess weld material that would otherwise increase localized constraining forces at the weld locations as compared to other portions of the stent 10 , 10 ′.
[0044] Useful welding methods include, but are not limited to, laser welding, electron beam welding, resistance welding, tungsten inert gas welding, metal inert gas welding and combinations thereof. In laser and electron beam welding the wires are partially melted by the energy provided by the laser or electron beam. In gas tungsten arc welding (GTAW or TIG welding), an arc is formed between an electrode, typically tungsten, and the metal being welded. In metal inert gas (MIG) welding, an arc is generated between a filler electrode and the metal being welded with metal melted from the filler electrode being added to the metal being welded. Resistance welding uses the application of electric current and sometimes mechanical pressure to create a weld between two pieces of metal. The weld areas may be shielded with an inert gas. Suitable, but non-limiting, inert gasses include argon and argon/gas admixtures, such as argon/hydrogen or argon/helium.
[0045] FIG. 9 depicts an electro-chemical cell 30 for removing weld material to thereby form the low profile weld 24 , 24 ′ of the present invention. The cell 30 includes an electrolyte 32 contained within a container 34 . The stent 10 with welds 24 , 24 ′ at stent end 12 is placed within the electrolyte 32 . A cathode 36 is also placed within the electrolyte 32 . A wire 38 connects the cathode 36 to the negative terminal 40 of voltage or current source 46 . A wire 42 connects the stent 10 to the positive terminal 44 of the voltage or current source 46 . Upon application of voltage or current from the source 46 the cell 30 becomes operational. Material, such as weld material, is dissolved from the stent 10 into the electrolyte 32 . Useful electrolytes include NaClO 3 electrolyte, NaNO 3 electrolyte, NaCl electrolyte, Na 2 Cr 2 O 7 electrolyte, HOCH 2 CH 2 OH electrolyte and combinations thereof. Typical, but non-limiting, current densities are in the magnitude of about 50 to about 150 amps/cm 2 . The electrolyte 32 may be in motion at low velocities or unstirred. As the anode metal is dissolved electrochemically, the dissolution rate is not influenced by the hardness or other physical characteristics of the metal.
[0046] Desirably, the wires 22 are made from nitinol, stainless steel, cobalt-based alloy such as Elgiloy, platinum, gold, titanium, tantalum, niobium, and combinations thereof. Further, the wires 22 have an inner core of tantalum gold, platinum, iridium or combination of thereof and an outer member or layer of nitinol to provide a composite wire for improved radiocapicity or visibility. Further details of such composite wires may be found in U.S. Patent Application Publication 2002/0035396 A1, the contents of which is incorporated herein by reference. Preferably, the wires 22 are made from nitinol. Further, the filling weld material, if required by welding processes such as MIG, may also be made from nitinol, stainless steel, cobalt-based alloy such as Elgiloy, platinum, gold, titanium, tantalum, niobium, and combinations thereof, preferably nitinol. The material of the cathode is no critical and can be made out of any suitable metal. The filling weld material and the wire 22 may be made of the same material, for example nitinol.
[0047] As the chemical electro-chemical polishing 30 removes material from portions of the stent 10 that are disposed within the electrolyte 32 , there are several means to selectively remove material from the stent 10 , such as welds 24 , 24 ′, burrs or other imperfections (not shown), and the like. One technique for selectively removing material is through the use of a photoresist or insulator, which is an organic polymer or resin that can be applied to selective areas of the stent 10 to avoid the electrochemical polishing of covered parts 30 as the photoresist insulates the selected from the action of the electrolyte. For example, as depicted in FIG. 5A , portions of the stent wires 22 may be coated with a photoresist prior to placement in the cell 30 . After chemical or electro-chemical polishing is completed the photoresist may be removed by application of a suitable solvent. Alternatively, jet electro-chemical polishing or etching could be used to specifically etch weld regions. Jet etching includes the localized application of electrolyte at moderate velocity, such as about 3 to about 30 m/s, to selectively polish desired areas, such as stent welds.
[0048] Alternatively, chemical polishing, chemical etching and the like may be used to remove portions of the weld 24 , 24 ′ and optionally portions of the stent wire 22 . Chemical polishing or etching is similar to the above described electrochemical methods, expect an oxidizing acid is added to the electrolyte and associated equipment (current or voltage source, cathode, etc.) is optionally not necessary. Useful, but not limiting, oxidizing acid-containing electrolytes include electrolytes having hydrofluoric acid, nitric acid, and combinations thereof.
[0049] The present invention, however, is not limited to low profile welds just at terminatingly adjacent wires, such as wires 22 of FIG. 5 or 5 A. As depicted in FIGS. 10-14 , certain stent wires 56 , 62 may be extended beyond adjacent wires 50 , 64 , and then looped back to proximal wires 52 , 60 and 58 , 64 , respectively. Adjacent portions of wires 50 and 56 are abuttingly disposed at abutting region 68 . Similarly, adjacent portions of wires 52 and 60 and the adjacent portion of the extended loop portion 66 are abuttingly disposed at abutting region 70 ; adjacent portions of wires 54 and 62 are abuttingly disposed at abutting region 72 ; and adjacent portions of wires 58 and 64 and the adjacent portion of the extended loop portion 67 are abuttingly disposed at abutting region 74 . Desirably, the abuttingly disposed wire portions in the abutting regions are substantially parallel to one and the other, for example, but not limited to, being within about plus or minus 10 degrees of parallelism to one and the other, preferably, but not limited to within about plus or minus 5 degrees of parallelism.
[0050] As depicted in FIG. 11 , the wires at the abutting regions 68 , 70 , 72 , 74 may be secured by welds 76 . Desirably, welds 76 are low profile welds having low profiles from electrochemical polishing according to the present invention. In another aspect of the invention, each abutting region is a weld region of the wire and each region of the wire that does not form a part of a weld is a non-weld region of the wire. As can be seen for example in FIGS. 4-5A , 10 - 11 , 15 - 17 , and 19 , at least two weld regions form a part of a weld 20 , 92 . As shown for example in FIG. 11 , some welds 76 have two weld regions and other welds 76 have three weld regions. As shown in the figures, a wire can have one or more weld regions distributed along the length of the wire. The weld region of a wire can form an end region of the wire or can be a distance away from an end of the wires, as shown for example by wires 50 and 56 of FIGS. 10-11 . An example of a non-weld region is loop 66 of wire 56 , which extends between two weld regions.
[0051] Desirably, the extended loop portions 66 , 67 are of an arch with equilateral sides design, which can be referred to as a cathedral type of arch or loop. As depicted in FIG. 12 , the equilaterally arched loop 78 has an apex or vertex 80 . As used herein, the term “vertex” and its variants refer to the intersection of two geometric lines or curves. As used herein, the term “apex” and its variants refer to a vertex at the top or summit of a loop. Desirably, the equilaterally arched loop 78 does not have any bends, which are defined as areas having dissimilar curvatures on either side of a point, except for the apex 80 . In other words, the equilaterally arched loop 78 has an apex, but not other sharp bends. Desirably, the equilaterally arched loop 78 has one vertex (or apex 80 ) having similar curvatures on either side of the one vertex (or apex 80 ), but does not contain a second vertex having dissimilar curvatures on either side of the second vertex.
[0052] The equilaterally arched loop design offers several advantages, including reduced deployment force, as compared to prior art loop designs having a plurality of vertices or sharp bends. When a stent is constrained on or in a delivery system (not shown) the multiple sharp bends in the end loops of the stent typically impinge on the wall of the delivery system and become slightly imbedded thereat, thereby distorting the outer sheath of the delivery system. This results in significantly greater deployment force values. Further, as the equilaterally arched loop has only one sharp bend, i.e., its apex, and is defined otherwise by a gradual curvature, the gradual curvature portions do not become imbedded in the wall of the delivery system, thereby significantly reducing the resultant deployment force.
[0053] In another aspect of the present invention as depicted in FIG. 13 , an equilaterally arched loop 82 may have an apex 84 and vertices 86 having substantially straight line portions 88 . In such a case, the vertices 86 and the straight line portions 88 have low profile welds 90 thereover to adjoin other adjacently abutting stent wires (not shown). The equilaterally arched loops 66 , 67 , 78 , 82 of the present invention may be suitably formed by winding their stent wires about shaped pins 98 on a mandrel 100 as depicted in FIG. 19 . Further, either or both of the ends 12 , 14 of the stent 10 , 10 ′, including end 12 with equilaterally arched loops 66 , 67 , 78 , 82 , may have a suture or sutures (not shown) attached thereto. Such sutures are useful for positioning, repositioning, and/or removing the stent 10 , 10 ′.
[0054] In still a further aspect of the present invention, the stent 10 may have other designs at open end 12 that are useful for positioning, repositioning, and/or removing stent 10 . As depicted in FIG. 15 , wires may be extended from all or some of the adjacent wire engaging portions 92 . The ends of the extended wires may be formed into coils 90 . As depicted in FIG. 16 , wires may be extended from all or some of the adjacent wire engaging portions 92 . The ends of the extended wires may be formed into a coil 94 , which is in the shape of a hook and commonly referred to as a pigtail. Additionally, the stent 10 shown in FIG. 16 has a group of welds positioned a distance away from the coil 94 . Each weld 92 shown in FIG. 16 has two weld regions with one weld region being an end region of a wire and the other weld region being a distance away from an end of a wire. Still further, the open end 12 of stent 10 may be of reduced diameter as compared to the other portions of the stent 10 . The reduced diameter portion facilitates access to the stent end 12 for positioning, repositioning, and/or removing stent 10 . The stent end 12 of the stent 10 of FIG. 17 may include any of the previously described loops or coils thereat. Alternatively, or in addition to, the stent end 12 , as depicted in FIG. 18 , may have a band 96 disposed thereover, which is also useful for positioning, repositioning, and/or removing stent 10 . Band 96 may be made of any biocompatible material, including polymers, plastics and metals. The band 96 may be attached to the stent end 12 by adhesive, mechanical or physical means, such as adhesive bonding, welding, suturing, fusing, and the like.
[0055] In another aspect of the invention, the stent comprises groups of welds at different longitudinal positions. For example, the stent shown in FIG. 15 has two groups of welds 92 : a first weld group at a first longitudinal distance away from the coils 90 , and a second weld group at a second longitudinal distance away from the coils 90 , with the first weld group being between positioned between the coils and the second weld group. As shown in FIG. 15 , the welds of the first weld group are longitudinally aligned and the welds of the second weld group are longitudinally aligned. Each weld 92 has two weld regions with one weld region being an end region of a wire and the other weld region being a distance away from an end of a wire. As can be seen in FIG. 15 , each wire forming a coil 90 has a first weld region and a second weld region. The first weld region of a coil forming wire is a first distance away from the coil forming end region of the wire and the first weld region forms a part of a weld of the first weld group. The second weld region of a coil forming wire is a second distance away from the coil forming end region and the second weld region forms a part of a weld of the second weld group.
[0056] In another aspect of the invention, the stent 10 shown in FIG. 15 comprises a plurality of wires comprising first wires, second wires, and third wires. As can be seen in FIG. 15 , the first wires have an end positioned a first distance from the coils 90 ; the second wires have an end positioned a second distance from the coils 90 where the second distance is less than the first distance; and the third wires have an end that forms a part of a coil 90 . Each weld of the above described first weld group of the stent 10 has one third wire and one second wire. The welds of the above described second weld group of the stent 10 can be subdivided into a first subgroup and a second subgroup, with each weld of the first subgroup having one first wire and one second wire and each weld of the second subgroup having one first wire and one third wire.
[0057] As depicted in FIG. 20 , the stent 10 may be fully, substantially or partially covered with silicone 102 in also the form of a tubular structure. The silicone 102 may be disposed on external surfaces 104 of the stent 10 , as depicted in FIG. 21 , or disposed on the internal surfaces 106 of the stent 10 , as depicted in FIG. 22 , or combinations thereof.
[0058] With any embodiment of the stent 10 , 10 ′ is usable to maintain patency of a bodily vessel, such as in the coronary or peripheral vasculature, esophagus, trachea, bronchi colon, biliary tract, urinary tract, prostate, brain, and the like. Also, the stent 10 , 10 ′ may be treated with any of the following: anti-thrombogenic agents (such as heparin, heparin derivatives, urokinase, and PPack (dextrophenylalanine proline arginine chloromethylketone); anti-proliferative agents (such as enoxaprin, angiopeptin, or monoclonal antibodies capable of blocking smooth muscle cell proliferation, hirudin, and acetylsalicylic acid); anti-inflammatory agents (such as dexamethasone, prednisolone, corticosterone, budesonide, estrogen, sulfasalazine, and mesalamine); antineoplastic/antiproliferative/anti-miotic agents (such as paclitaxel, 5-fluorouracil, cisplatin, vinblastine, vincristine, epothilones, endostatin, angiostatin and thymidine kinase inhibitors); anesthetic agents (such as lidocaine, bupivacaine, and ropivacaine); anti-coagulants (such as D-Phe-Pro-Arg chloromethyl keton, an RGD peptide-containing compound, heparin, antithrombin compounds, platelet receptor antagonists, anti-thrombin antibodies, anti-platelet receptor antibodies, aspirin, prostaglandin inhibitors, platelet inhibitors and tick antiplatelet peptides); vascular cell growth promotors (such as growth factor inhibitors, growth factor receptor antagonists, transcriptional activators, and translational promoters); vascular cell growth inhibitors (such as growth factor inhibitors, growth factor receptor antagonists, transcriptional repressors, translational repressors, replication inhibitors, inhibitory antibodies, antibodies directed against growth factors, bifunctional molecules consisting of a growth factor and a cytotoxin, bifunctional molecules consisting of an antibody and a cytotoxin); cholesterol-lowering agents; vasodilating agents; and agents which interfere with endogenous vascoactive mechanisms.
[0059] The invention being thus described, it will now be evident to those skilled in the art that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are intended to be included within the scope of the following claims. | A prosthesis including a composite wire forming a mesh, the mesh having a variable diameter wherein at least one end region has a larger diameter than a middle portion; the mesh having an exterior surface and an interior surface, wherein at least one of the surfaces is covered with silicone; and a retrieval loop positioned at at least one end of the mesh. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention is in the field of recombinant DNA technology and relates to avipox promoters useful for the expression of foreign DNA inserted into a fowlpox virus vector.
2. Description of the Prior Art
Poxviruses are large viruses with a complex morphology containing linear double-stranded DNA genomes. They are among the few groups of DNA viruses that replicate within the cytoplasm of the cell. They are subclassified into six genera: orthopoxviruses, avipoxviruses, capripoxviruses, leporipoxviruses, parapoxviruses and entomopoxviruses. Vaccinia virus (VV), an orthopoxvirus, is the most widely studied of the poxviruses, and is the subject of U.S. Pat. No. 4,603,112 (Paoletti et al.,). Fowlpox virus (FPV) is an avipoxvirus or arian poxvirus.
Recent advances in recombinant DNA technology have allowed VV to be used as a vector to carry and express foreign genes. Foreign DNA is introduced into the VV genome by a process of homologous recombination. Homologous recombination involves essentially (1) pre-selecting a length of the VV genome in some region which does not impair the replication and normal functioning of the virus (hereinafter called a "non-essential region"), (2) making a construct comprising a VV promoter and a length of foreign DNA within a copy of the non-essential region (NER) so that the foreign DNA is under the control of the promoter and so that the promoter-foreign DNA combination is flanked by extensive sequences of non-essential region of VV DNA, (3) co-infecting appropriate tissue culture cells with the VV and with the construct and (4) selecting cells containing VV in which the pre-selected length has been recombined in vivo so that it is replaced in the genome by the construct DNA. The recombinant VV expresses the foreign gene in vivo, stimulating the immunity to the protein in an appropriate host. The procedure has considerable potential for use in vaccination.
More recently, similar technology has been applied to fowlpox virus (FPV). Although VV promoters have been used successfully in laboratory constructs of FPV, it is undesirable to incorporate elements of such VV, an orthopoxvirus which has a wide host range recombinant vaccine, for fear of recombination events which could pose a health risk. There is therefore a need to develop FPV promoters for use in recombinant FPV. Certain FPV promoters have been described in UK Patent Application Publication No. 2211504A or PCT Application WO/89/03879 (NRDC). However, each promoter has its own peculiar characteristics of strength and timing of promotion. A choice of promoters is therefore very highly desirable.
One of the major proteins of VV is the 4a core protein, DNA coding for which has been sequenced by E. Van Meir and R. Wittek, Archives of Virology 102, 19-27 (1988). The mRNA for such a protein might be strongly promoted if it exists in FPV. The task of locating and cloning new FPV promoters is made more difficult because only very limited data have been published about the DNA sequence of the FPV genome. A greater amount of the VV genome has been sequenced, but the FPV genome is much larger than that of VV. Estimates have put it at from 240 to 360 kbp compared with 186 kbp in VV. There is no publicly available library of FPV DNA. Homologies and heterologies between a few parts of the FPV and VV genomes are known.
SUMMARY OF THE INVENTION
It has now been found that FPV does have a counterpart to the 4a protein of VV and that it is preceded by a strong promoter.
The science of promoters of poxvirus DNA is at present poorly understood. It is known that certain regions to the 5' or "upstream" end of a gene serve to assist in transcribing genomic DNA into messenger RNA by binding the RNA polymerase involved in the transcription so that the mRNA which contains the start codon of the gene can be transcribed. Such upstream regions are referred to as the "promoter". It is often not possible a priori to say for certain which nucleotides of the upstream sequence are essential and which are inessential for promotion, nor is the minimum or maximum length of the promoter known with great precision. Although this lack of precision in the whereabouts and length of the promoter might at first sight seem rather unsatisfactory, it is not a problem in practice, since there is normally no harm in Including additional DNA beyond the region which serves to transcribe the DNA. Further as described later, it is possible by tedious experiment to determine this region more precisely. In all these circumstances, it is therefore more appropriate to define the promoter by reference to the gene which it precedes, rather than by reference to the sequence of the promoter.
The 4a gene can be defined in various ways, always remembering, of course, that there will doubtless be minor differences in its sequence between one strain or type of FPV and another, or between different avipoxviruses. One convenient, arbitrary, way of defining it is by reference to an appropriate length of the amino acid sequence which it encodes. It may reasonably be assumed that the first 20 or, more preferably, the first 30 amino acids, say, would form a unique sequence in FPV. Accordingly, one convenient definition of the FPV 4a gene is the gene which encodes a protein of 800-1000 amino acids (especially 860-920 amino acids) in a sequence (SEQ ID NO: 1) beginning
Met Met Leu Ile Lys Asn Ile Val Thr Leu
Asp Gln Leu Glu Ser Ser Asp Tyr Leu Tyr.
It will be appreciated, of course, that variations in the first 20 amino acids are likely to occur between different FPV strains. Probably there would be at least 90% homology over the whole gene, but there may well be less homology over the first 20 amino acids, perhaps up to 3 or 4 differences. It is confidently believed, however, that no one skilled in the field will be in any doubt as to which gene is intended, whatever the precise degree of aberration in the amino acid sequence of the first 20 or 30.
The FP4a gene is believed to lie in a central region of the genome, but its location is unknown at present. Applicants have identified it by a laborious procedure which comprised making a random library of part of the FPV genome, sequencing it, comparing the sequences with those of the VV 4a gene, and fortunately finding that sequences having some degree of homology were present in the library. Although the degree of homology at the amino acid level measured over the first 302 amino acids, was only 33%, successful identification was achieved.
The invention includes a DNA molecule which consists substantially of the non-coding DNA to the 5'-end of the 4a gene and comprising the promoter thereof. "Non-coding" means not coding for the 4a gene: it could code for another gene (and appears to do so) as well as serving as a promoter for the 4a gene. Any reasonable length of such DNA, typically up to 200, usually up to 160, and especially up to 100 nucleotides (or base-pairs in the case of ds DNA) of the 5'-end (even if it codes for DNA within the next gene along the genome), is herein referred to as "promoter DNA".
The invention also includes a recombination vector comprising a cloning vector containing a non-essential region (NER) sequence of FPV, said NER being interrupted by DNA which consists of or includes (a) promoter DNA of the invention, followed by (b) a foreign gene (i.e. a gene which it is desired to insert into the FPV vector) transcribable by the promoter.
In one particular aspect, the invention includes a recombination vector which comprises in order:
(1) a first homologously recombinable sequence of the fowlpox virus (FPV) genome,
(2) a sequence within a first portion of a non-essential region (NER) of the FPV genome,
(3) promoter DNA according to the invention,
(4) a foreign gene transcribably downstream of the promoter (whereby when the fowlpox virus RNA polymerase binds to the promoter it will transcribe the foreign gene into mRNA) and
(5) a sequence within a second portion of the same NER of the FPV genome, the first and second sequences being in the same relative orientation as are the first and second portions of the NER within the FPV genome, and
(6) a second homologously recombinable sequence of the FPV genome, said sequences (1) and (6) flanking the NER in the FPV genome and being in the same relative orientation in the recombination vector as they are within the FPV genome.
In another aspect, the invention includes a DNA construct which comprises a promoter of the invention transcribably linked to a foreign gene. Such a construct or "cassette" can be inserted in a cloning vector, which can then be used as a recombinant vector useful in preparing a recombination vector of the invention.
The invention further includes hosts harbouring the recombination and recombinant vectors of the invention, especially a bacterial host harbouring a plasmid vector.
The invention is further directed to a recombinant FPV which is the product of homologous recombination of FPV with a recombination vector of the invention containing a foreign gene; the process of homologous recombination; animal cells infected with such a recombinant FPV; a process of in vitro culture of these infected cells; and a method of vaccinating a responsive animal, especially a chicken, which comprises inoculating it with the recombination vector of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
While the precise length of DNA required for promotion is not known, it is generally reckoned to be up to 100 base pairs from the RNA start site, but this can be as much as 60 base pairs away from the gene start site (the ATG codon). Accordingly a DNA sequence contained within 160 base pairs, less preferably 100 bp, to the 5'-end of the gene (immediately preceding the start codon) is of particular interest for the purposes of the invention. The DNA sequences of these 160 base pairs are shown below (arbitarily divided into blocks of 10 for ease of reading) for the FPV 4a and in the 5' to 3' direction. ##STR1## In the above sequences an ATG start codon follows on at the right-hand or 3'-end.
Just how much of the 5'-non-coding sequence is necessary for efficient promotion is not known precisely. However, experiments can be carried out to answer this question, and In fact some have been performed for VV. These are fully described in the above-mentioned UK Patent Application Publication 2211504A, on pages 12 and 13, the disclosure of which is herein incorporated by reference.
Since some changes In sequence are permissible without loss of the promotional effect, it will be appreciated that it is necessary that the invention should cover sequences which are variant, by substitution as well as by deletion or addition from the non-coding sequences of preferred length up to 160 bp shown above. Incidentally, although the promoter has been referred to herein as an FPV promoter, it will be appreciated that similar 4a genes are virtually certain to be found in other avipoxviruses, such as canarypox or dovepox and to have similar promoters. These are included within the present Invention as being obvious equivalents of FPV.
The recombination vector could contain additional sequence to that herein referred to as promoter DNA. Additional sequence could comprise (a) additional sequence added to the 5'-end of the 60 bp (b) sequence Inserted into the 160 bp without destroying promoter activity or (c) part of the sequence of the FPV gene (inclusive of the ATG initiation codon and onwards), e.g. up to 100 bp thereof.
The above experiments require testing for the efficiency of the promoter. It is not necessary for this purpose to introduce a promoter-gene construct into FPV and monitor expression of the gene product. A shorter method, known as transient assay, is known for use with VV, M. A. Cochran et al., Proc. Natl. Acad. Sci. (USA) 82, 19-23 (1985). In transient assay, the promoter is linked to a gene with an easily assayable product, e.g. the lacZ gene of beta-galactosidase. A plasmid containing this construct is then introduced into a cell which has been infected with the virus. The viral RNA polymerase can transcribe off the promoter, even though the promoter has not been incorporated in the vital genome. Because expression only lasts while both the virus and the plasmid DNA are present in the cell together, this form of expression is known as `transient`.
In the practice of the invention for poultry, a foreign gene relevant to improving the condition of the poultry would be inserted into the fowlpox virus. Preferably the gene will be one appropriate to an in vivo sub-unit vaccine, for example one or more genes selected from Infectious Bronchitis Virus (IBV), Infectious Bursal Disease Virus, Newcastle Disease Virus (NDV), Marek's Disease Virus, Infectious Laryngotracheitis Virus and genes encoding antigenic proteins of Eimeria species. Particular genes of interest are the spike genes of IBV and the HN and F genes of NDV as described in PCT Patent Application Publication No. WO 86/05806 and European Patent Application Publication No. 227414A (both National Research Development Corporation). In order for the foreign gene to be correctly translated in vivo it is necessary for the foreign gene to have its own ATG start codon inserted In the region just following the promoter.
It is necessary to locate a non-essential region (NER) of the FPV, in which to insert the promoter of the invention and the desired foreign gene. In principle, they could be inserted anywhere in the FPV genome which would not harm the basic functions of the virus, or interfere with the action of the FPV promoter or the foreign gene. Preferably the NER is within the terminal inverted repeat of the FPV genome, as described in UK Patent Application Publication No. 2,220,941 or its PCT equivalent Publication No. WO89/12684 both filed on 22 Jun. 1989, the disclosure of which is herein incorporated by reference. Two copies of the foreign gene would then be expected to become inserted in the FPV genome, one towards each end.
The preparation of recombinant and recombination vectors, inoculation of birds and all other methodologies relevant to the invention are as described in the aforesaid prior UK Patent Applications and all such disclosure is herein incorporated by reference for the purpose of brevity.
While the invention its intended primarily for the treatment of chickens it is potentially of interest in relation to other animals which might safely be infected with FPV. It Is even possible that it might be considered safe to infect humans with FPV after appropriate trials have taken place. In that event, the realistic choice of foreign gene would become very wide.
The following Example illustrates the invention.
EXAMPLE
When a FPV random sequence library was compared with the VV 4a protein sequence a number of matches were observed. A "prime-cut" probe was made from one of these, MFP268, which matched closest to the amino-end of the protein (near to the 5' end of the gene and used to probe a library of cloned EcoRI fragments of FPV. A number of positives were observed which contained inserts of approximately 1.8 kb. One of these clones, pMB442, was further characterised by DNA sequencing of random fragments of pMB442 generated by sonication. The sequence of 1434 bp from one of the EcoRI sites is presented in SEQ ID NO: 3, along with a translation of part of the FPV 4a gene open reading frame (ORF). The portion of the 4a gene ORF sequenced is from nucleotides 466 to 1392. The symbols N represent vector nucleotides.)
Shown below is a comparison of the ends of the promoter sequences of VV (SEQ ID NO: 4) and FPV (SEQ ID NO: 5) in front of the genes. Apart from around the ATG start codon where both show the consensus late promoter sequence TAAATG they are not particularly similar. ##STR2##
In order to test the strength of the FPV 4a promoter, a fragment was cloned from pMB463 using the enzymes BclI and SsPI (pMB463 is the same plasmid as pMB442 but was grown In E. coli WK262, a dam minus strain of E. coli which allows the DNA to be cleaved by BclI which is inhibited by dam methylation. The BclI and SspI restriction sites TGATCA and AATATT involved in the cloning correspond to positions 246-251 and 481-486 respectively in SEQ ID NO: 3. The DNA was then end-repaired and cloned into SmaI-cut plasmid pNM480, described by Minton, Gene 31 269-273 (1984). The pNM480 plasmid has an EcoRI site to one side of the SmaI site and a HindIII site to the other. It also contains BamHI, SalI and PstI sites between the SmaI and HindIII. After transformation into E. coli TGl, colonies which were blue on Xgal Amp plates were screened by mini-DNA preparations and cleavage with EcoRI and HindIII (expected insert about 240 bp).
Two clones, pMB500, pMB501, which appeared to contain only small inserts, were purified on CsCl gradients and the sequences at the insertion sites checked by direct double stranded sequencing using the M13 "minus 40" universal primer. pMB500 contained the 4a promoter from the BclI site, to a point a bit beyond the expected SspI site, namely as far as nucleotide 543, but still in frame. (Why this happened is unclear).
The promoter was then tested in a transient assay system as described in UKPA Publication No. 2211504A but using plasmid pMB500. For comparison, the 4b promoter in plasmid pNM481 (construct pNM4b 30) was also tested. 0.1, 0.3 and 0.5 μg of the plasmid DNA was added 2 hours post infection by FPV strain HP444 (HP438+6 passages) at 1 pfu per cell. The optical densities at 405 nm (proportional to concentration of beta-galactosidase) were as follows:
______________________________________Cell background 0.017Cell + virus background 0.038 4a 4bCell + virus + 0.1 μg plasmid 0.198 0.2770.3 μg plasmid 0.386 0.3880.5 μg plasmid 0.459 0.558______________________________________
For these results it will be seen that the 4a promoter is approximately as strong a promoter as the 4b.
The 4a promoter can be used in the same way as the 4b, as described in UKPA Publication No. 2211504A.
__________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 5(2) INFORMATION FOR SEQ ID NO: 1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 20 amino acid residues(B) TYPE: amino acid(ii) MOLECULE TYPE: peptide(iii) HYPOTHETICAL - yes, predicted from fowlpox virus 4a gene.(v) FRAGMENT TYPE: N-terminal fragment(xi) SEQUENCE DESCRIPTION: SEQ ID NO: 1MetMet LeuIleLysAsnIleValThrLeuAspGlnLeuGluSerSer151015AspTyrLeuTyr20(2) INFORMATION FOR SEQ ID NO: 2:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 160 base pairs (B) TYPE: Nucleic acid(C) STRANDEDNESS: Double-stranded(D) TOPOLOGY: Linear(ii) MOLECULE TYPE: Genomic DNA(A) DESCRIPTION: DNA sequence of 160 base pairsto the 5'-end of the fowlpoxvirus 4a gene (immediately precedingthe start codon)(vii) IMMEDIATE SOURCE: Fowlpox Virus 4a gene from BeaudetteC strain.(A) LIBRARY: Random sequence library of fowlpox virusEcoRI fragments(B) CLONE: pMB442(xi) SEQUENCE DESCRIPTION: SEQ ID NO: 2ACAACATTTATAGTCTTGAGTGCTGATAACTGTCCGTTAGTAAGTTCATAGTTTTTATTA60CACGGATATA CGTCTTCTGAAAAGGCTGTTAAGTTATATTCTTTGGCTATATTTGTTATA120TCTGTTACCATCAATCCAGTCATTTATTATCATATAATAA160(2) INFORMATION FOR SEQ ID NO: 3:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 1434 base pairs(B) TYPE: Nucleic acid (C) STRANDEDNESS: Double-stranded(D) TOPOLOGY: Linear(ii) MOLECULE TYPE: Genomic DNA(A) DESCRIPTION: An EcoRI fragment of fowlpox virusencoding the region of the 4a gene andits promoter(vii) IMMEDIATE SOURCE: Fowlpox virus Beaudette C strain(A) LIBRARY: Random sequence library of EcoRI fragments(B) CLONE: pMB442(xi) SEQUENCE DESCRIPTION: SEQ ID NO: 3:NNNGAATTCCGATTCTAAGAGGGTTCTTATTAAAAAGGGTGTTTGTAAAATCTAACAAGT60TTTTGCTTTTAGTTTTCTTTTTACGAAGTTCGGCAATTTCTTGTTCGAGTAAATGAACCC120GTTTATTATCATCAAATACAGCTGATAAAGAAGGAGTCTGTTGTATAT TGTTACTTTGAA180TATAATTATCTTTTTCATCGTTGAATGAATGATGGCTACCTATTTCAGATACTATGCAAC240GATCATGATCATCGTCGTCATTATAAGTTACATCCTTCTCATAATTATCTGACCTGGTTG300TTAATACAACATTTATAGTCTTGAGTGCTGATA ACTGTCCGTTAGTAAGTTCATAGTTTT360TATTACACGGATATACGTCTTCTGAAAAGGCTGTTAAGTTATATTCTTTGGCTATATTTG420TTATATCTGTTACCATCAATCCAGTCATTTATTATCATATAATAAATGATGTTA472 MetMetLeuATAAAGAATATTGTAACTCTAGATCAGTTAGAATCTTCAGATTATCTC522IleLysAsnIleValThrLeuAspGlnLeuGluSerSerAspTyrLeu5 1015TATAAATTGATTTCTAGTGTTTTACCTTCGTTATGTCTAGATTACAAA570TyrLysLeuIleSerSerValLeuProSerLeuCysLeuAspTyrLys2025 3035ATAGATCCAAAACTAGCGAATGGATACGTACATGCGTTAGATACTATA618IleAspProLysLeuAlaAsnGlyTyrValHisAlaLeuAspThrIle40 4550TACAGTCCAGAATTAATTAGTATACTTACAGACGGTGAAAGATCACAA666TyrSerProGluLeuIleSerIleLeuThrAspGlyGluArgSerGln5560 65CAGTTAGATACACTGGGTATTAATTACATTCTTTCCAGAAAAAATGAT714GlnLeuAspThrLeuGlyIleAsnTyrIleLeuSerArgLysAsnAsp7075 80TTAGGTATTTATTTTCCTATAAATATCAGAGAAAACGGAGAAATAGTA762LeuGlyIleTyrPheProIleAsnIleArgGluAsnGlyGluIleVal859095TCTACG TGGAATAAAAATACCGGTGGGTATACGAATCCTATACCATGT810SerThrTrpAsnLysAsnThrGlyGlyTyrThrAsnProIleProCys100105110ACTATATCTTTCAACGATC TTCCTCCATTTACAAAAATATTGATACAG858ThrIleSerPheAsnAspLeuProProPheThrLysIleLeuIleGln120125130ATAAGAACCATGGGTTGTGAG GCTCACGCTAGATACTTCGGTGGATAC906IleArgThrMetGlyCysGluAlaHisAlaArgTyrPheGlyGlyTyr135140145GTAGAACATCCTTCGTCGCCTAATA TTCTATCCCCAAAAATAAATCCT954ValGluHisProSerSerProAsnIleLeuSerProLysIleAsnPro150155160AATATCAGTTTTGCAAATTCTTACATACATAGT CTTACTTATCCATAT1002AsnIleSerPheAlaAsnSerTyrIleHisSerLeuThrTyrProTyr165170175ATAGAGGGAAGAGCTGATTATTCTACTTACAGACCATTGTTGA TTAAT1050IleGluGlyArgAlaAspTyrSerThrTyrArgProLeuLeuIleAsn180185190195GGTATTATGGAAAAGAAGGATTTAGCTAATCTGTTGAATGTA AGAGCG1098GlyIleMetGluLysLysAspLeuAlaAsnLeuLeuAsnValArgAla200205210CTATTAGAACCTATGTCTAGAGCTATATTCGACGCTATATTTA AAATA1146LeuLeuGluProMetSerArgAlaIlePheAspAlaIlePheLysIle215220225CAATTTCATTGTAACGCTAATAACATTGTACTTGTACAAAATCCTAAT 1194GlnPheHisCysAsnAlaAsnAsnIleValLeuValGlnAsnProAsn230235240ATAGACACGGATCTTATAACGATGCAGACACTAAAGTATCTAGTTATG1242Il eAspThrAspLeuIleThrMetGlnThrLeuLysTyrLeuValMet245250255TATTTCCAGCATTTTTCTGGTTTTACGTTAAGGGATATATATTTGGGA1290TyrPheGlnHis PheSerGlyPheThrLeuArgAspIleTyrLeuGly260265270275GGAGTACGAATACGTGTTGATAATTCTATGTTAGCGTCTTATGTTGTA1338GlyValArgIl eArgValAspAsnSerMetLeuAlaSerTyrValVal280285290TCAATTTATTTTAGTAAAGAGATAAAGTATATAGAAGATAACAAGTAT1386SerIleTyrPhe SerLysGluIleLysTyrIleGluAspAsnLysTyr295300305TTTCGTTAGACTATATTGATCAGTTTGTATTTAGGCCAGATAATAGCA1434PheArg309(2 ) INFORMATION FOR SEQ ID NO: 4:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 36 base pairs(B) TYPE: Nucleic acid(C) STRANDEDNESS: Double-stranded(D) TOPOLOGY: Linear(ii) MOLECULE TYPE: Genomic DNA(A) Description: End sequence of the Vaccinia Virus 4agene promoter, up to and includingstart codon.(x i) SEQUENCE DESCRIPTION: SEQ ID NO: 4:TCACTGGTACGGTCGTCATTTAATACTAAATAAATG(2) INFORMATION FOR SEQ ID NO: 5:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 36 base pairs(B) TYPE: Nucleic acids(C) STRANDEDNESS: Double-stranded(D) TOPOLOGY: Linear(ii) MOLECULE TYPE: Genomic DNA(A) DESCRIPTION: End sequence of the fowlpox virus 4a gene promoter, up to and includingstart codon.(xi) SEQUENCE DESCRIPTION: SEQ ID NO: 5:CCATCAATCCAGTCATTTATTATCATATAATAAATG | Fowlpox virus (FPV) or other avipox virus promoter DNA for use in expressing a foreign gene inserted in a FPV vector by homologous recombination, which comprises the promoter of the following 4a gene, said 4a gene encoding a protein of very roughly about 890 amino acids in a sequence beginning
Met Met Leu Ile Lys Asn Ile Val Thr Leu
Asp Gln Leu Glu Ser Ser Asp Tyr Leu Tyr. | 2 |
The present invention generally relates to the art of die casting and more particularly relates to a vacuum die casting process.
In a die casting process in which castings are successively made, molten metal is typically loaded into a shot sleeve apparatus which has a plunger mechanism that pushes the metal into the cavity of the die mold which has the desired shape of the object that is being cast.
It is generally known that metal die casting operations produce improved quality castings if the die cavity in which the casting is formed is evacuated of air prior to injection of the casting material into the cavity. It has also been found that fewer imperfections, in terms of surface spalling, the presence of bubbles and the like, occur if the metal is injected into the die cavity solely as a result of the movement of the plunger through the sleeve, and that no premature flow of the metal from the channel into the die cavity occurs from any other influence, such as by the vacuum force in the cavity pulling the metal into the cavity. If the plunger is effectively sealed so that no air can pass from behind it, then the vacuum in the die cavity will not be effective to pull casting material from the channel into the die before the plunger actually pushes it into the die cavity.
The die cavity is evacuated by applying a vacuum to the cavity, and this is generally done by opening a valve that communicates the die cavity with a source of vacuum. Before the metal reaches the cavity, it must first travel through a runner or channel that extends from the shot sleeve apparatus to the die cavity. It is preferred that the shot sleeve apparatus move at a slower rate while the metal is being pushed through the channel, but when it is injected into the cavity itself, it is done at a relatively fast rate. The vacuum valve is generally opened just before placing a shot of molten metal into the cavity and is then closed at some time during the injection of the metal into the cavity itself.
It is highly desirable that successive casting operations be carried out smoothly and efficiently, with a minimum of downtime. It is common for many prior art apparatus to experience malfunctions that result in the casting apparatus being disassembled to remove hardened casting material from internal surfaces and lines, which is often very time consuming and expensive.
Accordingly, it is a primary object of the present invention to provide an improved process for vacuum die casting that helps prevent malfunctions from occurring that would lead to such expensive disassembly and removal of casting material.
Another object of the present invention is to provide such an improved process that is controlled by a processing means which receives information relating to the status of important parameters of the process, and which aborts a casting operation if important parameters are not met.
A related object of the present invention is to provide such an improved process that can abort a casting operation at any one of several steps during the operation, with the consequences of the aborting being less consequential the earlier in the process such aborting takes place.
Yet another object of the present invention lies in the provision of lengthening the mean time between failures of a die casting apparatus because of the preventative aspects of the process.
A more detailed object of the present invention is to provide an improved process that tests and monitors the pressure levels in various parts of the apparatus, including the die cavity itself and in the positive and vacuum pressure lines. The process includes steps for cooling the vacuum valve and cleaning the same valve as well as various lines during a casting operation, and has the capability of aborting the operation if certain measured parameters are not acceptable.
Other objects and advantages will become apparent upon reading the following detailed description, while referring to the attached drawings, in which:
FIG. 1 is a schematic block diagram of the apparatus that can be used to practice the process of the present invention;
FIGS. 2 and 3 together comprise, a flow chart of the process of the present invention, which is controlled by a processing means; and,
FIG. 4 is a side elevation, partially in section, of a die casting apparatus in which the process of the present invention can be practiced.
DETAILED DESCRIPTION
Broadly stated, the present invention is directed to an improved process for performing a die casting operation which is successively carried out to manufacture castings. The process is adapted for use with a die casting apparatus which utilizes vacuum to evacuate the die cavity prior to injection of the casting material into the cavity. While the process is well suited for metal castings, it is also adapted for making castings of other materials. The process is also particularly well suited for use with apparatus that is disclosed in patent application entitled SEALED SHOT SLEEVE APPARATUS FOR VACUUM DIE CASTING, Ser. No. 874,740which discloses a shot sleeve apparatus that is effective to prevent premature injection of casting material into the die cavity itself as a result of the vacuum pulling material from the channel or runner into the cavity before the plunger mechanism actually injects the material therein. The process is also particularly well suited for use with an apparatus disclosed in patent application entitled VACUUM VALVE FOR DIE CASTING, Ser. No. 874,629 which describes a vacuum valve of the type generally shown in FIG. 4 herein, which efficiently communicates vacuum to the die cavity and which is designed to facilitate maintenance work to clear the valve in the event of a malfunction. The superior operation of the vacuum valve is achieved by the apparatus disclosed in patent application entitled DOUBLE SOLENOID VALVE ACTUATOR, Ser. No. 874,755 and the necessary and desirable vacuum levels are accomplished using the teachings of patent application entitled VACUUM VALVE DESIGN FOR DIE CASTING, Ser. No. 874,368
While the improved process of the present invention is particularly well suited for being carried out with the apparatus disclosed in the apparatus of the aforementioned patent applications, it can be used with other apparatus that have similar and analogous components, such as a vacuum valve that is near the die cavity, sources of vacuum and positive air pressure, with associated valves adjacent the sources and a plunger means for injecting a shot of molten material into the die cavity.
Turning now to the drawings, and particularly FIG. 1, the process embodying the present invention can be carried out using apparatus as shown, which includes a processing means 10 which is electrically connected to a die vacuum valve, indicated generally at 12 in FIG. 1 and in FIG. 4, and which is also referred to herein as the first valve. The processor 10 is also connected to a vacuum supply valve 14, which is also referred to herein as the second valve. The processor 10 is similarly connected to a positive air supply valve 16 and processor receives signals from a vacuum/pressure sensor 18. The processor is also connected to a controller 20 for the plunger mechanism and it sends and receives signals relating to the functioning of the plunger controller during the process.
Turning now to FIG. 4, the components that have been identified in FIG. 1 are also shown in FIG. 4, in addition to other structural components of the die casting apparatus in which the process of the present invention can be performed. The vacuum valve 12 has a valve body 22 that is mounted in a die 24 and the valve 12 has a valve seat 26 in which a valve member 28 seats and moves to the right to open the valve. The valve member 28 effectively isolates a die cavity 29 and a channel 30 from an inside valve chamber 32 of the valve 12. The valve member 28 is opened and closed by operation of a double solenoid arrangement 34 that is comprehensively described in the aforementioned application Ser. No. 874,755. The valve chamber 32 has a port 36 that extends to and is in communication with a vacuum line 38 that extends to the vacuum supply valve 14 which is in communication with a vacuum pump 40 that provides the source of vacuum to the apparatus. Inside the port 36 is a tube 42 that extends to the vacuum/pressure sensor 18 that is a transducer and generates electrical signals that are representative of the pressure that is measured in the tube 42. The tube 42 is also in communication with the positive air supply valve 16 which is in communication through line 44 to a source of positive air pressure 46. When the valve 16 is opened, positive pressure is injected through the tube 42 into the chamber 32 as is desired. Similarly, by virtue of the tube 42, the vacuum transducer 18 effectively measures the pressure in the chamber 32 and when the valve member 28 is moved to the right from the position shown in FIG. 4, it will measure the pressure level in the runner 30 and in the die cavity 29 itself.
When molten metal or other casting material is to be injected into the die cavity, the plunger controller 20 (FIG. 1) causes the plunger mechanism, indicated generally at 48, to be activated and it preferably moves the molten metal that has been loaded into the shot sleeve apparatus that has been comprehensively described and illustrated in the aforementioned application Ser. No. 874,740 which is specifically incorporated by reference herein, and the plunger moves at a relatively slow rate that is within the range of approximately 10 to approximately 40 inches per second, and preferably approximately 15 inches per second to force the molten metal into a runner 50 until the molten metal reaches just short of the cavity itself, during which case the plunger controller 20 increases the speed of the plunger, which is preferably hydraulically driven, so that it moves at a rate of approximately 75 to 80 inches per second and rapidly forces molten metal into the die cavity 29.
During the slow movement of the plunger, the valve member 28 is opened to communicate the cavity 29 to the source of vacuum to evacuate the cavity and it is preferred that the valve member 28 close before the plunger is moved at its fast rate and before any molten casting material is actually injected into the die cavity itself. As is disclosed in the aforementioned application Ser. No. 874,755, the valve member 28 is extremely fast acting in its closing and preferably moves from its fully opened position to a closed position in approximately 10 to 15 milliseconds. This insures that the valve will be closed before molten metal could possibly reach the valve and thereby prevents it from being fouled or contaminated, which would require that the valve 12 be removed and cleared of any material so that the valve member 28 would effectively seal the internal chamber 32. The valve closing in approximately 10-15 milliseconds is fast enough to prevent fouling of the valve inasmuch as it requires approximately 30-35 milliseconds to complete the fast injection of the casting material into the die cavity.
Turning now to the process embodying the present invention, the process comprises a series of steps which begins with that of determining the amount of leakage that is present in the die cavity and aborting the casting operation if the amount of leakage exceeds a predetermined value. The process then clears the valve seat 26 of the first valve 12 with a rush of air and thereafter cools the same while keeping it clear of debris. The process then pressurizes the line 38 between the first valve 12 and the second valve 14 and determines if any leakage is present in that line and if leakage is determined, the casting operation is then aborted if the amount of leakage exceeds a predetermined value. The process then supplies a vacuum to the chamber 32 with the valve member 28 seated on seat 26, i.e., the first valve 12 is closed and it measures the vacuum level in the chamber 32 and aborts the casting operation if the level is not at a predetermined minimum level, preferably at approximately 28 to 29 inches of mercury. The process then starts the plunger means 48 and applies vacuum to the die cavity by the processor 10 generating signals to the plunger controller 20 to start the plunger apparatus in operation which involves moving the plunger at the slower rate while opening the valves 12 and 14 to communicate the vacuum from the vacuum pump to the die cavity itself. The vacuum level is then measured before the casting material reaches the die cavity 29 and if the vacuum level is not at a second predetermined minimum level, i.e., approximately 24 to 27 inches of mercury, the processor 10 commands the plunger controller 20 to abort the casting operation. If the level of vacuum in the cavity is at or above its predetermined minimum level, then the plunger controller 20 is commanded to perform the fast mode of plunger movement to inject the casting material into the die cavity.
The above description generally describes the process, but the actual steps that are carried out to accomplish the process are also shown in the flow charts of FIGS. 2 and 3 which are specific instructions that are programmed in the memory means that is a part of the processor 10. In this regard, the processor 10 also includes the plunger controller 20 and is preferably a model SLC05/02 controller manufactured by the Allen Bradley Company of Milwaukee, Wis. Referring to FIG. 2, when a casting operation is started, the second valve 14 is opened and line 38 is evacuated. The second valve 14 is then closed and the vacuum/pressure transducer 18 measures the vacuum decay time together with the processor 10. It should be mentioned that the vacuum/pressure transducer is of conventional design, but is of the type which can measure pressures above and below atmospheric pressure.
Since line 38 is in communication with line 36, the transducer or sensor 18 effectively measures the vacuum level in the chamber 32, the port 36 and line 38 via the tube 42. It should be understood that the opening and closing of the second valve 14 to perform this vacuum decay measurement is done with the valve 12 closed, i.e., the valve member 28 is seated on seat 26. The vacuum decay time is determined by the pressure transducer providing the signal indicating the pressure level at a start time, and it is then compared with a later measurement taken approximately 1 second after the first and if the difference between the two values is more than approximately 1/2 to 1 inches of mercury, then it is assumed that the first valve 12 is contaminated and the process is aborted and the operator notified of a process fault.
The next step is to open both the first valve 12 and the second valve 14 which results in a rush of air from the evacuation of the die cavity being created which will clear the valve seat 26 of debris. This is done before the plunger controller is activated by the processor 10.
With the valve 12 opened, the second valve 14 is then closed and the positive air supply valve 16 is opened which results in compressed air from the positive air supply 46, which preferably is at a level of approximately 30 p.s.i., being blown through line 44, valve 16 and the tube 42 into the chamber 32 for approximately 1 to 2 seconds. This has the effect of blowing compressed air by the seat 26 and the valve member 28 for keeping these components clear of debris and also cooling the valve member 28. The 30 p.s.i. level of the positive air pressure is chosen to accommodate the transducer 18 which is operable over a range of 75 p.s.i. and to keep the air from forcing open the valve 12, which has the valve member held closed by a spring, as is comprehensively set forth in the aforementioned application entitled DOUBLE SOLENOID VALVE ACTUATOR, Ser. No. 874,755.
After the last described step is completed, the valve 12 is then closed and by virtue of the second valve 14 still being closed, the line 38 is pressurized at the approximately 30 p.s.i. level. The pressure decay time is then measured in a similar fashion as the prior vacuum decay time. If the difference between successive measurements of the pressure is greater than approximately 1 inch of mercury over a time period of approximately 1 second, the processor 10 aborts the operation and notifies the operator.
In preparation for the injection of casting material into the cavity, the pressure level in the valve chamber 32 is measured with the first valve 12 closed and the second valve 14 opened. If the desired vacuum level is not attained, which is preferably approximately 28 to 29 inches of mercury, the process is aborted and the operator is notified of a fault.
If the vacuum level is at or above the predetermined level, then the plunger controller 20 is commanded to start its operation and when it has effectively sealed the shot chamber thereof, i.e., air cannot pass through the shot sleeve, the runner communicating the shot sleeve with the die cavity, the first valve 12 is opened. The sealing of the shot chamber is accomplished when the plunger reaches a predetermined position during its stroke. The opening of the first valve 12 has the effect of evacuating the cavity itself. While the plunger is moving in its slower speed mode of operation which injects the casting material into the runner leading to the cavity, the vacuum level is measured and if it is not sufficiently high, i.e., approximately 24 to 27 inches of mercury, the process is aborted and the operator notified of a process fault.
It should be understood that the die cavity is formed by die components which must be separated from one another to remove the resulting casting that is made. The interface between components defines parting lines which permit some degree of leakage by their inherent nature. The leakage that inevitable occurs results in the vacuum level declining over time, but levels within the range of approximately 24 to 27 inches of mercury are generally considered sufficient to result in superior quality castings being formed. If the vacuum level does reach or exceed the second predetermined level, then the plunger controller 20 operates in the fast mode of operation to inject the casting material into the die cavity.
Generally simultaneously with the plunger controller moving the plunger in its fast shot mode, the first valve is also closed, which because of its fast acting capabilities, will reliably result in the valve member 28 seating with the seat 26 which will prevent any casting material from fouling the valve. Once the casting material has been injected into the cavity, the plunger controller 20 issues commands for returning the plunger to its retracted position in preparation for a subsequent casting operation.
From the foregoing, it should be appreciated and understood that an improved die casting process has been described which offers many significant advantages and desirable features over prior art processes. The capability of accurately monitoring a die casting operation results in reliability and prevents malfunctions that commonly occur in such process. At various important steps in a die casting operation, pressure levels are monitored and the process has the capability of aborting a casting operation at multiple times during the operation.
While various embodiments of the present invention have been shown and described, it should be understood that various alternatives, substitutions and equivalents can be used, and the present invention should only be limited by the claims and equivalents thereof.
Various features of the present invention are set forth in the following claims. | The process calls for testing and monitoring the pressure levels in different parts of the die casting apparatus during a casting operation, including the die cavity itself and in positive and vacuum pressure lines. The process also includes process steps which cools a vacuum valve adjacent the die cavity and cleans the valve and lines during a casting operation. The process calls for aborting a casting operation at various time during the operation if certain measured parameters are not acceptable. | 1 |
Polyester has two supreme virtues which make it very desirable for use in clothing: it is cheap and it is durable. However, it also has a host of drawbacks which have prevented its complete acceptance. Lifetimes of effort have been spent in attempts to formulate finishes which will overcome these drawbacks, but there is currently no panacea and the various finishes currently used generally alleviate some shortcomings at the expense of others. One of the problems associated with polyester has been its tendency to retain electrostatic charges often causing it to cling to the wearer in an unflattering way, showing bulges which the wearer would prefer to hide in the drape of the garment. For less frivolous reasons, antistatic properties are extremely important for nurses' uniforms, operating room garments and any other textiles which will be used in potentially explosive atmospheres. Another serious deficiency of polyester is that it tends to retain oil and thus becomes permanently soiled. Various finishes will overcome either of these problems but previously no finish has been commercially suitable for simultaneously imparting durable soil release and antistatic properties to polyester. In most cases, the antistatic properties could be sacrificed for soil release properties, certainly, no housewife would have it otherwise; but in special garments where antistatic properties were essential, soil release had to be compromised. Since these garments are often white, substandard soil release properties are a major deficiency. A method has now been found for imparting durable soil release and antistatic properties to polyester. This is achieved by treating the polyester with a cellulose derivative then applying a polyamine and curing the polyamine and the cellulose derivative with an epoxide.
Suitable cellulose derivatives include cellulose ethers and esters having a degree of substitution of between about 0.5 and about 2.6. If the degree of substitution is less than about 0.5, it is difficult to fix the cellulose derivative to the polyester while if the degree of substitution is more than about 2.6, it is difficult to crosslink the cellulose derivative and the polyamine with the polyepoxide.
Suitable polyamines are represented by the structural formula:
H[--X--CH.sub.2 CH.sub.2 --(OCH.sub.2 CH.sub.2).sub.m --O--Z--O--(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 ].sub.p --X--H
wherein --Z-- is a divalent radical which is inert to reaction with amines, X is a member of the class consisting of ##STR1## wherein --D-- is a member of the class consisting of hydrogen, lower alkyl and amino lower alkyl and --Y-- is a divalent aliphatic which contains only carbon and hydrogen, m and n are from about 3 to about 40 and p is less than about 10.
The durable soil release and antistatic properties are imparted to the polyester by first fixing the cellulose derivative to the polyester and then applying the polyamine and curing it with an epoxide.
DETAILED DESCRIPTION OF THE INVENTION
Suitable cellulose derivatives are represented by the formula ##STR2## wherein each R is chosen from the group consisting of --H, --C n H 2n+1 , and ##STR3## and n is from about 1 to about 4, x is at least about 50 and wherein on an average basis from about 0.5 to about 2.6 of the R groups on each repeating unit are other than hydrogen.
In the preferred cellulose derivatives each R is chosen from the group consisting of --H, ##STR4## and --C n H 2n+1 wherein n is from about 0.9 to about 2.3. The most preferred cellulose derivative is a cellulose acetate having an acetyl content of between about 24 and 36% wherein x is from about 100 to about 200.
The amount of the cellulose derivative applied to the polyester should be at least about 0.01% of the weight of the polyester. Preferably, the amount applied will be from about 0.05 to 0.4% of the weight of the fabric and the best results are obtained when the amount is from about 0.1 to about 0.2% of the weight of the fabric.
The cellulose derivative may be applied from a liquid dispersion by any suitable contacting method such as padding, exhaustion, spraying or similar methods. Especially desirable results can be obtained when the cellulose derivative is exhausted onto the polyester from a liquid dispersion. Whichever method is used, the dispersion will typically contain from about 0.001 to about 0.5% by weight of the cellulose derivative so that the amount of cellulose derivative applied will be at least about 0.01% of the weight of the polyester. After the cellulose derivative is applied to the polyester, it should be fixed. The method chosen for fixing depends upon the method chosen for application. These methods are well known but basically if the dispersion is sprayed or padded onto the polyester, the cellulose derivative is fixed by evaporating the liquid. Any suitable drying technique may be employed but care should be exercised to insure that neither the polyester nor the finish is degraded by excessively high temperature. If exhaustion is employed, the cellulose derivative is, of course, fixed during the exhaustion process. Exhaustion is an especially desirable method of applying and fixing the cellulose derivative since the fabric can be simultaneously dyed and further since intermediate drying can be avoided between fixing of the cellulose derivative and crosslinking the polyamine with the polyepoxide.
After the cellulose derivative has been fixed to the polyester, the polyamine and the epoxide are applied to the fabric. Suitable polyamines are described in detail in U.S. Pat. Nos. 3,021,232 and 2,982,751. Basically, these polyamines are represented by the structural formula
H[--X--CH.sub.2 CH.sub.2 --(OCH.sub.2 CH.sub.2).sub.m --O--Z--O--(CH.sub.2 CH.sub.2 O).sub.n --CH.sub.2 CH.sub.2 ].sub.p --X--H
wherein --Z-- is a divalent radical, X is a member of the class consisting of ##STR5## wherein --D-- is a member of the class consisting of hydrogen, lower alkyl and amino lower alkyl and --Y-- is a divalent aliphatic which contains only carbon and hydrogen, m and n are from about 3 to about 40, p is less than about 10. Since the character of Z is not critical, provided it is inert to reaction with amines, it may be any member of the class consisting of ##STR6## and --A--, wherein --A-- is a member of the class consisting of divalent aliphatic, alicyclic, aromatic and heterocyclic radicals. Preferably --A-- is a hydrocarbon moiety.
The preferred polyamines are represented by the structural formula:
H[--X--CH.sub.2 CH.sub.2 --(OCH.sub.2 CH.sub.2).sub.q --OCH.sub.2 CH.sub.2 ].sub.p --X--H
wherein X is a member of the class consisting of ##STR7## wherein --D-- is a member of the class consisting of hydrogen, lower alkyl and amino lower alkyl and --Y-- is a divalent aliphatic which contains only carbon and hydrogen, q is from about 6 to about 40 and p is less than about 10.
While any polyepoxide which is capable of crosslinking the polyamine and the cellulose derivative may be used, the preferred polyepoxides have the structural formula ##STR8## wherein R 1 , R 2 and R 3 are chosen from the class consisting of aliphatic, alicyclic, aromatic, heteroaromatic, ester and ether groups.
Still more preferred are the polyepoxides represented by the structural formula ##STR9## wherein n is from about 1 to about 15.
The polyamine and the polyepoxide may be applied simultaneously or in either order so long as both are present on the fabric for curing. If the polyamine and polyepoxide are applied simultaneously from an admixture it is sometimes advantageous for that admixture to be slightly acidic to retard premature reaction but this is not always necessary if the holding time is sufficiently short.
The polyamine and the polyepoxide may be applied by any method which applies a sufficient amount to the fabric. Suitable methods include padding, spraying, dipping and immersion. After the polyamine and polyepoxide contact the polyester, the pH is not critical, it may be acid, basic or neutral and crosslinking will occur. Typically, the polyether polyamine will be at least 0.05% of the weight of the polyester. Preferably, the amount of polyether polyamine applied will be between about 0.2 and 10% of the weight of the polyester and more preferably between about 1 and 5%. The amount of epoxide applied should be sufficient to crosslink the polyamine and the cellulose derivatives. Typically, the amount of epoxide will be at least about 1% of the weight of the polyamine while in preferred embodiment, the amount of the epoxide applied should be between about 5 and about 20% of the weight of the polyamine and more preferably between about 8 and 12%.
After the polyamine and epoxide have been applied, crosslinking is accomplished by drying and curing at an elevated temperature.
Typically, curing will take place at temperatures of at least about 100° C. The temperature chosen should not be so high as to degrade either the polyester or the finish. Conveniently, a catalyst such as zinc fluoroborate may be included to accelerate curing or crosslinking.
The following example is provided to more fully illustrate the invention which is defined solely by the claims:
EXAMPLE
Cellulose acetate having an acetyl content of 32% was exhausted onto polyester fabric from an aqueous dispersion at 130° C. in an amount equal to 0.3% of the weight of the fabric.
An aqueous formulation was prepared having the following composition:
7.5% Aston 123 (a highly ethoxylated polyamine) manufactured by Refined Onyx
0.75% Accelerator DT (an ethoxylated epoxide) manufactured by Refined Onyx
0.38% Zinc Fluoroborate
This aqueous formulation was padded onto treated polyester fabric and an untreated control fabric at a pickup of about 100% of the weight of the fabric. Both fabrics were then dried and cured at 350° F. for 5 minutes. The resistivity of both samples was measured after curing and again after 1, 5 and 10 washes in a standard home washing machine using 100 grams of AATCC detergent at 120° F.
______________________________________ Electrical Resistivity in Ohms per Square as Measured to AATCC Test Method 76 - 1975 at 70° F.; 65% Relative Humidity Treated Sample Untreated Control______________________________________Initial 3.0 × 10.sup.9 1.4 × 10.sup.10 1 Wash 5.6 × 10.sup.9 2.1 × 10.sup.12 5 Washes 2.7 × 10.sup.11 5.6 × 10.sup.1310 Washes 2.0 × 10.sup.10 5.7 × 10.sup.14______________________________________ | A polyester textile product having durable antistatic and soil release properties, said product being impregnated with the reaction product of; a cellulose ether or ester, a polyamine and a polyepoxide. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of copending International Patent Application PCT/EP/2004/012273 filed on Oct. 29, 2004 and designating the United States, which claims priority of German Patent Application DE 103 51 627.1 filed on Nov. 5, 2003, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to Bartonella henselae as a component of a pharmaceutical composition for the modulation of the angiogenesis; a nucleic acid molecule that is derived from the gene encoding the Bartonella henselae adhesin A protein (BadA), a vector comprising said nucleic acid molecule; a host containing said nucleic acid molecule or said vector; a (poly)peptide encoded by said nucleic acid molecule; a composition comprising Bartonella henselae bacteria; a composition comprising aforesaid (poly)peptide; a method for treating a human or animal being in need of the modulation of the angiogenesis, a method for detecting an infection by Bartonella in a human or animal being, as well as a method for immunizing a cat.
2. Related Prior Art
Angiogenesis or neovascularisation refers to a process in which under physiological conditions new blood vessels are sprouting out of the existing vascular system. Angiogenesis can, e.g., be observed during embryogenesis in the corpus luteum (menstruation). Furthermore, angiogenesis has a pathophysiological relevance, it can be observed during the wound healing, in diabetic retinopathy, haemangiomas, psoriasis, as well as in malignant tumors. In this connection, ischaemic diseases are especially relevant, which are very often characterized by a disorder of the angiogenesis.
Against this background especially in medicine and pharmacology there is a considerable need for pharmacological effective substances by which the angiogenesis can be modulated.
SUMMARY OF THE INVENTION
Therefore, the object of the present invention is to provide a substance for modulating the angiogenesis. Furthermore, such a substance should be provided that can easily and cost-effectively be obtained or prepared.
According to the invention this object is achieved by the usage of Bartonella henselae as a compound of a pharmaceutical composition for the modulation of the angiogenesis.
This object can also be realized by the following method, comprising the steps: (a) providing Bartonella henselae and (b) formulating Bartonella henselae into a pharmaceutically acceptable carrier.
The inventors could surprisingly demonstrate that incubating biological replicating material, such as HeLa cells, with Bartonella henselae results in an a manipulation of the genetic program of said biological material, that is responsible for the regulation of the angiogenesis. In other words, the inventors have succeeded in demonstrating that Bartonella henselae is a substance that is suitable for the targeted modulation of the angiogenesis.
The finding that a gram-negative bacterium of the genus Bartonella , namely Bartonella henselae , enables the modulation of the angiogenesis and has therewith a therapeutical capacity was especially surprising, since this bacterium is largely described in the art as a trigger for the induction of a number of different diseases: Bartonella henselae was detected in the blood of immunosuppressed patients, for example HIV patients. Such patients which were infected by Bartonella henselae , show symptoms of the bacillary angiomatosis, bacillary peliosis (infestation of viscera), fever, bacteraemia and endocarditis. In immunocompetent hosts Bartonella henselae is the main pathogen that causes the so-called cat scratch disease (CSD).
It is also known that Bartonella henselae stimulates the production of growth factors or cytokines, for example of vascular endothelial growth factor (VEGF; cf. for this Kempf et al. (2001), “Evidence of a leading role for VEGF in Bartonella henselae -induced endothelial cell proliferations”, Cell. Microbiol. 3(9), 623-632; Resto-Ruiz et al. (2002), “Induction of a potentional paracrine angiogenetic loop between human THP-1 macrophages and human microvascular endothelial cells during Bartonella henselae infection”, Infection and Immunity 70(8), 4564-4570.
However, there are no hints in the art, which demonstrate or even suggest a relation between Bartonella henselae and the modulation of the angiogenesis.
Within the scope of the invention modulation of the angiogenesis refers to every largely targeted manipulation of the angiogenesis in a human or animal organism or parts or organs thereof, respectively, by Bartonella henselae or by parts of this bacterium, such as the stimulation, induction or inhibition of the angiogenesis.
It is preferred if the entire bacterium is used for the modulation of the angiogenesis.
This means that according to this embodiment the angiogenesis-modulating activity is based on the whole bacterium, the latter, therefore, can be used as such as an effective agent without any further processing measures, for example by performing a targeted infection. This measure has the advantage that the whole bacterium is available in large amounts and can be cultivated and reproduced by means of well-established microbiological methods.
According to a preferred embodiment of the invention, for modulating the angiogenesis a genetically modified bacterium is used.
A genetically modified bacterium refers to such a Bartonella henselae bacterium that differs in its pheno- or genotype in some way from that of the corresponding wild type bacterium. This measure has the advantage, that on the one hand the angiogenesis-modulating activity of the bacterium can be altered by means of molecular biological methods in a targeted fashion, and on the other hand possible pathogenic factors can be simultaneously knocked-out in a targeted fashion. Methods for the genetic modification of the bacterium are well-known in the art; cf. for example Sambrook, J. and Russell, D. W. (2001), “Molecular Cloning—A Laboratory Manual”, Cold Spring Harbor Laboratory Press, New York, 3rd Edition.
According to the invention it is also preferred, if a killed bacterium is used for the modulation of the angiogenesis.
According to the invention a killed bacterium refers to such a bacterium that has lost its dividing activity and/or metabolic activity, however, such a bacterium is still able to modulate the angiogenesis. This measure has the advantage that such a Bartonella henselae bacterium is still in the position for presenting angiogenesis-modulating activity in biological material, as this was found by the inventors, however, it does not evolve any pathogenic activity.
According to a variation of the invention, for modulating the angiogenesis a peptide is used, that comprises a fragment of the adhesin A protein of Bartonella henselae (BadA).
This variation is also realized by the following method, comprising the steps: (a) Providing BadA and (b) formulating BadA into a pharmaceutically acceptable carrier. I.e., the Bartonella henselae bacterium is reduced to its BadA protein.
The inventors were able to identify a new protein referred to as Bartonella henselae adhesin A (BadA) as a crucial bacterial factor that is involved in the modulation of the angiogenesis. BadA is a bacterial protein having a molecular weight of 340 kD, and is encoded by a gene having the length of 9.3 kB. The DNA sequence of the BadA gene is presented in the attached sequence listing and referred to as SEQ ID No. 1. This protein is expressed at the bacterial surface of Bartonella henselae , and is visible in the electron microscope due to its enormous size.
As the inventors have realized, within the scope of the present invention and according to this preferred embodiment, for modulating the angiogenesis a peptide fragment can be used that is characteristic for BadA, i.e. such a fragment that displays the biological activity of BadA, which is responsible for the modulation of the angiogenesis, as, e.g., a segment of the whole protein, that is responsible for the adhesion of the bacterium to the host cells or the endothelial tissue of the host. Segments of the BadA protein which do not contribute to the angiogenesis-modulating activity, such as protein domains which merely serve for anchoring the protein in the membrane can be neglected. It goes without saying, that within the scope of the invention for modulating the angiogenesis also the whole BadA protein can be used, as well as fusion proteins which comprise a corresponding fragment of BadA displaying angiogenesis-modulating activity. With the present invention also the usage of such peptides is encompassed, which comprise a fragment of BadA that is modified compared to the wild type BadA, for example due to modified or substituted amino acids, as long as by this measure the angiogenesis-modulating activity of BadA is not lost.
On account of the therapeutical relevance of the findings of the inventors, it is preferred according to the invention if the modulation of the angiogenesis in the afore-mentioned usages occurs within the frame of the treatment of an ischaemic disease.
Especially in ischaemic diseases, i.e. such diseases characterized by a decreased or interrupted blood circulation through an organ, a part of an organ or a tissue resulting from disordered arterial blood supply, a targeted modulation of the angiogenesis is envisaged in order to normalize the circulation, that is so far not possible in the art or merely in an unsatisfactory way. Here, the present invention gives remedy by activating or upregulating genetic factors, such as growth factors or cytokines, resulting in the induction of the angiogenesis in an affected patient.
This measure has the advantage that herewith especially ischaemic conditions are redressed or reduced, and aid can be given to affected patients in a targeted manner. The inventors were able to show that Bartonella henselae or BadA have a special angiogenesis-stimulating potential that results from an up-regulation of different genes inducing the angiogenesis in biological material, if said biological material is incubated together with Bartonella henselae or BadA for a certain time, or if cells are infected by Bartonella henselae.
Very often especially in tumor diseases the angiogenesis should be manipulated in a targeted fashion in order to, e.g., modulate or inhibit the blood flow in tumors. Therefore, it is preferred according to the invention, if in the afore-explained usages the modulation of the angiogenesis occurs within the frame of the treatment of a tumor disease. Of course, while doing so further anti-carcinogenic measures can be performed, such as a chemotherapy.
In this connection on account of the present invention it is possible to analyze substances which are not known so far in view of their capacity to modulate the angiogenesis by screening these substances in an in vitro assay system. In such an assay system it can be studied whether such substances are competitive with Bartonella henselae or BadA, e.g. whether they have a similar, i.e. angiogenesis-stimulating activity, or whether they have an activity that is contradictory to that of Bartonella henselae or BadA, and, therefore, inhibit the angiogenesis.
Another subject of the present invention relates to a nucleic acid molecule encoding a (poly)peptide that is associated with the modulation of the angiogenesis, said nucleic acid molecule comprises a segment having the sequence SEQ ID No. 1.
The sequence SEQ ID No. 1 that is shown in FIG. 7 , is the sequence of the gene encoding the bacterial adhesin A protein of Bartonella henselae (BadA) and has a size of 9.3 kB. According to the invention, the afore-described nucleic acid molecule also encompasses such a molecule that encodes the whole BadA protein but also such a molecule that encodes protein segments which display BadA activity, i.e. angiogenesis-modulating activity. Furthermore, according to the invention also such nucleic acid molecules are meant, which encode (poly)peptides derived from BadA and in which, e.g., different amino acids were replaced or chemically modified, as long as this (poly)peptide still displays BadA activity, i.e. angiogenesis-modulating activity. Furthermore, according to the invention this object also encompasses such a nucleic acid molecule that comprises at its 5′- and/or 3′-ends additional sequences which are independent from SEQ ID No. 1 and which, e.g., serve for the expression, replication, purification, etc. of the genetic information or the (poly)peptide, respectively.
Another object of the present invention is a vector that comprises the before-described nucleic acid molecule, i.e. a corresponding genetically modified element, such as a plasmid, virus, bacteriophage or a cosmid, that can be used for transferring and/or inserting the nucleic acid molecule into a host cell. A further object of the invention is a host, such as a bacterium, a cell or an organism, into which the before-described nucleic acid molecule or the vector comprising this nucleic acid molecule was introduced. Besides, the present invention relates to a (poly)peptide that is encoded by the before-described nucleic acid molecule.
Against this background the present invention also relates to a composition that comprises Bartonella henselae bacteria or the before-explained (poly)peptide that is derived from the Bartonella henselae adhesin A protein (BadA) or that corresponds to BadA.
In this composition the bacteria can either be present alive or deadened. Moreover, also genetically modified bacteria can be used in this connection. By means of both measures pathogenic factors can be eliminated, whereas the angiogenesis-modulating activity is conserved or is even enhanced.
These compositions are preferably pharmaceutical compositions for the modulation of the angiogenesis and comprise a pharmaceutically acceptable carrier as well as, if appropriate, further auxiliary agents. Such pharmaceutical auxiliary agents are well-known in the art; cf. for example A. Kibbe, “Handbook of Pharmaceutical Excipients”, American Pharmaceutical Association and Pharmaceutical Press, 3rd edition (2000).
Another object of the present invention is a method for detecting a Bartonella infection in a human or animal being, comprising the following steps: (a) providing a biological sample of a living being; (b) analyzing the biological sample for the existence of antibodies against the Bartonella henselae adhesin A protein (BadA), and (c) correlating a positive finding in step (b) with an infection by Bartonella.
Up to now, in the art Bartonella infections are detected serologically under employment of an immunofluorescence assay. Therefor, for example monkey kidney epithelial cells are co-cultivated with Bartonella . Subsequently, microscopic slides are covered with the cell lysate that contains whole bacteria and cell debris. These slides were incubated with a serum of a patient. If such a serum contains antibodies against Bartonella , such antibodies will bind to the intact bacteria and could be visualized by means of a labeled secondary antibody (e.g. anti-human IgG) under fluorescence excitation. The manufacture of such antigen preparations and the performance of such immunofluorescence analyses are very costly, expensive and require special skilled staff and involve several potential sources of error. To the contrary, the before-explained method according to the invention can be easily handled, is reasonably practicable and produces correct results with a high liability.
Within the frame of this method, in the biological sample, e.g. in the blood serum, the presence of antibodies against the BadA protein or against fragments of this protein can be detected, i.e. by the usage of patient sera, for example within the frame of an immunoblot via the detection of specific antibodies in the serum, and it can be shown in an indirect way that in these patients an infection by Bartonella bacteria has been occurred in the past.
Another object of the present invention relates to a method for immunizing a cat against an infection by Bartonella henselae and/or BadA, comprising the steps: (a) providing a vaccinable solution containing Bartonella henselae and/or BadA, and (b) administering said solution to a cat.
The Bartonella henselae bacteria can be killed or genetically modified. Furthermore, the BadA protein can be altered or genetically modified as explained above in more detail. Step (b) can be repeated for several times until an activation of the immune system has taken place.
By this method it is ensured that cats as the main carrier of Bartonella henselae and causers of the cat scratch disease (CSD), will no longer be receptive for an infection by Bartonella henselae and, therefore, humans who are in contact with those cats are not endangered for becoming infected due to transmission of the bacterium from these cats.
It is to be understood that the features recited above and those yet to be explained below can be used not only in the respective combination indicated, but also in other combinations or in isolation, without departing from the scope of the present invention.
The present invention is now explained in more detail by means of embodiments, from which further advantages arise.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 the progress of an infection of HeLa cells by Bartonella henselae , analyzed by confocal laser scanning microscopy;
FIG. 2 the induction of proangiogenetic host cell transcripts and proteins in HeLa cells after an infection by Bartonella henselae;
FIG. 3 the activation of HIF-1α in HeLa cells after an infection by Bartonella henselae;
FIG. 4 the activation of HIF-1α in BA-patients' samples;
FIG. 5 the preservation of the viability of HeLa cells after an infection by Bartonella henselae;
FIG. 6 the induction of proangiogenetic factors in HeLa cells after an infection by Bartonella henselae depending on BadA;
FIG. 7A-D the nucleotide sequence SEQ ID No. 1 that is derived from BadA;
FIG. 8 the adhesion of Bartonella henselae depending on BadA, and
FIG. 9 the immunoreactivity of sera of CSD patients, a rabbit infected with viable Bartonella henselae , and a mouse immunized with heat-killed Bartonella henselae , for BadA.
DESCRIPTION OF PREFERRED EMBODIMENTS
Example 1
Induction of a Genetic Program that Modifies the Angiogenesis by Bartonella henselae
The inventors have infected HeLa cells with Bartonella henselae . 6 hours after the infection, these cells were compared to non-infected HeLa cells in a standard RNA microarray analysis (AFFYMETRIX MICROARRAY SUITE 5.0; AFFYMETRIX DATA MINING TOOL 3.0) in order to determine whether the infection results in an alteration of the genetic program of the cells. The infection itself was controlled by means of confocal laser scanning micros-copy. The result of such a microscopic analysis is shown in FIG. 1 .
The left picture of the infected HeLa cells in FIG. 1 reflects the situation 1 hour, the picture in the middle 3 hours, and the right picture 6 hours after infection. The light structures which are located in the cytoplasm and which can be clearly seen in the central and the right picture correspond to bacteria which were detected by means of FITC-conjugated antibodies which were directed against the bacterium. The analysis of these pictures revealed that 6 hours after the infection>99% of the HeLa cells were infected.
The RNA microarray analysis showed that in the HeLa cells at least 7 genes were more than twofold up-regulated, which, as this has been described, are involved in the regulation of the angiogenesis and the vascularisation: Interleukin-8 (IL-8, 6,41-fold induction), Stanniocalcin-2 (STC2, 5,16-fold induction), Adrenomedullin (ADN, 3,88-fold induction), Ephrin A1 (EFNA1, 3,74-fold induction), Vascular Endothelial Growth Factor (VEGF, 3,54-fold induction), Insulin-like Growth Factor-Binding Protein-3 (IGFBP-3, 2,67-fold induction) and Endothelin 2 (ET-2, 2,13-fold induction). Except of IL-8 all of the analyzed induced genes are directly or indirectly regulated via the Hypoxia Inducible Factor-1 (HIF-1), the key transcription factor of the angiogenesis, suggesting that the main trigger for the induction of the genetic program by Bartonella henselae that modifies the angiogenesis, is HIF-1.
The results which were obtained from RNA microarray analysis were verified by means of a quantitative real-time PCR or a semi-quantitative RT PCR, and on a protein level by means of Western blotting. The result of such an experiment is shown in FIG. 2 .
For this, HeLa cells were infected by Bartonella henselae ( B.h. ), the total RNA was extracted 6 h after the infection and was transcribed into cDNA. The gene induction was evaluated by means of real-time PCR (VEGF, IL-8) or RT PCR (ADM, IGFBP-3, HK2). In order to determine the level of secreted protein, cells were infected and the supernatants of the cell cultures were analyzed 48 h after the infection by ELISA [VEGF (VEGF 165 -ELISA-Kit, Quantikine, R & D Systems, Wiesbaden); IL-8 (Schulte et al. (2000), “ Yersinia enterocolitica invasin protein triggers IL-8 production in epithelial cells via activation of Rel p65-p65 homodimers”, FASEB J 14, 1471-1484)] or RIA [ADM (RKD10-10, Phoenix Pharmaceuticals, Karlsruhe, Germany); IGFBP-3 (Blum et al. (1990), “A specific radioimmunoassay for the growth hormone (GH)-dependent somatomedin-binding protein: its use for diagnosis of GH deficiency”, J Clin. Endocrinol. Metab 70, 1292-1298)]. For Western blotting [HK2 (antibody SC6521, Santa Cruz)] 8 h after the infection cell extracts were prepared. C: Control, non-infected cells.
Also, these results verify the findings of the inventors, that an incubation of biological material, or an infection of HeLa cells with Bartonella henselae result in an induction of a genetic program that modifies angiogenesis. The level of mRNA and of protein of all angiogenesis-modulating factors which have been analyzed, were clearly increased after the infection.
Example 2
Activation of HIF-1 by Bartonella henselae
In the following, the inventors have examined whether the transcription factor HIF-1 is also be induced in the host cell after an infection by Bartonella henselae has taken place. The results of corresponding experiments are shown in FIG. 3 .
Picture (a) shows the detection of HIF-1 protein in HeLa cells 4 h after the infection by means of immunofluorescent staining under the usage of monoclonal antibodies which are specifically directed against HIF-1α (MB100- 131, Novus Biologicals, Littleton, Colo., USA) and TRITC-labeled secondary antibodies (Dianova, Hamburg, Germany), (upper row). The nuclei and bacteria were stained by DAPI (lower row). The depicted bar corresponds to 20 μm. It can be seen that 4 h after the infection with Bartonella henselae in the infected HeLa cells HIF-1α-associated signals appear in the nucleus ( B.h. , central picture, light structures). This response can also be seen in hypoxia-treated cells (cf. Raleigh et al. (1998), Cancer Res. 58, 3765-3768), (H, right picture). In contrast, in non-infected HeLa cells virtually no HIF-1α can be detected (C, left picture).
The induction of HIF-1α protein in the HeLa cells was also verified by means of Western blots which were performed 4 h after the infection. The so obtained results ( FIG. 3 b ) are consistent with those resulting from the immunofluorescence analysis. Here also a clear increase of the HIF-1α protein level can be observed in the HeLa cells 3 h after the infection by Bartonella henselae , whereas in non-infected control cells virtually no HIF-1α protein could be detected (cf. lanes 3-6 compared to 1 and 2).
The activation of HIF-1α was also verified by means of electromobility shift assays (EMSA) under usage of nucleic extracts ( FIG. 3 c ). In competition experiments, nucleic extracts of Bartonella henselae -infected HeLa cells were incubated with a labeled HIF-1α probe in the presence of a 100-fold excess of non-labeled competitor probe (comp.). It follows that the transcription factor HIF-1 is in fact present in the nucleus and can bind to the corresponding target sequences of the host cell DNA.
In transfection experiments in which a VEGF promoter luziferase reporter was used, that is specifically regulated by HIF-1 (cf. Ikeda et al., (1995), J Biol. Chem. 270, 19761-19766) it turned out that the infection of HeLa cells by Bartonella henselae ( B.h. ) results in a VEGF gene transcription that is increased to a 3- to 4-fold level; by hypoxia (H) an 8- to 20-fold stimulation can be observed ( FIG. 3 d ).
By the results which are shown in FIG. 3 arising from four independent methods it is demonstrated by the inventors, that by Bartonella henselae a modulation or activation of the angiogenesis occurs via an up-regulation of the HIF-1 transcription factor.
Example 3
Activation of HIF-1 in BA Biopsy Specimen
In order to analyze whether also in vivo in Bartonella henselae -infected tissues a HIF-1 activation occurs, sections of histological verified BA (bacillary angiomatosis) or BP (bacillary peliosis) lesions were examined for HIF-1α. The result of a corresponding experiment is shown in FIG. 4 .
Picture (a) shows the analysis of the skin of a non-affected control person, and in pictures (b) and (c) the analysis of two histologically verified BA patients' samples are shown. For the detection of HIF-1α in the tissues a labeled antibody was used that is directed against HIF-1α (MB100-131, loc. cit.). It could be shown that in the patient samples (pictures (b), (c)) HIF-1α was very clearly present in the nuclei of histiocytes or macrophages which have infiltrated the BA lesions, whereas in the control tissue (picture (a)) the HIF-1α-associated signal is much weaker (see arrows).
These results prove that by an incubation or infection of biological material, such as for example HeLa cells, with Bartonella henselae a modulation of the angiogenesis via the induction of HIF-1 is not only possible in vitro, but also in vivo.
Example 4
Bartonella henselae -infected HeLa Cells are Viable
HeLa cells were infected by Bartonella henselae and by Y. enterocolitica and the cellular morphology and the cellular viability was evaluated 12, 24 and 48 h after the infection. The result of such an experiment is shown in FIG. 5 .
Picture (a) shows the evaluation of a Giemsa staining and picture (b) the evaluation of a MTS assay (CELLTITER-96 AQ NEOUS ; Promega, Mannheim, Germany). The viability of non-infected control cells (C) was set to 100%. Each calculated value corre-sponds to the average out of three samples of each group. * indicates a significant difference compared to the control (p<0.05).
It arises from this experiment that the infection of the HeLa cells by Bartonella henselae ( B.h. ) up to 45 h after the infection does not result in a decrease of the cellular viability (cf. FIG. 3 a , central column; FIG. 3 b , central lanes). To the contrary, the cellular viability was dramatically decreased after an infection by Y. enterocoliticia ( Y.e. ) (cf. FIG. 3 a , right column, FIG. 3 b , right lanes).
This experiment indicates the pharmacological tolerance or suitability of Bartonella henselae and its therapeutical potential as an active agent of a pharmaceutical composition.
Example 5
Induction of an Angiogenesis-modifying Genetic Program by the Adhesin A Protein of Bartonella henselae (BadA)
Since the before-shown experiments demonstrate that the incubation or infection of biological material, such as HeLa cells or tissues, by Bartonella henselae results in an up-regulation of angiogenesis-modifying genes, which are controlled by the key transcription factor of the angiogenesis HIF- 1, it was also analyzed by the inventors, whether a specific bacterial protein can be found that is responsible for this biological effect. In connection with this it was also tested, whether the surface protein of Bartonella henselae , BadA, having a molecular weight of 340 kD and that has been detected by the inventors, is involved in the modulation of the angiogenesis or the up-regulation of angiogenesis-modulating host cell components, such as the Vascular Endothelial Growth Factor (VEGF), Interleukin-8 (IL-8), Insulin-like Growth Factor Binding Protein-3 (IGFBP-3). In these experiments two mutants of Bartonella henselae were used, which do not express the BadA protein (BadK mutants), as well as wild type Bartonella henselae as a control. With these Bartonella henselae bacteria HeLa cells were infected and cultivated, the cell culture supernatants were removed 8, 24, 48 and 72 h after the infection, centrifuged and frozen at −20° C. The VEGF concentration in the supernatants was determined by the usage of a human VEGF 165 ELISA Kit (cit. loc.), IL-8 was determined by means of ELISA, as described in Schulte et al. (cit. loc.). The IGFBP-3 that was secreted into the cell culture supernatant was measured under the usage of a specific RIA, cf. concerning this Blum et al. (cit. loc). The result of such an experiment is shown in FIG. 6 .
This experiment shows that an infection of HeLa cells by the two BadA − mutants (-♦- first mutant; -▴- second mutant) does not result in any increase of the production of angiogenesis-modulating factors, whereas the infection by wild type Bartonella henselae (-▪-) causes a clear increase of angiogenesis-modulating cytokines in the correspondingly infected HeLa cells.
In further experiments the BadA− mutants were complemented by the introduction of an expression vector that expresses functional BadA protein, i.e. the mutants were subsequently again in the condition to synthesize BadA and to insert it into the membrane. While performing the before-mentioned experiment, it could be demonstrated that such complemented BadA− mutants are again in the condition to stimulate the production of angiogenesis-modulating factors, such as VEGF (data not shown).
It follows that BadA is a crucial bacteria factor of Bartonella henselae that is responsible for modulating the angiogenesis and, therewith, is suitable as an active agent in a pharmaceutical composition for the modulation of the angiogenesis.
The DNA nucleotide sequence encoding the bacterial BadA protein is indicated as SEQ ID No. 1 and shown in FIG. 7 . As usual, the presentation starts with the 5′-end that comprises the initiation codon (ATG), and extends to the 3′-end that comprises the stop codon (TAA). The last 111 nucleotides at the 3′-end encode the so-called membrane anchor domain that is responsible for insertion of the protein into the bacterial membrane.
Example 6
BadA as the Key Factor in the Adhesion of Bartonella henselae to Endothelial Cells
After that, the inventors have analyzed whether BadA is involved in the adhesion of Bartonella henselae to endothelial cells, among other things in order to get information about the possible mode of action of the modulation of the angiogenesis.
For this, endothelial cells were infected by the before-mentioned Bartonella henselae bacteria (wild type, two different BadA − mutants) and 30 min after the infection the amount of adhering bacteria was determined. For doing this, the cell culture supernatants were carefully removed, the cells were thoroughly washed with Clicks (RPMI 1640 medium), lysed and the total amount of adhering bacteria was determined. The results of such an experiment are shown in FIG. 8 .
In the upper illustrations as a control it is demonstrated by transmission electron microscope that wild type Bartonella henselae expresses, as expected, BadA on its surface (see arrows, left picture), whereas the two BadA − mutants do not express any BadA (central and right picture).
Furthermore, it is shown by this experiment that a BadA − mutation results in a dramatical decrease of the adhesion of the corresponding mutant to endothelial cells (lower picture; compare central and right column to left column).
The before-described observations concerning the adhesion of the wild type or genetically modified Bartonella henselae bacteria, were also verified by means of immunofluorescence analysis via laser scanning microscopy staining (data not shown).
In further experiments, the BadA − mutants were complemented by the introduction of an expression vector that expresses functional BadA protein (cf. example 5). While performing these before-explained experiments it turned out that such complemented BadA − mutants are again in the position to adhere to endothelial cells. It could also be demonstrated that BadA − mutants, in contrast to Bartonella henselae wild type bacteria, were no more able to bind to fibronectin and collagen. This loss was recovered by the introduction of the above-mentioned BadA encoding expression vector into the mutants (data not shown).
These results indicate that the modulation of the angiogenesis by Bartonella henselae is mediated by the adhesion of BadA to the biological material, for example to the endothelial cells.
Example 7
BadA as a Diagnostic Marker for Infections by Bartonella
In another experiment the inventors have analyzed whether antibodies directed against BadA can be found in human sera of patients who are affected by an infection with Bartonella henselae , or of rabbits and mice infected with viable or heat-killed Bartonella henselae.
For this wild type bacteria of Bartonella henselae and BadA − mutants of Bartonella henselae were separated by electrophoresis and transferred onto a blotting membrane. The membrane was incubated with human sera which came from patients suffering from cat scratch disease (CSD), or from healthy control patients, or from infected rabbits and mice. The result of such an experiment is depicted in FIG. 9 .
In the respective upper lanes wild type bacteria lysate (WT) was separated, whereas in the respective lower lanes BadA − bacteria lysate (BadA − ) was separated, blotted and afterwards incubated with sera of CSD patients, sera of rabbits infected by viable Bartonella henselae , or sera of mice infected by heat-killed Bartonella henselae . In the lowest two lanes, wild type and BadA − bacteria lysate were separated and incubated with serum of a healthy control person.
The arrow indicates the position of the separated BadA. It can be seen that by means of the sera that came from a CSD-affected patient (patient), or infected mice or rabbits, BadA protein is detected, consequently their immune systems have produced antibodies against the BadA protein, whereas in the human serum that came from the healthy control person (Kontr.) no antibodies against BadA are contained and therefore no immunoreactive band on the level of the BadA protein appears. Since the BadA − mutants do not comprise any BadA protein no immunoreactive band on the level of the BadA protein can be found.
In total, seven out of eleven sera coming from CSD patients showed a reactivity against BadA, compared to one out of nine sera coming from healthy control persons.
These experiments demonstrate that BadA is a suitable diagnostic marker for identifying Bartonella infections. | The present invention relates to Bartonella henselae as a component of a pharmaceutical composition for the modulation of the angiogenesis; a nucleic acid molecule that is derived from the gene encoding the Bartonella henselae adhesin A protein (BadA), a vector comprising said nucleic acid molecule; a host containing said nucleic acid molecule or said vector; a (poly)peptide encoded by said nucleic acid molecule; a composition comprising Bartonella henselae bacteria; a composition comprising aforesaid (poly)peptide; a method for treating a human or animal being in need of the modulation of the angiogenesis, a method for detecting an infection by Bartonella in a human or animal being, as well as a method for immunizing a cat. | 2 |
RELATED APPLICATIONS
[0001] This is a continuation-in-part application of a prior filed and currently pending application having Ser. No. 10,266,529 filed on Oct. 8, 2002 and entitled, “Apparatus and Method for Flushing and Cleaning Engine Lubrication Systems.” This application also relates to pending application Ser. No. 10,640,606, filed on Aug. 12, 2003, and Ser. No. 10,666,583 filed on Sep. 17, 2003, and Ser. No. 10,770,896 filed on Feb. 2, 2004.
INCORPORATION BY REFERENCE
[0002] Applicant(s) hereby incorporate herein by reference, any and all U.S. patents, U.S. patent applications, and other documents and printed matter cited or referred to in this application.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] This invention relates generally to automotive radiator flush systems and their methods of use and more particularly to an automated or manually operated system and its method of use and especially to such a system with controls for switching to various modes of operation using ganged valves and gas tight tanks.
[0005] 2. Description of Related Art
[0006] The following art defines the present state of this field:
[0007] Cassia, U.S. Pat. No. 5,103,878 describes a flush cap for a vehicle cooling system wherein the flush cap has an inlet through which fresh water enters and an outlet through which dirty coolant leaves. The method employs the flush cap to flush the cooling system of the vehicle. The radiator cap can be adapted to drain a radiator using a hose attached to the outlet of the cap.
[0008] Akazawa, U.S. Pat. No. 5,615,716 describes an engine coolant changing apparatus for changing an engine coolant such as LLC (long-life coolant) in an engine coolant path containing a radiator, comprising coolant storing means possessing a pressure action port and a liquid inlet and outlet, detaching mechanism to be attached or detached to or from a filler port of a radiator, communicating device for communicating between the liquid inlet and outlet and the detaching device, and pressure action device for applying a negative pressure to the pressure action port to overheat the coolant to a low temperature by driving an engine when discharging the coolant from an engine coolant system, and applying a positive pressure to the pressure action port when feeding a fresh liquid, so that the coolant can be changed promptly in a short time, without requiring manipulation of radiator drain cock or jack-up of the vehicle.
[0009] Turcotte et al., U.S. Pat. No. 5,649,574 describes a removal and refill apparatus for use in removing and/or refilling coolant in an automotive cooling system. The automotive cooling system typically includes a radiator, overflow bottle, engine, water pump, and heater core elements. A method for utilizing the coolant removal and refill apparatus utilizing vacuum and pressure is described for use with the removal and refill apparatus.
[0010] Fletcher, Jr. et al., U.S. Pat. No. 5,845,684 describes a clean and easy-to-use, portable upright apparatus, and a method for its use, which can be used to flush and fill the radiator and coolant systems of motorized vehicles in approximately 15 minutes, the apparatus comprising a self-priming pump, a waste collection tank, a tank for holding new or recycled coolant, a filter assembly, and a wheeled support structure for conveniently and efficiently housing the pump, tanks, filter assembly, and the several hoses needed to perform the flush and fill procedure. Applications may include, but are not limited to, flushing coolant from automobile radiators and refilling them with new or recycled coolant.
[0011] Klamm, U.S. Pat. No. 6,345,215 describes an apparatus for adding coolant to a cooling system of a motor vehicle including a cap with a resilient sleeve that expands against the inside wall of a radiator filler neck to provide an air-tight connection. A valve attached to the cap controls the flow of air and coolant through the cap. A gauge on the cap indicates the pressure inside the radiator. A venturi assembly connected to the valve provides a source of vacuum for evacuating air from the cooling system. Thereafter, coolant is drawn through the cap by the vacuum created in the system.
[0012] Awad, U.S. Pat. No. 6,523,580, describes an apparatus comprising a wheeled cart, and mounted on the wheeled cart a plurality of containers placed in adjacent upright attitudes. A support framework engages the wheeled cart and further provides a support framework engaging an operator's panel with operator's controls. A suction developing device, pressure developing device, conduit switching device, and conduit manifolding device, are enabled for acting together to apply vacuum and pressure exertion on fluids for driving such fluids between the containers and an automotive radiator through a system of conduits.
[0013] Awad, U.S. Pat. No. 6,604,557, describes a method of replacing radiator fluid in an automotive radiator including providing two gas tight containers, a fluid conducting hose with a gas tight nozzle fitted into a radiator fill pipe nipple. The method further includes the steps of filling one of the containers with a fresh radiator fluid, drawing a high vacuum on a second one of the containers, drawing spent radiator fluid into the second one of the containers using only suction from the container, thereby leaving the automotive radiator under a partial vacuum and then drawing the fresh radiator fluid, from the first one of the containers, into the radiator using only suction from the partial vacuum in the radiator. A radiator flush step may also be applied following the same method, using two additional containers, one with initial high vacuum and the other containing flush fluid.
[0014] Gayet, EP 1013908 describes a coolant fluid replacement device for an automobile, utilizing an open loop distribution circuit within the coolant loop during the replacement of the used coolant. The coolant loop comprises a radiator that includes an inlet from the engine and an outlet to the engine. During the coolant replacement process, the device is connected between the coolant pumps of the vehicle system. The new fluid is stored in a first reservoir. As the new fluid is pumped into the system, the old fluid is forced out into a second reservoir.
[0015] The prior art teaches automotive maintenance and especially in the field of radiator fluid replacement, but does not teach the use of ganged control valves for fast switching from withdrawal phase to delivery phase using suction and especially providing of both suction and fluid delivery switching using a ganged valve. The present invention fulfills these needs and provides further related advantages as described in the following summary.
SUMMARY OF THE INVENTION
[0016] In the field of automotive maintenance, the exchange of cooling, lubricating and other fluids is an ongoing necessity. However, the prior art teaches methods that are clearly unsanitary, environmentally undesirable, time consuming and messy. The present apparatus and its method of use provides a distinct improvement in equipment cost and use. Its applications extend from automotive fluid exchange to use in industry in general. A fluid exchange system, mounted on a mobile cart or fixed in place, as on an assembly line, provides ganged valves to enable the use of suction to withdraw fluid from one tank leaving the tank with a partial vacuum, and then replacing the fluid using suction from the tank to a fluid supply vessel. The ganged valve permits the simultaneous directing of suction and liquid flow for both withdrawal and replacement as the ganged valves are moved from one position to another.
[0017] The present invention teaches certain benefits in construction and use which give rise to the objectives described below.
[0018] A primary objective of the present invention is to provide an apparatus and method of use of such apparatus that provides advantages not taught by the prior art.
[0019] Another objective is to provide such an invention capable of moving fluids between storage containers and an automotive radiator with only an initial vacuum drawn on one of the containers.
[0020] A further objective is to provide the quick switching from withdrawal of a spent cooling fluid or the like to replacement with a new fluid.
[0021] A still further objective is to provide dual switching of pressure or suction along with the moving of a liquid fluid in a fluid exchange system.
[0022] Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The accompanying drawings illustrate the present invention. In such drawings:
[0024] FIGS. 1, 2 and 3 show a component diagram of a preferred embodiment of the present apparatus;
[0025] FIG. 1 shows withdrawal of fluid from a tank in the present system using suction;
[0026] FIG. 2 shows replacement of the fluid using residual vacuum in the tank; and
[0027] FIG. 3 shows delivery of the withdrawn fluid to a collection tank.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The above described drawing figures illustrate the present invention in at least one of its preferred, best mode embodiments, which is further defined in detail in the following description. Those having ordinary skill in the art may be able to make alterations and modifications in the present invention without departing from its spirit and scope. Therefore, it must be understood that the illustrated embodiments have been set forth only for the purposes of example and that they should not be taken as limiting the invention as defined in the following.
[0029] A fluid exchange apparatus comprises components including a receiver tank 10 , a discharge tank 20 ; an air inlet 30 , a mode valve 40 , a vacuum inductor 50 , a dual valve set 60 having an A-valve 62 conductive between alternative first flow paths, and a B-valve 64 conductive between alternative second flow paths. The A-valve 62 and the B-valve 64 are ganged, i.e., joined to move between their respective first and second alternative flow paths simultaneously. A conduit means 70 such as plastic or metal tubing, joins the components 10 - 60 in the arrangement shown in FIGS. 1-3 and such interconnections of components into a fluid flow system is considered to be known by those of skill in the art. In the figures it is shown that pressurized air is introduced to the system at upper left and enters the system through air inlet 30 preferably comprising a fitting 32 that accepts a hose 34 through which compressed air is delivered to inlet valve 36 . Inlet valve 36 , in portions of the present method of use, is adjusted to enable air to enter the system. Preferably, a pressure regulator with gauge 38 , is made a part of the system in order to adjust the inlet air pressure to a satisfactory working level as is well known in the art. A mode valve 40 is placed as shown in the figures and mode valve 40 , may be set as in FIG. 1 , to deliver the air pressure and flow to a vacuum inductor 50 , preferably of the Venturi principal type as shown, so as to produce suction in the system. The mode valve 40 may alternatively be placed as shown in FIG. 3 so as to deliver air pressure and flow to the system rather than suction.
[0030] Attention is drawn to the dual valve set 60 , which, in general, may be an assembly of more than two valves as desired. However, in the present example, the dual valve set 60 provides the function necessary to achieve the objectives previously described. It should be noticed that valve set 60 , when its handle is in the first position shown in FIGS. 1 or 3 , enables fluid flow between the left conduit and the center conduit respectively for both the A-valve and the B-valve, while with the handle set in the further position shown in FIG. 2 , fluid flow is enabled between the right conduit and the center conduit, again, for both the A-valve and the B-valve. This fluid switching function and its importance will become apparent from the further description below.
[0031] Now, with the mode valve 40 in its first position, and the dual valve set in its initial position as shown in FIG. 1 , air flow introduced at the air inlet 30 is conducted through the vacuum inductor 50 establishing suction at the receiver tank 10 through the A-valve 62 , and thereby drawing fluid from the working fluid tank 80 , which may be an automotive radiator or similar tank, into the receiver tank 10 through the B-valve 64 . Sealing fixture 90 , a conical-shaped rubber stopper through which conduction means 70 extends, enables a vacuum to be formed within the working fluid tank 80 as fluid is drawn from it. The arrows in the figures show the direction of flow in the system.
[0032] Once this fluid transfer has been accomplished, the dual valve set 60 is placed into its further position, as shown in FIG. 2 (see the valve handle in FIGS. 1 and 2 ), after the air inlet valve 36 is closed. Now, ambient air is drawn into the system through the vent pipe of inductor 50 and conducted to the discharge tank 20 through the A-valve; thereby enabling fluid from the discharge tank 20 to flow into the working fluid tank 80 through the B-valve due to vacuum suction from the tank 80 . It should be clear that in this step the motive force for moving fluid from tank 20 to tank 80 is not outside air pressure, and it is not suction developed at inductor 50 , but rather it is the low pressure (vacuum) condition left in tank 80 after removing its fluid. To accomplish this, tank 80 would have to be fully sealed including the advantageous use of sealing fixture 90 .
[0033] In the present example the application involves drawing spent radiator coolant fluid from an automotive radiator (tank 80 ), and replacing it with new radiator coolant fluid. However, one of skill will find other obvious applications for the present apparatus and method.
[0034] When necessary to discharge the spent fluid in the receiver tank 10 in preparation of further fluid cycling, as described above, the mode valve 40 is placed in its second position, and the dual valve set 60 is placed in its initial position, as shown in FIG. 3 , so as to deliver pressurized air through the inlet valve 36 to direct fluid from the receiver tank 10 into a collection tank 100 .
[0035] The enablements described in detail above are considered novel over the prior art of record and are considered critical to the operation of at least one aspect of one best mode embodiment of the instant invention and to the achievement of the above described objectives. The words used in this specification to describe the instant embodiments are to be understood not only in the sense of their commonly defined meanings, but to include by special definition in this specification: structure, material or acts beyond the scope of the commonly defined meanings. Thus if an element can be understood in the context of this specification as including more than one meaning, then its use must be understood as being generic to all possible meanings supported by the specification and by the word or words describing the element.
[0036] The definitions of the words or elements of the embodiments of the herein described invention and its related embodiments not described are, therefore, defined in this specification to include not only the combination of elements which are literally set forth, but all equivalent structure, material or acts for performing substantially the same function in substantially the same way to obtain substantially the same result. In this sense it is therefore contemplated that an equivalent substitution of two or more elements may be made for any one of the elements in the invention and its various embodiments or that a single element may be substituted for two or more elements in a claim.
[0037] Changes from the claimed subject matter as viewed by a person with ordinary skill in the art, now known or later devised, are expressly contemplated as being equivalents within the scope of the invention and its various embodiments. Therefore, obvious substitutions now or later known to one with ordinary skill in the art are defined to be within the scope of the defined elements. The invention and its various embodiments are thus to be understood to include what is specifically illustrated and described above, what is conceptually equivalent, what can be obviously substituted, and also what essentially incorporates the essential idea of the invention.
[0038] While the invention has been described with reference to at least one preferred embodiment, it is to be clearly understood by those skilled in the art that the invention is not limited thereto. Rather, the scope of the invention is to be interpreted only in conjunction with the appended claims and it is made clear, here, that the inventor(s) believe that the claimed subject matter is the invention. | A fluid exchange system provides ganged valves to enable the use of suction to withdraw fluid from a tank leaving the tank with a partial vacuum, and then replacing the fluid in the tank by suction from the tank to a fluid supply vessel. The ganged valve permits the simultaneous directing of suction and liquid flow for both withdrawal and replacement as the ganged valves are moved from one position to another. | 5 |
BACKGROUND
[0001] 1. Field
[0002] Embodiments of the present invention generally relate to method and apparatus for processing a semiconductor substrate. More particularly, embodiments of the present invention provide method and apparatus for processing a semiconductor substrate with improved uniformity.
[0003] 2. Description of the Related Art
[0004] When processing substrates in a plasma environment, the uniformity of the plasma will affect the uniformity of processing. For example, in an etching process, more material is likely to be removed or etched from the substrate near the center of the substrate as compared to the edge of the substrate when plasma of the processing gases is greater in the area of the chamber corresponding to the center of the substrate. Similarly, if the plasma is greater in the area of the chamber corresponding to the edge of the substrate, more material may be removed or etched from the substrate at the edge of the substrate compared to the center of the substrate
[0005] Non-uniformity in plasma processes can significantly decrease device performance and lead to waste because the deposited layer or etched portion is not consistent across the substrate.
[0006] Excellent process uniformity has become increasingly important as semiconductor devices become continuously more complex. Uniformity is important in both the feature-scale (<1 micron) and the wafer-scale (300 mm). Non-uniformities arise from a variety of reasons, for example variation of concentration of different ingredients of a processing gas, such as etching and passivating species, ion bombardment flux and energy, and temperature within the feature profile and across the wafer.
[0007] One of the non-uniformities observed is CD (critical dimension) bias edge roll-off. CD bias refers to the difference between the critical dimension of a feature before and after processing. CD bias edge roll-off refers to decrease of CD bias toward an edge of a substrate compared to CD bias near a central region of the substrate.
[0008] FIG. 1 schematically illustrates a CD bias edge roll-off of a hard mask etching process in a gate etching application. FIG. 1 demonstrates a critical dimension from bottom measurement of isolated features across a radius of a substrate after etching. The x-axis of FIG. 1 indicates a distance from the center of the substrate, and the y-axis indicates a critical dimension measurement. The CD bias edge roll-off is obvious from the decrease of the critical dimension measurement from 110 mm to 150 mm, i.e. towards the edge of the substrate. Additionally, FIG. 1 also illustrates non-uniformity near a center of the substrate where the critical dimension measurements are lower than a middle section of the substrate.
[0009] Traditionally, non-uniformity during etch, such as the CD bias edge roll-off shown in FIG. 1 , is controlled by maintaining a temperature gradient across the substrate using heaters in the substrate support. However, in most applications, adjusting the substrate temperature gradient is still an inadequate method to tune the CD bias edge roll-off.
[0010] Therefore, there is a need for apparatus and method for processing a semiconductor substrate with reduced CD bias edge roll-off and other non-uniformity.
SUMMARY
[0011] Embodiments of the present invention generally provide apparatus and methods for processing a semiconductor substrate. Particularly, the embodiments of the present invention provide apparatus and method for processing a substrate with increased uniformity.
[0012] One embodiment of the present invention provides an apparatus for processing a substrate comprising a chamber body defining a processing volume, a substrate support disposed in the processing volume, a showerhead disposed in the processing volume opposite to the substrate support, wherein the showerhead is configured to provide one or more processing gases to the processing volume, the showerhead has two or more distribution zones each independently controllable, and a plasma generation assembly configured to ignite a plasma from the processing gases in the processing gas in the processing volume.
[0013] Another embodiment of the present invention provides a method for processing a substrate comprising positioning the substrate on a substrate support disposed in a plasma chamber, flowing a first processing gas towards a top surface of the substrate, flowing a second processing gas towards an edge region of the substrate, wherein the first processing gas and the second processing gas are different, and striking a plasma of the processing gases in the plasma chamber.
[0014] Yet another embodiment of the present invention provides a method for adjusting process uniformity in an etching process comprising positioning a substrate on a substrate support disposed in a plasma chamber, flowing processing gases to the plasma chamber, wherein flowing the processing gases comprises flowing a first processing gas towards a central region of the substrate being processed at a first flow rate, flowing the first processing gas towards a region radially outwards the central region of the substrate at a second flow rate, and flowing a second processing gas towards an edge region of the substrate, and generating a plasma of the processing gases in the plasma chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] So that the manner in which the above recited features of embodiments of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0016] FIG. 1 (prior art) schematically illustrates a CD bias edge roll-off of a hard mask etching process in gate etching application.
[0017] FIG. 2 is a schematic sectional side view of a plasma chamber in accordance with one embodiment of the present invention.
[0018] FIG. 3 is a schematic top of a showerhead for a plasma chamber in accordance with one embodiment of the present invention.
[0019] FIGS. 4A-4B illustrate results of a method for reducing CD bias edge roll-off in accordance with one embodiment of the present invention.
[0020] FIGS. 5A-5B illustrate results of a method for improving CD bias uniformity across a substrate in accordance with one embodiment of the present invention.
[0021] FIGS. 6A-6B illustrate effects of adjusted spacing on CD bias uniformity.
[0022] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements disclosed in one embodiment may be beneficially utilized on other embodiments without specific recitation.
DETAILED DESCRIPTION
[0023] Embodiments of the present invention generally provide apparatus and method for improving process uniformity. More particularly, the embodiments of the present invention provide apparatus and method for CD bias uniformity and edge roll-off. In one embodiment, a multi-zone showerhead is used for an etching process. In one embodiment, additional passivating gas is supplied to a plasma chamber from an outermost zone of the multi-zone showerhead while processing gas comprising both etching gas and passivating gas is supplied from one or more inner zones of the showerhead. Edge roll-off may be reduced by adjusting the passivating gas provided from the outermost zone of the showerhead. The overall CD bias uniformity may be adjusted by adjusting a ratio of flow rates among one or more inner zones of the showerhead. In another embodiment, the CD bias may be adjusted by adjusting spacing between the substrate and the showerhead.
[0024] FIG. 2 is a schematic sectional side view of a plasma reactor 200 in accordance with one embodiment of the present invention. The plasma reactor 200 comprises a processing chamber 202 configured to process a substrate 204 therein.
[0025] The processing chamber 202 comprises a chamber wall 228 , a chamber bottom 227 , and a chamber lid 229 . The chamber wall 228 , chamber bottom 227 , and the chamber lid 229 define a processing volume 218 .
[0026] A substrate support 206 is disposed in the processing volume 218 configured to support the substrate 204 during processing. The substrate support 206 may move vertically and rotate about a central axis driven by a moving mechanism 262 . In one embodiment, the substrate support 206 may be a conventional electrostatic chuck that actively holds the substrate 204 during processing.
[0027] In one embodiment, the substrate support 206 may be temperature controlled by a temperature controller 261 adapted to cool and heat the substrate support 206 to a desired temperature. The temperature controller 261 may use conventional means, such as embedded resistive heating elements, or fluid cooling channels that are coupled to a heat exchanger.
[0028] A showerhead 208 is disposed in the processing volume 218 through the chamber lid 229 . The shower head 208 is disposed opposite the substrate support 206 and is configured to provide one or more processing gases to the processing volume 218 through a plurality of holes 209 .
[0029] In one embodiment, the showerhead 208 may have multiple zones each configured to deliver processing gases to a certain area of the processing volume 218 and certain area of the substrate 204 . Each of the multiple zones may be independently connected to the gas source 212 , thus, allowing control of gas species and flow rate provided to different areas of the processing volume 218 .
[0030] In one embodiment, the showerhead 208 may have multiple zones arranged in a concentric manner. As shown in FIG. 2 , the showerhead 208 has an inner zone 230 corresponding to a central region of the substrate support 206 , an edge zone 232 corresponding to an edge region of the substrate support 206 , and a middle zone 231 radially outwards from the inner zone 230 and inwards from the edge zone 232 . Each of the inner zone 230 , middle zone 231 and edge zone 232 is independently connected to the gas source 212 .
[0031] The gas source 212 may be a gas panel with multiple outputs each adapted to output an independent flow of an independent combination of species. A system controller 213 may be used to control flow rate and ratio of species provided from the gas source 212 to the inner zone 230 , middle zone 231 and edge zone 232 .
[0032] During processing, a plasma is generated within the processing volume 218 by a plasma generating assembly to process the substrate 204 . In one embodiment, the plasma generating assembly may include a capacitor having the showerhead 208 and the substrate support 206 as electrodes. In one embodiment, a RF (radio frequency) power source 235 may be connected to the substrate support 206 through an impedance match network 234 , and the showerhead 208 is grounded. A plasma may be generated in the processing volume 218 between the showerhead 208 and the substrate 204 when a RF power is applied to the substrate support 206 .
[0033] It should be noted that other configurations of plasma may be applied, for example, a capacitive plasma generator with a RF power source applied to the showerhead 208 and the substrate support 206 is grounded, a capacitive plasma generator using electrodes other than the showerhead 208 and the substrate support 206 , an inductively coupled plasma generator, or a combination of capacitive and inductive plasma generator. Inductive coils may be disposed above the showerhead 208 of the plasma reactor 200 for generating inductively coupled plasma. Exemplary inductive coupled plasma generator may be found in U.S. patent application Ser. No. 11/960,111, entitled “Apparatus and Method for Processing a Substrate Using Inductively Coupled Plasma Technology,” which is incorporated herein by reference.
[0034] The showerhead 208 of the plasma reactor 200 is configured to adjust performance across the substrate 204 by adjusting flow rate and gas species supplied to different regions over the substrate 204 .
[0035] FIG. 3 is a schematic bottom view of the showerhead 208 for the plasma reactor 200 of FIG. 2 . The showerhead 208 has a substantially circular bottom surface 208 a configured to be disposed opposite the substrate support 206 in a parallel manner. The plurality of the holes 209 connects with the gas source 212 through different gas passages. In this configuration, the holes 209 are distributed in the inner zone 230 , the middle zone 231 and the edge zone 232 . The holes 209 within each of the zones 230 , 231 , 232 are connected respectively to an output of the gas source 212 .
[0036] Even though the showerhead 208 described here has three concentric zones for independent gas control, other arrangements, for example, more or less concentric zones, zones of different shapes, may be used for the same purpose.
[0037] Embodiments of the present invention provide method for improving process uniformity across a substrate. The method comprises one of adjusting flow rates to different regions of a processing chamber, adjusting components in the processing gas supplied to different regions, adjusting spacing between electrodes of a capacitive plasma generator, or combinations thereof.
[0038] FIGS. 4-6 illustrate results from examples of plasma etching processes incorporated with embodiments of the present invention. The examples discussed below are hard mask etching process performed in a capacitive coupled plasma reactor having a showerhead with three zones, similar to the plasma reactor 200 of FIG. 2 .
[0039] The etching process is generally performed by positioning a substrate to be etched in a plasma chamber, flowing a processing gas into the chamber, and etching the substrate by generating a plasma of the processing gas in the plasma chamber. The processing gas generally comprises an etching gas and a passivating gas mixed in a certain ratio. The processing gas may also comprise a carrier gas. The etching gas may be CF 4 , C 2 F 6 , C 4 F 8 ,Cl 2 , BCl 3 , CCl 4 , NF 3 , SF 6 , HBr, BBr 3 , C 2 F 2 , O 2 , H 2 , CH 4 , COS SO 2 , and combinations thereof, depending on the material to be etched. The passivating gas may comprise CHF 3 , CH 2 F 2 , CH 3 F, SiCl 4 , HBr, and the combinations thereof, depending on the material to be etched and the etching gas used. The carrier gas may be any inert gas, such as Ar, He, N2, and combinations thereof. It is to be appreciated that other suitable etching gases and passivating gases can also be used.
[0040] The examples listed below use a capacitively coupled CF 4 /CHF 3 plasma to etch a silicon nitride hard mask, wherein CF 4 acts as etching gas and CHF 3 acts as passivating gas. The processing gas, CF 4 and CHF 3 in this case, is distributed to the chamber through a tri-zone showerhead. Flow rates, gas ratio, and spacing may be adjusted to adjust CD bias result across the substrate.
[0041] The showerhead used in the examples has three zones. Zone 1 covers a circular region of about 3.36 inch in diameter corresponding to a central region of the substrate being processed. Zone 2 covers a circular region with an inner diameter of about 3.36 inch and an outer diameter of about 7.68 inch. Zone 3 covers a circular region with an inner diameter of about 7.68 inch and an outer diameter of about 12 inch.
[0042] It has been observed that chemical etching processes exhibit a significant loading effect resulting from the depletion of active etching species by reaction with the film being etched. Thus, the etch rate depends on the etchable area either on the feature-scale (microloading) or on the substrate-scale (macroloading). On the feature-scale, microloading is brought about by differences in the feature dimension and pattern density. For example, isolated features etch at a different rate than dense features. Therefore, macroloading and microloading tunability is an essential requisite to a successful etching process. Thus, examples below are performed on both substrates with isolated features and substrates with dense features to examine macroloading and microloading tunability.
[0043] FIGS. 4A-4B illustrate results of a method for reducing CD bias edge roll-off by supplying additional passivating gas to an edge region of the substrate in accordance with one embodiment of the present invention.
EXAMPLE 1
[0044] FIGS. 4A-4B illustrate effects of varying passivating gas flow in Zone 3 while the other processing parameters remain the same. FIG. 4A shows CD bias results for etching on substrates having isolated features. FIG. 4B shows CD bias results for etching on substrates with densely packed features.
[0045] The following illustrates an exemplary etching process with the following parameters:
Temperature: about 60° C. Chamber pressure: about 90 mTorr Spacing: about 2.3 inch (the distance between shower head and substrate being processed, as shown by distance 233 of FIG. 2 ) RF power: about 500 W and 60 MHz Flow rates in Zone 1 : 300 sccm of CF 4 , 220 sccm of CHF 3 Flow rates in Zone 2 : 0 sccm of CF 4 , 0 sccm of CHF 3 Flow rates in Zone 3 : 0 sccm of CF 4 , 10/50/100 sccm of CHF 3
[0053] As shown in FIGS. 4A-4B , edge roll-off is reduced by supplying additional passivating gas CHF 3 to Zone 3 for both substrates with isolated features and dense features. Substrates with dense features are more susceptible to edge roll-off. The edge roll-off can be substantially eliminated by flowing 100 sccm passivating gas to Zone 3 .
[0054] Even though only the passivating gas is supplied near the edge region in Example 1, any adjustment to provide additional passivating gas near the edge region may be applied. For example, both etching gas and passivating gas may be supplied to all regions of the substrate, only a higher ratio of passivating gas is supplied near the edge compared to the central region of the substrate.
[0055] FIGS. 5A-5B illustrate results of a method for improving CD bias uniformity across a substrate by tuning ratio of flow rates among regions of the substrate in accordance with one embodiment of the present invention.
EXAMPLE 2
[0056] FIGS. 5A-5B illustrate effects of varying ratio of flow rates between Zone 1 and Zone 2 while the other processing parameters remain the same. FIG. 5A shows CD bias results for etching on substrates having isolated features. FIG. 5B shows CD bias results for etching on substrates with densely packed features.
[0057] The following illustrates an exemplary etching process with the following parameters:
Temperature: about 60° C. Chamber pressure: about 90 mTorr Spacing: about 2.3 inch RF power: about 500 W and 60 MHz Flow rates in Zone 1 : 300*x sccm of CF 4 , 220*x sccm of CHF 3 Flow rates in Zone 2 : 300*(1−x) sccm of CF 4 , 220*(1−x) sccm of CHF 3 , x=1, 1/3, 1/3.5 Flow rates in Zone 3 : 0 sccm of CF 4 , 100 sccm of CHF 3
[0065] As shown in FIGS. 5A-5B , CD uniformity is improved by adjusting flow ratio of Zone 1 and Zone 2 for both substrates with isolated features and dense features. Thus, CD uniformity may be improved by adjusting ratio of flow rates of processing gas to different regions of a substrate. Particularly, CD uniformity may be improved by adjusting ratio of flow rate along a radius of a substrate being processed.
EXAMPLE 3
[0066] FIGS. 6A-6B illustrate effects of adjusted spacing on CD bias uniformity while the other processing parameters remain the same. FIG. 6A shows CD bias results for etching on substrates having isolated features. FIG. 6B shows CD bias results for etching on substrates with densely packed features.
[0067] The following illustrates an exemplary etching process with the following parameters:
Temperature: about 60° C. Chamber pressure: about 90 mTorr Spacing: about 2.3 inch/5.0 inch RF power: about 500 W and 60 MHz Flow rates in Zone 1 : 86 sccm of CF 4 , 63 sccm of CHF 3 Flow rates in Zone 2 : 214 sccm of CF 4 , 146 sccm of CHF 3 Flow rates in Zone 3 : 0 sccm of CF 4 , 100 sccm of CHF 3
[0075] FIGS. 6A-6B illustrate that CD bias may be changed evenly across the substrate by changing the spacing. Substrates with dense features are less responsive to the change of spacing compared to substrates with isolated features. Edge areas are slightly less responsive to the change of spacing.
[0076] The approaches illustrated in Examples above may be combined to achieve a desired processing profile across a substrate. Additionally, a desired processing profile may be any profiles depending on a process, for example, a uniform profile, an edge weak profile (where edge areas are processed less than central areas), or an edge strong profile (wherein edge areas are processed more than central areas).
[0077] Even though an etching process is described in accordance with embodiments of the present invention, embodiments of the present invention may be applied to improve uniformity across a substrate for any suitable processes, for example deposition and implantation.
[0078] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | Embodiments of the present invention provide apparatus and method for processing a substrate with increased uniformity. One embodiment of the present invention provides an apparatus for processing a substrate. The apparatus comprises a chamber body defining a processing volume, a substrate support disposed in the processing volume, a showerhead disposed in the processing volume opposite to the substrate support, and a plasma generation assembly configured to ignite a plasma from the processing gases in the processing gas in the processing volume. The showerhead is configured to provide one or more processing gases to the processing volume. The showerhead has two or more distribution zones each independently controllable. | 2 |
FIELD OF THE INVENTION
The field of this invention is anchor systems for well tools and, more particularly, high expansion bridge plugs or packers.
BACKGROUND OF THE INVENTION
Well tools frequently need to be anchored in casing for proper operation. In situations where the tool has to be delivered through tubing and set in casing, the anchor assembly must extend substantially from the run in position to grab the casing. This happens because the tool must be no bigger than a small dimension to be run smoothly through tubing and yet must expand substantially in percentage terms to grab the casing. In the case of a plug or packer, substantial directional forces are transmitted to the anchor system when such tools are set.
The designs of anchor systems in high expansion service have shown limited abilities to retain grip and some have released their grip under load. Generally these designs involve a release when the wickers on the end of a link that contacts the casing simply shear and the grip is lost. In the past, high expansion anchor systems involved rotating individual links that engage the casing with wickers mounted on an end. Examples of this design are U.S. Pat. Nos. 6,311,778 and 6,318,461. A through tubing design using similar anchor assemblies is shown in U.S. Re 32,831. In applications where high expansion is not an issue, the known technique of pushing slips out with cones has been employed, as shown in U.S. Pat. No. 6,220,348.
The problem with past designs is that they had a limited grip area due primarily to their layout of having wickers at the end of a thin link engage the casing wall. Even though multiple links would get independently actuated around the periphery of the packer or plug, the links were narrow and their grip limited for that reason. Even a plurality of such individual links could not support a tool in extreme loading conditions. What is needed and provided by the present invention is a way to increase the bite area of the gripping member that engages the casing wall. This has been accomplished in part due to the placement of the gripping member at the intersection of a plurality of links as well as controls built into the linkage to control the final movement of the gripping surface. Provisions for pin connection failure have been made so that the anchor of the present invention could still retain a grip if such a connection weakened or failed under heavy load. These and other advantages of the present invention will be more apparent to one skilled in the art from a review of the description of the preferred embodiment and the claims below.
SUMMARY OF THE INVENTION
An anchor system for high expansion applications is described. It features a gripping member that holds together a pair of links. The movement of the links is regulated to assure the gripping member moves into proper contact with the casing. Meshing gears or a pin and slot can do this, for example. The gripping member is shaped such that it can still transmit load through the links even if the pin connections fail. The gripping member is preferably contoured to the shape of the casing inner wall to enhance grip.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the run in position of the anchor using gears between the links;
FIG. 2 is the view of FIG. 1 in the set position;
FIG. 3 is an alternative embodiment of FIG. 1 shown in the run in position; and
FIG. 4 is the view of FIG. 3 in the set position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, only the anchor assembly is illustrated with it being understood that it can be a part of any downhole tool that needs anchoring. The tool will generally have a mandrel 10 with a lower hub 12 and an upper hub 14 . One of those hubs will move in tandem with the mandrel 10 while the other will be held stationary, during the setting procedure. In the embodiment illustrated in FIGS. 1 and 2, the upper hub 14 is movable toward the stationary lower hub 12 . There is a plurality of anchor assemblies A, and only one will be described with the understanding that the others are preferably identical to it. Each assembly A has an upper link 16 , pivotally mounted at its upper end 17 to upper hub 14 by a pin 18 . Lower link 20 is pinned at its lower end 22 to lower hub 12 by pin 24 . Slip 26 has wickers 28 for contacting the casing (not shown). Link 16 is pinned to slip 26 by pin 30 . Link 20 is pinned to slip 26 at pin 32 . Referring to FIG. 2, slip 26 has rounded interior areas 34 and 36 to accept ends 38 and 40 of links 16 and 20 respectively in the event of weakening or failure of either of pins 30 or 32 . Additionally, ends 38 and 40 feature meshing gears 42 and 44 so that the movement of links 16 and 20 is tied together to ensure that the slip 26 comes out flush against the casing (not shown). The gears 42 and 44 remove a degree of freedom for the slip 26 and prevent it from changing the relative positions of pins 30 and 32 as the links 16 and 20 rotate into the position shown in FIG. 2 .
As an alternative to gears 42 and 44 , FIGS. 3 and 4 illustrate another way to insure the flush contact of the casing wall by slips 26 . FIG. 3 shows the run in position, but the operation of the alternative design can be more easily seen in FIG. 4 . In this embodiment, there are no gears 42 and 44 . Instead, pinned to link 16 is guide link 46 that has a slot 48 . Pin 50 provides the connection to link 16 . Inserted in slot 48 is pin 49 of guide link 52 , which is connected, by pin 54 to link 20 . With this arrangement, the movements of links 16 and 20 are kept equal as hub 12 moves toward hub 14 . This ensures that slip 26 will engage the casing in a flush manner. The rounded areas 34 and 36 are also more clearly seen in FIG. 4 . It shows that upon failure of pin 30 or 32 the load from links 16 or 20 can be transferred to the curved areas 34 or 36 . In view of the close proximity of the ends 38 and 40 , a failure of either pin 30 or 32 when slip 26 is in contact with the casing could also be absorbed by one end 38 abutting end 40 while bearing against the curved areas 34 or 36 .
The slips 26 can be curved to better conform to the casing inner wall. The gap between pins 30 and 32 can be increased to allow making the slip 26 taller to increase its contact area with the casing. The guiding of the movement as between links 16 and 20 allows the slips 26 to move outwardly in a flush orientation to the casing wall for a maximum secure grip. The gears 42 and 44 can be replaced with a friction contact between links 16 and 20 , although a more positive displacement type of contact like meshing gears 42 and 44 or guide links such as 46 and 52 are preferred. The advantage of the present invention over the prior systems where only the wickers at the end of a tilted link are used for anchoring can readily be seen. Because of the unique support system to drive a slip supported by a plurality of links, the contact area is dramatically improved so the grip is enhanced. The curved areas provide a backup incase severe loading causes a pin 30 or 32 to stretch or fail. The positive guiding of the connected links assures contact of the casing in a flush manner over a far greater area than prior designs. The holding forces are substantially increased. The guiding system for links 16 and 20 also facilitates release of the anchor A. As previously stated the anchor A can be used on a variety of downhole tools, whether run in into casing or through tubing. The method of actuating the anchor can be using any known device that can cause the required relative movement to get hubs 12 and 14 to move toward each other. Known devices that can provide the force to separate hubs 12 and 14 can accomplish release. A variety of surface treatments can be used instead of wickers 28 to enhance grip including using hardened inserts. Another advantage of the present invention is that slip 26 resists forces in opposed directions to allow simplification of the overall anchor structure. In the past, anchor structures have had to use separate anchoring mechanisms to resist forces that came from opposite directions. In the present invention the link pairs, with their associated slip can resist forces from opposed directions. The face of the slips 26 can have wickers or other surface treatments that are mirror images on a single slip to facilitate anchoring against forces from opposed directions. They can have one continuous arc or be a series of curves having different radii. Multiple hubs controlling pairs of links that have a slip holding them together as described above can be used to add additional grip. The slips would then translate out at different elevations along the body 10 . The present invention is useful in high expansion applications where driving slips out with cones is insufficient to span the gap necessary to get anchoring forces against the casing.
The foregoing disclosure and description of the invention are illustrative and explanatory thereof, and various changes in the size, shape and materials, as well as in the details of the illustrated construction, may be made without departing from the spirit of the invention. | An anchor system for high expansion applications is described. It features a gripping member that holds together a pair of links. The movement of the links is regulated to assure the gripping member moves into proper contact with the casing. Meshing gears or a pin and slot can do this, for example. The gripping member is shaped such that it can still transmit load through the links even if the pin connections fail. The gripping member is preferably contoured to the shape of the casing inner wall to enhance grip. | 4 |
PRIORITY REFERENCE TO PRIOR APPLICATION
This application claims benefit of Taiwanese patent application serial number 091122910, entitled “Contactless and Intelligence-Wise Code Identification Chip System,” filed on Oct. 3, 2002, by inventor Chun-Ping Lin.
FIELD OF THE INVENTION
The present invention is relative to a contactless and intelligence-wise code identification chip system, especially for the system that transfers the identification code by the time slots.
BACKGROUND OF THE INVENTION
General identification codes are stored in the magnetic cards, and every card has one identification code. When a magnetic card is rushed through a card reader, the card reader could be able to identify the card user by the identification code stored in the card. But it is inconvenient for a user to take a card and rush through the card reader for identifying. So, a contactless identification code system is developed to improve the drawback of the conventional magnetic cards. The Contactless identification code system is able to identify the identification code by induction coil 12 in the card reader 11 i s able to produce a magnetic field. There is a contactless identification code IC 14 and an induction coil 15 in the card 13 . An identification code is also set in this card. When the card 13 closes to the code reader, the induction coil 15 will be coupled and provides the electric power of the IC 14 according to the electromagnetic induction theory. Then the code stored in the IC will passes to the card reader 11 to identify. So, by closing the card, the card reader, but not rushing through it, can identify a user's code.
The prior art is designed for identifying one card every time. If several cards are taken close to the code reader for identifying concurrently, then the ID collision will be happened and the code identification would be wrong. Therefore, the prior art can't apply to the card identification toys or supermarket clerks for identifying several same or different items concurrently.
SUMMARY OF THE INVENTION
The main object of present invention is to provide a contactless and intelligence-wise code identification chip system for identifying the identification codes one by one in several code chips. And the ID collision will not happen to make the code identification fail even though these code chips with the same code. The accuracy of code identification almost can be 100%, so we can apply the contactless and intelligence-wise code identification chip system to the card identification toys or supermarket clerks to identify several same or different items concurrently.
BRIEF DESCRIPTION OF THE INVENTION
According to the present invention, a contactless and intelligence-wise code identification chip system for transferring an identification code by a plurality of time slots. The plurality of chips include the identification code and are able to generate random numbers. The random number is used to select one of the time slots for allocating the identification code. And, the contactless and intelligence-wise code reader can read the identification code from the plurality of time slots by a polling method.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code identification chip is induced by a magnetic field energy, and transfers the identification code to the contactless and intelligence-wise code reader.
In accordance with one aspect of the present invention, the random number is an integer among 0 to N, and N is an integer larger than 1.
In accordance with one aspect of the present invention, an interval of the time slot is 2 ms.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader reads the identification code from the plurality of time slots by the polling method at least once.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader also includes a memory unit to record the time slot and the identification code.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader also includes an output unit to output a content of the memory unit.
According to the present invention, the method provides a plurality of contactless and intelligence-wise code identification chips to transfer an identification code by a plurality of time slots, and comprising steps of:
Generate a random number by the contactless and intelligence-wise code identification chip, the random number being used to select one of time slots for allocating the identification code; and
Read the identification code from the plurality of time slots by the contactless code reader with a polling method.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code identification chip is induced by a magnetic field energy, and transfers the identification code to the contactless and intelligence-wise code reader.
In accordance with one aspect of the present invention, the random number is an integer among 0 to N, and N is an integer larger than 1.
In accordance with one aspect of the present invention, the interval of the time slot is 2 ms.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader reads the identification code from the plurality of time slots by the polling method at least once.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader also includes a memory unit to record the time slot and the identification code.
In accordance with one aspect of the present invention, the contactless and intelligence-wise code reader also includes an output unit to output the content of the memory unit.
The present invention may best be understood through the following description with reference to the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the block diagram of prior contactless code identification system.
FIG. 2 shows a preferred embodiment of the contactless and intelligence-wise code identification chip system according to the present invention.
FIG. 3 shows a preferred embodiment of different code chip but generate the same random number.
FIG. 4 shows a preferred embodiment of different code chip with the same identification code.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 2 is a preferred embodiment of the contactless and intelligence-wise code identification chip system according to the present invention. As shown in FIG. 2 , there are three contactless and intelligence-wise code identification chips IC 1 , IC 2 , and IC 3 with identification codes ID 1 , ID 2 , and ID 3 respectively, and they are put into the magnetic field of the induction coil 12 of the contactless and intelligence-wise code reader 21 . After IC 1 , IC 2 , and IC 3 getting energy from the electrical magnetic field, they will randomly generate the random numbers to allocate ID 1 , ID 2 , and ID 3 into the time slots respectively. In FIG. 2 , the random numbers are 1, 3, and 30; therefore the time slots for IC 1 , IC 2 , and IC 3 are T 1 , T 3 , and T 30 respectively.
The contactless and intelligence-wise code reader 21 reads every time slot by polling for the identification code. So, in the preferred embodiment, the contactless and intelligence-wise code reader 21 will polling from T 0 to T 63 (actually, it also may be infinite number); then the reader will get ID 1 in T 1 , ID 2 in T 3 , and ID 3 in T 30 . ID 1 , ID 2 and ID 3 will be stored in the memory unit 211 and output by the output unit 212 .
Because of the random numbers are randomly generated by the contactless and intelligence-wise code identification chips, there would be the same random number generated by the different chips and several identification codes would be allocated in the same time slot. As shown in FIG. 3 , IC 1 and IC 2 generate the same random number. That will lead ID 1 and ID 2 both to be allocated in T 2 , and the contactless and intelligence-wise code reader 21 will get ID 1 and ID 2 concurrently in T 2 . In order to avoid incorrect code identification, IC 1 , IC 2 , and IC 3 must re-generate new random numbers for next time slot polling.
FIG. 4 shows another special case. IC 1 and IC 2 have the same identification code ID 1 , but the random numbers are 1 and 3 respectively. So ID 1 of IC 1 will be allocated in T 1 , and ID 1 of IC 2 will be allocated in T 3 . The contactless and intelligence-wise code reader 21 can easily identify the identification codes by the different time slots.
Further more, if the conditions of FIG. 3 and FIG. 4 happen at the same time, that is, the different chips have the same identification code and be allocated in the same time slot, it will be difficult to identify the identification codes. In order to enhance the exactness and accuracy for the code identification, the code identification method must repeat for one more times until getting the same result, then we can make sure the result is exact.
Considering the cost of manufacturing, the technique of “chip pads coding” can be applied to the present invention. The theory of chip pads coding is based on the third power (3^x) extension of each input pad. For example, we may create 3^3=27 kinds of identification codes with 3 input pads. As well as, the 243 different identification codes can be created with 5 input pads. Above all, these different codes can be created by only one mask when the chips are produced. With this design, the contactless and intelligence-wise code identification chip can be mass-produced with very low cost on the application of identification code.
The present invention is very suitable for the toy development. For example, in the card identification game machine the chips can be implanted into the cards having graphs. So, the reader can identify the cards when children take these cards close to it. Of course, the children may take several cards to the code reader concurrently, and the reader of present invention will not fail. Despite the cards with a different or the same identification codes are taken close to the code reader, the code reader can identify them one by one, and reads out all the names of the graph on the cards.
The present invention is provided to improve the prior art, which can identify the identification codes one by one among several code chips. The ID collision will not happen even though these code chips with the some code. Above all, the accuracy of code identification almost can be 100%, so we can apply the contactless and intelligence-wise code identification chip system to the card identification toys or the supermarket clerks to identify several same or different items concurrently.
While the invention has been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention need not be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims that are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures. | The present invention provides a kind of contactless and intelligence-wise code identification chip system. The contactless and intelligence-wise code identification chips have an identification code respectively. The chips can generate a random number to select one of time slots for allocating said identification code. The contactless and intelligence-wise code reader can read the identification code from time slots by the polling method. | 6 |
BACKGROUND
[0001] Solid-state light emitting devices, such as light-emitting diodes (LEDs) and laser diodes, have become more common in curing applications such as those using ultra-violet light. Solid-state light emitters have several advantages over traditional mercury arc lamps including that they use less power, are generally safer, and are cooler when they operate.
[0002] However, even though they generally operate at cooler temperatures than arc lamps, they do generate heat. Since the light emitters generally use semiconductor technologies, extra heat causes leakage current and other issues that result in degraded output. Management of heat in these devices has become important.
[0003] One traditional cooling technique uses a heat sink, which generally consists of thermally conductive materials mounted to the substrates upon which the light emitters reside. Some sort of cooling or thermal transfer system generally interacts with the back side of the heat sink, such as heat dissipating fins, fans, liquid cooling, etc., to draw the heat away from the light emitter substrates. The efficiency of these devices remains lower than desired, and liquid cooling systems can complicate packaging and size restraints.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 shows an embodiment of a solid-state light fixture having vapor chamber cooling.
[0005] FIG. 2 shows a cut view of an LED-based light fixture having vapor chamber cooling.
[0006] FIG. 3 shows an embodiment of a solid-state light fixture having vapor chamber cooling with a liquid-cooled structure.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0007] Several approaches exist for cooling LED and other solid-state light fixtures including air and liquid cooled systems. Air cooled systems typically involve a heat sink, generally a piece of thermally conductive material like aluminum or copper, mounted to the back side of the substrate or substrates of the arrays of light emitting elements. Heat generated by the solid-state or semiconductor light emitting elements transfers through the thermally conductive heat sink out the back side of the module, away from the elements. This process may be assisted by the user of fins on the back side of the heat sink, and air circulation, such as with a fan.
[0008] Liquid cooled systems typically involve a liquid enclosed in some sort of vessel that traverses the back side of the array of elements. The liquid receives the heat from the array and moves it to another area where some sort of cooler removes the heat so that when the liquid returns to the back side of the array, it can accept more heat. The cooler may consist of a refrigeration unit through which the liquid moves. The cooler may also consist of air cooling systems, but the overall system relies upon liquid for heat transfer and is therefore considered a liquid cooling system.
[0009] While both of these options provide a solution to the problems of cooling solid-state light fixtures, they have problems. Air cooled systems typically do not provide as high a level of cooling as desired. These systems may run a little ‘hot’ reducing the efficiency and effectiveness of the light fixtures. Liquid cooled systems typically have complicated packaging requirements to accommodate both the liquid channels, which must be sealed so as to not damage the electronics, and the cooling system to cool the liquid.
[0010] Another viable option involves using a vapor chamber type cooling system in the place of a traditional heat sink. A vapor chamber may take many forms, but a common form includes a chamber ‘inside’ the heat sink. The chamber typically has three regions. A first region is the transportation region in which a liquid resides. A vaporization region may have a wicking material within it to wick the liquid away from the region in which the heat from the arrays transfers. Finally, a condensation region typically resides the furthest away from the heat transfer/transportation region.
[0011] As the liquid turns to gas in the transportation region, the vaporization region moves the gas to the condensation region. As the gas cools and returns to liquid form, it moves back through the vaporization region into the transportation region.
[0012] FIG. 1 shows an embodiment of a vapor chamber cooled solid-state light module. The light module 10 has an array 12 of individual light emitting elements formed into an array. The array may reside on one substrate, or may consist of several smaller arrays each on individual substrates, such as 14 and 16 , but the term array used here will encompass both possibilities. The light module may also include control electronics and optics, not shown.
[0013] The array 12 mounts to the front face of the heat sink 18 , possibly with a thermal interface material, like thermal grease. The heat sink appears in this view to consist of a traditional heat sink, typically a large block of thermally conductive material such as copper, aluminum, or brass, with cooling structures 20 . In this embodiment, the cooling structures 20 consist of fins for an air cooled heat sink, but may instead consist of liquid cooled or other air cooling features like a fan with or without the fins, typically arranged on the surface of the heat sink opposite the surface upon which the light emitters reside.
[0014] If one were to cut the heat sink 18 along the section line A, the resulting view appears in FIG. 2 . As can be seen in FIG. 2 , the heat sink 18 is revealed to include a vapor chamber 22 . The vapor chamber 22 contains the liquid and the three zones mentioned above. The liquid will generally consist of water, although other liquids such as alcohol, ethylene glycol, of a fluorocarbon-based fluid may be used. The liquid should have good wicking properties and not be too viscous. The vapor chamber 22 may also be pressurized to lower the boiling point of the liquid to increase the efficiency of the system.
[0015] The vapor chamber appears to be like any other heat sink, except that it may have a slightly greater thickness to accommodate the chamber. This allows for a smaller profile than other liquid cooled systems, but still provides the higher thermal transfer characteristics than a typical air-cooled system.
[0016] In typical heat sinks, the fins towards the center of the heat sink end up receiving most of the heat from the light emitters. This limits the amount of heat that the heat sink dissipates because the fins that receive most of the heat have much smaller surface area than the surface area of all of the fins. The fins towards the top and the bottom of the heat sink, as oriented in the drawing, become essentially unused.
[0017] By employing a vapor chamber inside the heat sink, these fins become part of the heat dissipation path. The vapor expands and fills the chamber as it moves away from the heat source, so the heat is more evenly distributed against the second surface of the heat sink. This utilizes the fins that were previously unused. Advantages of this include allowing the heat source to run at higher temperatures than previous, since more heat will be dissipated, and the ability to have heat sinks that are much larger than the heat source. One could have a large heat sink with several fins that extend well beyond the size of the heat source. Without the vapor chamber, the extra fins would add no benefit.
[0018] In some instances, higher cooling requirements may benefit from use of a water or other liquid cooling approach. FIG. 3 shows an embodiment of this approach. The heat sink 18 , with the interior vapor chamber, is mounted to a pipe. The pipe has an inlet pipe portion 34 that circulates cool water or other liquid from a cooler unit, not shown. The cool liquid traverses the backside of the heat sink 18 , removing the heat from the vapor chamber. As mentioned above, this will cause the vapor to return to liquid state and move back towards the surface of the heat sink adjacent to the array of light-emitting elements. The liquid moves away from the heat sink 18 by outlet pipe 32 . Outlet pipe 32 then passes the liquid to the cooling unit, where it is cooled and then re-circulated to the heat sink. The cooling unit may take one of many forms including a fan, a refrigeration unit, etc.
[0019] There has been described to this point a particular embodiment for a vapor chamber cooled light module, with the understanding that the examples given above are merely for purposes of discussion and not intended to limit the scope of the embodiments or the following claims to any particular implementation. | A lighting module has an array of light emitters, a heat sink having a first surface, the array of light emitters being mounted to the first surface, a vapor chamber inside the heat sink, the vapor chamber including a liquid and arranged to absorb heat from the first surface until the liquid becomes vapor, and a cooling unit thermally coupled to a second surface of the heat sink opposite the first. | 5 |
RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/193,523, filed Jul. 28, 2011, now U.S. Patent No. 8,164,948, issued Apr. 24, 2012, which is a divisional of U.S. patent application Ser. No. 12/017,308, filed Jan. 21, 2008 (now U.S. Patent No. 8,004,882, issued Aug. 23, 2011), which is a continuation of U.S. patent application Ser. No. 11/146,997, filed Jun. 6, 2005 (now U.S. Patent No. 7,339,818, issued Mar. 4, 2008) which claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application No. 60/577,091, filed Jun. 4, 2004, the disclosures of each of which are hereby incorporated by reference in their entireties.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to semiconductor processing technology and, in particular, concerns a spin dependent logic device that may be used to construct high-speed non-volatile static random access memory (SRAM) cells.
2. Description of the Related Art
Since the introduction of the digital computer, electronic storage devices have been a vital resource for the retention of binary data. Some conventional semiconductor electronic storage devices utilize static latch structures as storage cells, which may be referred to as Static Random Access Memory (SRAM). As is generally known in the art, a conventional SRAM latch circuit utilizes complementary metal-oxide semiconductor (CMOS) circuitry. In one aspect, CMOS SRAM circuitry typically comprises two cross-coupled inverters, wherein the simultaneous activation of two access transistors regulates the flow of current through the cross-coupled inverter circuits for read and write functions. The inverter circuit is a fundamental CMOS circuit utilized in many memory and logic devices, such as SRAM memory, set-reset (SR) flip-flops, and various logic gates. In one aspect, a common CMOS inverter circuit comprises two series connected (drain-to-drain) and matched enhancement type metal-oxide semiconductor field-effect transistor (MOSFET) devices: one n-channel MOSFET and one p-channel MOSFET. Furthermore, the input to the inverter circuit is connected to the gate of each MOSFET device, and the output of the inverter circuit is accessed between the two MOSFET devices at the drain-to-drain connection.
SRAM devices experience fast access times, which makes SRAM a desirable memory storage device. Unfortunately, this type of semiconductor Random Access Memory (RAM) requires a continuous supply of power to maintain or preserve a defined logic-state. As a result, conventional SRAM is considered volatile memory due to the fact that data may be lost with the loss of a continuous supply of power.
Alternatively, Programmable Read Only Memory (PROM) devices, such as Erasable PROM (EPROM) and Electrically Erasable PROM (EEPROM), may be used as non-volatile memory devices in place of SRAM devices. PROM devices are user-modifiable read-only memory (ROM) devices that may be repeatedly erased and reprogrammed. EPROM devices are typically erased by shining an intense ultraviolet light on the circuitry of the memory chip and then reprogrammed in a generally known manner using electrical voltage. Unfortunately, EPROM devices need to be placed in a specially designed device for erasure and programming prior to re-write, which is substantially inconvenient under most circumstances. Unlike EPROM chips, EEPROMs do not need to be placed in a specially designed device for erasure and programming for re-write. Unfortunately, an EEPROM chip typically requires erasure and re-programming in its entirety and in a non-selective manner, which takes a considerable amount of time. In addition, EEPROM devices have limited re-programmability over the life of the device, which, in most cases, re-programmability is limited to tens or hundreds of thousands of times. Other disadvantages to PROM devices include slow read and write times, which may be substantially slower than SRAM devices. Therefore, conventional PROM devices are not typically used as non-volatile random access memory.
Based on the foregoing, there currently exists a need to replace traditional volatile SRAM with an improved solid-state non-volatile memory device that has the speed of conventional SRAM with the logic state preservation of PROM devices. Furthermore, there also exists a need to develop non-volatile memory devices that may be used in conventional applications while still maintaining a high-density fabrication process and technique.
SUMMARY OF THE INVENTION
The aforementioned needs may be satisfied by a memory device comprising, in one embodiment, a semiconductor substrate having a first surface and at least one integrated latch memory component formed on the first surface of the semiconductor substrate, wherein the at least one integrated latch memory component stores a selective logic state having a volatile memory status. In addition, the memory device may further comprise at least one spin dependent logic device formed on the semiconductor substrate, wherein the at least one spin dependent logic device is interconnected to the at least one integrated latch memory component so as to permit a non-volatile application to the selective logic state having a volatile memory status.
In one aspect, the memory device may comprise a static random access memory (SRAM) device. The integrated latch memory component may comprise at least one inverter circuit, wherein the at least one inverter circuit may utilize complementary metal-oxide semiconductor (CMOS) technology. The selective logic state may comprise a binary logic state. The volatile memory status may be defined as an unstable data retention status that is power dependent. The non-volatile memory status may be defined as a stable data retention status that is power independent.
In another aspect, the at least one spin dependent logic device may utilize a selectable resistance differential to store the selective logic state. The at least one spin dependent logic device may comprise a giant magneto-resistance (GMR) device, wherein the GMR device may comprise a device having a first pinned layer of a magnetic material that is magnetized in a first fixed direction and a second layer of magnetic material that may be magnetized in either the first fixed direction or a second direction. In addition, the first pinned layer may comprise a magnetic material selected from the group consisting of NiFeCo, NiFe, CoFe, Cu, Co, Ni, Fe, and Ta. Also, the second layer may comprise a magnetic material selected from the group consisting of NiFeCo, NiFe, CoFe, Cu, Co, Ni, Fe, and Ta.
The aforementioned needs may also be satisfied by an SRAM device formed on a semiconductor substrate. In one embodiment, the SRAM device may comprise a plurality of MOSFET devices formed on a first surface of the semiconductor substrate, wherein the plurality of MOSFET devices are logically interconnected so as to store a logic state with a volatile status. In addition, the memory device may further comprise at least one spin dependent logic device formed on the first surface of the semiconductor substrate, wherein the at least one spin dependent logic device is electrically interconnected to the plurality of MOSFET devices so as to provide a non-volatile operation of the SRAM device, wherein the logic state is stored with a non-volatile logic status.
The aforementioned needs may also be satisfied by a static memory device formed on a semiconductor substrate. In one embodiment, the static memory device may comprise a plurality of solid state components formed on the semiconductor substrate and logically interconnected to temporarily store a logic state having a power dependent storage status. In addition the static memory device may further comprise at least one integrated magneto-resistive component formed on the first surface of the semiconductor substrate and electrically interconnected to the plurality of solid state components, wherein the at least one integrated magnetic component provides a non-volatile storage status to the logic state.
The aforementioned needs may also be satisfied by an integrated memory device comprising, in one embodiment, a volatile memory component logically configured to temporarily store a selective logic state and a non-volatile memory component integrated with the volatile memory component to independently store the selective logic state as a measured resistance differential across the non-volatile memory component in a manner so as to prevent the loss of the selective logic state during a power interrupt.
The aforementioned needs may also be satisfied by a method for preserving a selective logic state with a power dependent status. In one embodiment, the method may comprise logically interconnecting a plurality of MOSFET devices on a first surface of a semiconductor substrate to temporarily store a selective logic state with a power dependent status. In addition, the method may further comprise integrating at least one magneto-resistive device with the plurality of MOSFET devices to independently store the selective logic state in a manner so as to prevent the loss of the selective logic state during a power interruption. These and other objects and advantages of the present teachings will become more fully apparent from the following description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other aspects, advantages, and novel features of the invention will become apparent upon reading the following detailed description and upon reference to the accompanying drawings. In the drawings, same elements have the same reference numerals in which:
FIG. 1A illustrates one embodiment of an inverter circuit with a magneto-resistive contact (MRC) interposedly coupled in series between two complementary transistors.
FIG. 1B illustrates another embodiment of an inverter circuit having two magneto-resistive contacts coupled in series with two complementary transistors.
FIG. 1C illustrates still another embodiment of an inverter circuit having two magneto-resistive contacts coupled in series with two complementary transistors.
FIG. 1D illustrates yet another embodiment of an inverter circuit with a magneto-resistive contact and a proximate conductor interposedly coupled in series between two complementary transistors.
FIG. 2A illustrates a cross-sectional view of one embodiment of a magneto-resistive contact.
FIG. 2B illustrates a perspective view of the MRC in FIG. 2A .
FIG. 2C illustrates a cross-sectional view of another embodiment of a magneto-resistive contact.
FIG. 2D illustrates a perspective view of the MRC in FIG. 2C .
FIG. 3 illustrates one embodiment of an MRC array.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Reference will now be made to the drawings wherein like numerals refer to like parts throughout. FIG. 1A illustrates one embodiment of an inverter circuit 100 with a magneto-resistive component or contact (MRC) 102 interposedly coupled in series between two complementary transistors 104 , 106 . In one aspect, the inverter circuit 100 may be utilized in an SRAM latch structure, such that the inverter circuit 100 utilizes complementary metal-oxide semiconductor (CMOS) technology, wherein a first transistor 104 is a p-channel MOSFET, and a second transistor 106 is an n-channel MOSFET. Solid state semiconductor devices, such as p-channel and n-channel MOSFET devices, may be implemented into circuits that are designed for digital logic and memory functions.
Additionally, the source terminal of the first transistor 104 is connected to a voltage source (Vs) 110 , and the drain terminal of the first transistor 104 is connected to the upper terminal of the MRC 102 . In addition, the lower terminal of the MRC 102 is connected to the drain terminal of the second transistor 106 , and the source terminal of the second transistor 106 is connected to a common ground terminal 112 . Moreover, an input terminal 114 of the inverter circuit 100 is connected to the gate terminals of the first and second transistors 104 , 106 , and an output terminal 116 of the inverter circuit 100 is connected to the drain terminal of the first transistor 104 and the upper terminal of the MRC 102 .
In one embodiment, the MRC 102 comprises a Giant-Magneto-Resistive (GMR) stacked structure that may be selectively programmed with the spintronic effect to a state of high resistance or to a state of low resistance. Advantageously, GMR devices employ a developing technology that offers the advantages of improved non-volatility and high-density fabrication. In addition, GMR structures utilize the spin polarization effect of electrons within ferromagnetic material and utilize multi-layers of ferromagnetic materials and a physical property known as magneto-resistance to read the memory storage logic states.
Binary logic states may require the sensing of a resistance differential to distinguish between “on” and “off” states. As is generally known, resistance is a measure of the inability of an electrical current to flow through a specific material, whereas current is the actual flow of electrons through a material. Therefore, if a material has a high resistance, then the ability of electrons to flow through the material may be inhibited. Conversely, a low resistive material tends to allow a higher degree of current to flow. GMR structures take advantage of this variable resistance concept by manipulating the alignments of spin states within multiple layers of magnetic material with proximate magnetic fields to increase or decrease the resistance between the multiple layers.
For example, current flow through a proximate conductive trace induces a magnetic field. In the presence of an orthogonal external magnetic field, the spin direction of stationary GMR electrons may be altered in one of two directions, either “up spin,” parallel to the magnetic field, or “down spin,” anti-parallel to the magnetic field. Thus, the spin orientation of the affected electrons are either directed “up” or “down” reaffirming the directional spin status of the electron or electrons within the concurrent external magnetic fields.
Moreover, magnetic GMR layers include a pinned (spin stationary) layer and a soft (spin programmable) layer. The selective programmability of the soft layer enables the GMR structure to serve as a logic state device, which stores binary data as directions of net magnetization vectors. In one aspect, current flow through two orthogonal conductive traces polarizes the spin characteristics of the electrons within the soft layer in either a parallel or antiparallel direction. In one aspect, the polarized spin of the soft layer electrons may be altered when influenced by two magnetic fields that are orthogonal to each other.
For example, if the individual magnetic layers are magnetized in the same direction (parallel), the structure exhibits a low electrical resistance. Whereas, if the individual magnetic layers are magnetized in opposite directions (anti-parallel), the structure exhibits a high electrical resistance. The “up” or “down” spin of the electrons are believed to interact with the net magnetization of the layered materials to either facilitate or impede the flow of electrons influenced by an applied electric field. When the layers are magnetically aligned in parallel, either the “up” or “down” electrons may travel through the magnetic material with a reduced electron scattering effect resulting in an overall lower resistance. However, in the case where layers are oppositely magnetized, both “up” and “down” electrons will be scattered by the anti-parallel orientation of the layers and, as a result, a higher percentage of electrons encounter a greater scattering effect corresponding to an overall higher resistance.
In one aspect, the spintronic effect utilizes the net spin-polarization of electrons in a magnetic material, such as Co, Fe, Ni, or any combinational alloy thereof, to produce a variable resistance differential across the material. The binary logic states typically require the sensing of a resistance differential between the upper and lower terminals of the MRC device 102 to distinguish between “on” and “off” states. As previously described, the sensing of a high resistive state may represent the “on” state, and the sensing of a low resistive state may represent an “off” state. Without departing from the scope of the present teachings, it should be appreciated that the converse may be true depending on the specific application of the device. In addition, the non-volatile programming of the GMR stacked structure adds significant advantage to an SRAM memory cell in that the MRC 102 retains the binary state through power-down, reset, and power-up of the SRAM memory cell. The structure and functionality of the MRC 102 will be discussed in greater detail herein below in FIG. 2 .
For explanative purposes, a high input at the gate terminal of a MOSFET refers to a voltage that is capable of inducing an n-channel MOSFET into an operational state and reducing a p-channel MOSFET into a non-operational state. Conversely, a low input at the gate terminal of a MOSFET refers to a voltage that is capable of reducing an n-channel MOSFET into a non-operational state and inducing a p-channel MOSFET into an operational state.
In one embodiment, the inverter circuit 100 operates as follows. When a low input appears at the input terminal 114 of the inverter circuit 100 , the low input is transferred to the gate terminals of the transistors 104 , 106 . The low input at the gate terminal of the first transistor 104 induces the p-channel into an operational state and allows current to flow from the source terminal to the drain terminal of the first transistor 104 . Conversely, the low input at the gate terminal of the second transistor 104 induces the n-channel into a non-operational state and prevents current flow between the drain terminal and the source terminal of the second transistor 106 . Therefore, the potential at the output terminal 116 is substantially similar to the potential at the voltage source 110 . Since the output voltage at the output terminal 116 is high, the MRC 102 is programmed to a high resistive state to allow current to source through the first transistor 104 from the voltage source 110 to the output terminal 116 . Advantageously, high resistance at the position of the MRC 102 would source the current from the drain terminal of the first transistor 104 to the output terminal 116 of the inverter circuit 100 . In a power-down, reset, and power-up sequence, the high resistive state of the MRC 102 would not change due to the non-volatility of GMR stacked structures. Therefore, at power-up, the inverter circuit 100 would sense the high resistive state of the MRC 102 and produce a high output voltage at the output terminal 116 of the inverter circuit 100 .
Alternatively, when a high input appears at the input terminal 114 of the inverter circuit 100 , the potential at the output terminal 116 is substantially similar to the potential at the ground terminal 112 . The high input also appears on the gate terminals of the first and second transistors 104 , 106 rendering the first transistor 104 to a non-operational state and the second transistor 106 to an operational state. Since the output voltage at the output terminal 116 is low, the MRC 102 is programmed to a low resistive state to allow current to sink through the second transistor 106 from the output terminal 116 to the ground terminal 112 . Advantageously, a low resistance differential across the MRC 102 would sink enough current from the output terminal 116 to provide a low output. In a power-down, reset, and power-up sequence, the low resistive state of the MRC 102 would not change due to the non-volatility of GMR stacked structures. Therefore, at power-up, the inverter circuit 100 would sense the low resistive state of the MRC 102 and produce a low output voltage at the output terminal 116 of the inverter circuit 100 .
In one aspect, integrated magneto-resistive devices, such as the MRC 102 , may be utilized as direct interconnects, selectable loads, and/or variable resistors, where the direct connection of magneto-resistive components to one or more semiconductor-based transistors is one advantageous feature. Copper (Cu) may be utilized as an interconnect if necessary for increased electron transfers at the point of contact. In addition, integrated magneto-resistive devices may function as current-perpendicular-to-the-plane (CPP) devices or current-in-plane (CIP) devices such that the dimensions of the integrated magneto-resistive devices are electrically configured to accommodate current flow and/or needed resistance differentials across the devices. It should be appreciated that, depending on the application of the MRC, the CCP or CIP configuration may be used by one skilled in the art without departing from the scope of the present teachings.
Additionally, the MRC may be switched by the magnetic field applied by a proximate conductor, or the MRC may be switched by injected current that uses the spin polarization effect that is concerned with the interaction of the spin of electrons and the magnetization. Applications of the device shown in FIGS. 1A-1D include a portion of a latch circuit element, a portion of a memory cell, and a portion of an embedded memory cell. Moreover, the MRC provides a contact between the transistor and one or more device layer(s), while also providing selectable magnetoresistance. The MRC, therefore, provides a contact that is integrated with a magnetic element. The MRC is, therefore, much smaller than a separate magnetoresistive element with a separate contact.
In one aspect, the integrated magneto-resistive devices may also function as memory or logic devices depending on latching, gain, or threshold properties of the device. In one aspect, the magneto-resistive component may be probed optically to access the magneto-resistive state of the device, for example, with the generally known Kerr effect. Moreover, the magneto-resistive component may also be thermographically accessed for writing and reading functions. One embodiment and application includes a non-volatile SRAM device such that the magneto-resistive device maintains the high-speed access times and the high density fabrication of conventional volatile SRAM, but achieves low power consumption with zero cut-off. Furthermore, the structure, composition, and functionality of the integrated magneto-resistive devices will be discussed in greater detail herein below.
FIG. 1B illustrates another embodiment of an inverter circuit 130 comprising two magneto-resistive contacts (MRC) 132 a , 132 b coupled in series with two complementary transistors 134 , 136 . Similar to the inverter circuit 100 disclosed in FIG. 1A , the inverter circuit 130 utilizes CMOS technology, wherein a first transistor 134 is a p-channel MOSFET, and a second transistor 136 is an n-channel MOSFET. The source terminal of the first transistor 134 is connected to the lower terminal of a first MRC 132 a , and the drain terminal of the first transistor 134 is connected to the drain terminal of the second transistor 136 . The upper terminal of the first MRC 132 a is connected to a voltage source (Vs) 140 . Furthermore, the source terminal of the second transistor 136 is connected to the upper terminal of the second MRC 132 b , and the lower terminal of the second MRC 132 b is connected to a common ground terminal 142 . Also, an input terminal 144 of the inverter circuit 130 is connected to the gate terminals of the first and second transistors 134 , 136 , and an output terminal 146 of the inverter circuit 100 is connected to the drain terminals of the first and second transistors 134 , 136 .
In this embodiment, when a low input appears at the input terminal 144 of the inverter circuit 130 , a high output appears at the output terminal 146 of the inverter circuit 130 . Therefore, the first MRC 132 a is programmed to a low resistive state, and the second MRC 132 b is programmed to a high resistive state. Advantageously, these programmed logic states significantly ensure that, at power-up, the inverter circuit 100 would sense the low resistive state of the first MRC 132 a and the high resistive state of the second MRC 132 b and produce a low output voltage at the output terminal 116 of the inverter circuit 100 . Conversely, the appearance of a high input at the input terminal 144 would produce a low input at the output terminal 146 . As a result, the first MRC 132 a is programmed to a high resistive state, and the second MRC 132 b is programmed to a low resistive state. Retaining the binary logic states during a power-down, reset, and power-up sequence is significantly fundamental to the concept of non-volatility such that the inverter circuit 100 would be capable of sensing the most recent binary logic state stored in the integrated magneto-resistive devices, such as MRC devices 144 , 146 .
FIG. 1C illustrates still another embodiment of an inverter circuit 160 comprising two magneto-resistive contacts (MRC) 162 a , 162 b coupled in series with two complementary transistors 134 , 136 . In this embodiment, the configuration of the inverter circuit 160 is similar to the configuration of the inverter circuit 130 in FIG. 1B except that the second MRC 132 b is positioned above the second transistor 136 . The second MRC 166 is positioned within the inverter circuit 160 such that the upper terminal of the MRC is connected to the drain terminal of the first transistor 134 , and the lower terminal of the second MRC 132 b is connected to the drain terminal of the second transistor 136 . In addition, the source terminal of the second transistor 136 is connected to the ground terminal 142 . Furthermore, the functionality of the inverter circuit 160 is similar in scope to the functionality of the inverter circuit 130 in FIG. 1B .
The embodiments of integrated magneto-resistive devices described herein are transistors integrated with one or more magneto-resistive contacts (MRCs) that provide electrical connectivity (for example, to connect to power, ground, and/or other circuits) and selectable change in resistance. The basic structure of the MRC device, which includes a transistor, such as a silicon-on-insulator or bulk CMOS transistor, and a single MRC is shown in FIGS. 2A-2D . In one aspect, the MRC device may be switched by a magnetic field applied by a proximate conductor, or the MRC device may be switched by injected current that uses the spin polarization effect to manipulate the magnetization of ferromagnetic layers. As previously described, applications of the MRC device include a portion of a latch circuit element, a portion of a memory cell, and a portion of an embedded memory cell, where, in one aspect, the MRC device provides a selectable magneto-resistive contact between a plurality of transistors. Furthermore, an integrated MRC device provides an integrated contact between magnetic-based circuit elements and semiconductor-based circuit elements. As will be described in greater detail herein below, an integrated MRC device is substantially smaller in geometry than a discrete magneto-resistive circuit element with separate conductive contacts. Advantageously, the reduced geometry of the MRC device allows for the utilization of desirable dense fabrication and manufacturing techniques.
FIG. 1D illustrates one embodiment of an inverter circuit 190 with a magneto-resistive contact (MRC) 102 and a proximate conductor 192 interposedly coupled in series between two complementary transistors 104 , 106 . In this embodiment, the configuration of the inverter circuit 190 is similar in scope to the configuration of the inverter circuit 100 in FIG. 1A with the addition of the proximate conductor 192 . Advantageously, the proximate conductor 192 may be utilized to switch the net magnetization vector of the MRC 102 from a parallel spin orientation to an anti-parallel spin orientation or vice versa depending on the direction of the current flow through the proximate conductor 192 . Additionally, the functionality of the MRC 102 and the process of switching the MRC 102 will be discussed in greater detail herein below. As shown in FIG. 1D , the MRC 102 may subject to one or more induced magnetic fields from the proximate conductor 192 that may be positioned adjacent to the MRC 102 . It should be appreciated that one or more proximate conductors 192 may be formed and/or positioned adjacent to one or more MRC 102 devices for the purpose of inducing one or more in-plane magnetic fields and/or perpendicular magnetic fields without departing from the scope of the present teachings.
FIG. 2A illustrates a cross-sectional view of one embodiment of a magneto-resistive contact (MRC) 200 . FIG. 2B illustrates a perspective view of the MRC 200 in FIG. 2A , wherein like numerals within FIGS. 2A and 2B correspond to like parts throughout. The MRC 200 is formed on an upper surface of a semiconductor based substrate 202 . In one aspect, the semiconductor substrate 202 is manufactured in a manner well known in the art with a substantially flat, smooth, non-rigid upper surface. Semiconductor refers to, but is not limited by, a material such as Silicon, Germanium, or Gallium Arsenide. In addition, the MRC 200 comprises a plurality of conductive traces 204 a , 204 b , 204 c , 204 d , a plurality of insulation layers 206 a , 206 b , and a first GMR stacked structure 201 including a magnetically fixed pinned layer 208 , a spacer layer 210 , and a magnetically programmable soft layer 212 .
In one embodiment, a first conductive trace 204 a is formed adjacent to the upper surface of the substrate 202 . It should be appreciated that the plurality of conductive traces 204 a , 204 b , 204 c , 204 d are formed of a conductive material, such as aluminum, copper, an aluminum/copper alloy, or doped polysilicon, which is deposited by vacuum evaporation, sputter-deposition, or chemical vapor deposition (CVD) techniques in a manner generally known in the art. In addition, the plurality of conductive traces 204 a , 204 b , 204 c , 204 d may comprise thin, flat, conductive interconnects. It should also be appreciated that the conductive traces 204 a , 204 b , 204 c , 204 d can vary dimensionally, including length, width, height, and thickness, depending on the implementation and desirable electrical characteristics without departing from the scope of the present teachings. In one aspect, the first conductive trace 204 a comprises a first point of reference for programming the net magnetization vector of the magnetically programmable soft layer 212 , wherein the first conductive trace 204 a provides a first magnetic field in a first direction relative to the GMR stacked structure 201 .
In one embodiment, a first insulation layer 206 a is formed adjacent to the upper surface of the first conductive trace 204 a . It should be appreciated that the plurality of insulation layers 206 a , 206 b are formed of a silicon-based material, such as silicon-dioxide (SiO 2 ) or a silicon-nitride (SiN x ). Additionally, the insulation layers 206 a , 206 b may function as a current flow barrier between conductive traces. In one aspect, a second conductive trace 204 a may be formed adjacent to the upper surface of the first insulation layer 206 a . In this embodiment, the second conductive trace 204 b is positioned substantially parallel to the first conductive trace 204 a . It should be appreciated that the second conductive trace 204 b may be oriented in a direction other than parallel without departing from the scope of the present teachings. Also, the second conductive trace 204 b may function as a lower conductive contact for the GMR stacked structure 201 , wherein the GMR structure 201 may be interconnected to other circuit elements in a manner as will be described in greater detail herein below.
In one embodiment, the magnetically fixed pinned layer 208 is formed adjacent to an upper surface of the second conductive trace 204 b . In various embodiments, the pinned layer 208 may comprise a magnetic-based material, such as a layer of NiFeCo, NiFe, CoFe, Cu, Co, Ni, Fe, or Ta. It should be appreciated that the pinned layer 208 can vary dimensionally, including length, width, height, and thickness, depending on the implementation and desirable electrical characteristics without departing from the scope of the present teachings. GMR stack layers, including the pinned layer 208 , are formed in a manner generally known in the art by deposition techniques such as sputter-deposition, physical vapor deposition, or ion-beam deposition. In one aspect, the pinned layer 208 is magnetized in a first fixed direction and functions as a first reference point for the net directional magnetization vectors of the GMR stacked structure 201 . The first fixed direction is relative to the collective rotational spin of the electrons within the layered material. Positioning the pinned layer 208 significantly adjacent to the second conductive trace surface 204 b provides a direct conductive link to the lower portion of the GMR stacked structure 201 as will be described in greater detail herein below.
In one embodiment, the spacer layer 210 is formed on an upper surface of the pinned layer 208 . In addition, the spacer layer 210 may comprise a layer of conductive material, such as copper. It should be appreciated that the spacer layer 210 can vary dimensionally, including length, width, height, and thickness, depending on the implementation and desirable electrical characteristics without departing from the scope of the present teachings. In one aspect, the spacer layer 210 is formed using fabrication techniques, such as vacuum evaporation, sputter-deposition, or chemical vapor deposition (CVD) in a manner known in the art. In addition, the spacer layer 210 functions as a conduit for excited electrons to flow through with low traversal resistance.
In another embodiment, the spacer layer 210 comprises a tunneling dielectric layer, wherein the tunneling dielectric layer comprises a layer of Al 2 O 3 that is approximately 10 to 15 Angstroms thick. It should be appreciated that the spacer layer 210 can vary dimensionally, including length, width, height, and thickness, depending on the implementation and desirable electrical characteristics without departing from the scope of the present teachings. Additionally, various fabrication techniques utilized for producing the tunneling dielectric layer 112 include, first, depositing a conductive aluminum layer in a manner well known in the art. Then, oxidation of the aluminum layer is achieved by one of several different methods: plasma oxidation, oxidation by air, and ion-beam oxidation, wherein all are derived in a manner well known in the art. In this embodiment, the tunneling dielectric layer functions as a conduit for excited electrons to flow through without causing dielectric breakdown at low voltages.
In one embodiment, the magnetically programmable soft layer 212 is formed on an upper surface of the tunneling dielectric layer 112 . In various embodiments, the magnetically programmable soft layer 114 comprises a magnetic material, such as a layer of NiFeCo, NiFe, CoFe, Cu, Co, Ni, Fe, or Ta. It should be appreciated that the soft layer 212 can vary dimensionally, including length, width, height, and thickness, depending on the implementation and desirable electrical characteristics without departing from the scope of the present teachings. In one aspect, the magnetically programmable soft layer 212 is magnetized in either a first fixed direction, that is parallel to the magnetization direction of the magnetically fixed pinned layer 208 , or a second direction, that is anti-parallel to the to the magnetization direction of the magnetically fixed pinned layer 208 . The magnetically programmable soft layer 212 provides a second reference point for the net directional magnetization vectors of the GMR stacked structure 201 . It should be appreciated that the GMR stacked structure 201 may comprise multi-layers of NiFeCo, NiFe, CoFe, Cu, Co, Ni, Fe, Ta, or any combination thereof without departing from the scope of the present teachings.
In one embodiment, attached adjacent to the upper surface of soft layer 212 is a third conductive trace 204 c . In this embodiment, the third conductive trace 204 c is positioned substantially parallel to the second conductive trace 204 b so as to prevent switching of the magnetically programmable soft layer 212 . The third conductive trace 204 c functions as an upper conductive contact for the GMR stacked structure 201 , wherein the GMR structure 201 may be interconnected to other circuit elements in a manner as will be described in greater detail herein below. In addition, a second insulation layer 206 b is formed adjacent to the upper surface of the third conductive trace 204 c in a manner and of a material as previously described with reference to the first insulation layer 206 a . It should be appreciated that the GMR stacked structure 201 may comprise additional layers as will be described in FIGS. 2C , 2 D without departing from the scope of the present teachings.
In one embodiment, a fourth conductive trace 204 d is formed adjacent to the upper surface of the second insulation layer 206 b . The fourth conductive trace 204 d may be positioned substantially perpendicular to the first conductive trace 204 a . In addition, the fourth conductive trace 204 d functions as a second reference point for programming the net magnetization vectors of the magnetically programmable soft layer 212 . In one aspect, the second conductive trace 204 d provides a second magnetic field in a second direction that is substantially perpendicular to the first direction of the first magnetic field generated by the first conductive trace 204 a.
In one embodiment, the MRC 200 in FIG. 2A may be connected to the circuit 100 in a manner as follows. The source terminal of the first transistor 104 remains connected to the voltage source (Vs) 110 , and the drain terminal of the first transistor 104 may be connected to the third conductive trace 204 c of the MRC 200 . In addition, the second conductive trace 204 b may be connected to the drain terminal of the second transistor 106 , and the source terminal of the second transistor 106 remains connected to the common ground terminal 112 . Moreover, the input terminal 114 of the inverter circuit 100 remains connected to the gate terminals of the first and second transistors 104 , 106 , and the output terminal 116 of the inverter circuit 100 may be connected to the drain terminal of the first transistor 104 and the third conductive trace 204 c of the MRC 200 . In this embodiment, the first and fourth conductive traces 204 a , 204 d , are used to program the net magnetization vectors of the soft layer 212 . The second and third conductive traces 204 b , 204 c are used to electrically connect the MRC 200 to a circuit 100 in a manner as described. It should be appreciated that the MRC 200 may be similarly integrated into the circuit configurations as described in FIGS. 1B , 1 C, 1 D.
FIGS. 2A , 2 B illustrate one embodiment a functional MRC cell that may be utilized in the various inverter circuit configurations in FIGS. 1A , 1 B, 1 C, 1 D. The operation of the MRC 200 is controlled by magneto-transport, wherein the magneto-resistance depends on the net magnetization vector of the GMR stacked structure 201 or, in other words, the spin orientation of the soft layer 212 with respect to the pinned layer 208 in the GMR stacked structure 201 . In one aspect, the spintronic effect utilizes the spin-polarization of electrons to generate a variable resistance differential across the GMR stacked structure 201 such that a parallel spin orientation between the pinned layer 208 and the soft layer 212 results in a relatively low resistance differential across the GMR stacked structure 201 , or, conversely, an anti-parallel spin orientation between the pinned layer 208 and the soft layer 212 results in a relatively high resistance differential across the GMR stacked structure 201 . In one embodiment, the means for writing to the MRC 200 is by direct polarized spin injection. Alternatively, another means for writing to the MRC 200 is by switching the net magnetization vector in the magnetically programmable soft layer 212 with two orthogonally applied magnetic fields in a manner such that the spin polarization switching may be induced by one or more proximate conductors, such as conductive traces 204 a , 204 d.
For example, a first current applied to the first conductive trace 204 a induces a first magnetic field in a first direction. A second current simultaneously applied to the fourth conductive trace 204 d induces a second magnetic field in a second direction that is substantially perpendicular to the first direction of the first magnetic field. The simultaneous generation of two orthogonal magnetic fields changes the spin orientation of the net magnetization vector within the soft layer 212 from a parallel spin orientation to an anti-parallel spin orientation. To change from an anti-parallel spin orientation to a parallel spin orientation, the applied currents may be reversed and flow in the opposite direction relative to the initial current flow direction. It should be appreciated that this example is disclosed for illustrative purposes and the directions of applied currents and the induced magnetic fields may be altered without departing from the scope of the present teachings.
FIG. 2C illustrates a cross-sectional view of another embodiment of a magneto-resistive contact (MRC) 220 . FIG. 2D illustrates a perspective view of the MRC 220 in FIG. 2C , wherein like numerals within FIGS. 2A-2D correspond to like parts throughout. The MRC 220 comprises similar scope and functionality of the MRC 200 in FIGS. 2A , 2 B with additional layers 224 , 226 a , 226 b . The MRC 220 is formed on an upper surface of the semiconductor based substrate 202 in a manner as previously described with reference to the MRC 200 in FIGS. 2A , 2 B. In addition, the MRC 200 comprises the plurality of conductive traces 204 a , 204 b , 204 c , 204 d , the plurality of insulation layers 206 a , 206 b , and a second GMR stacked structure 222 including the magnetically fixed pinned layer 208 , the spacer layer 210 , the magnetically programmable soft layer 212 , a third insulation layer 226 a , a fourth insulation layer 226 b , and a base layer 224 . The additional insulation layers 226 a , 226 b may be formed of a similar material and in a similar manner as previously described with reference to the insulation layers 206 a , 206 b in FIGS. 2A , 2 B. Furthermore, the base layer 224 may comprise Ta or Cu and be formed in manner using generally known deposition techniques.
In this embodiment, the second GMR stacked structure 222 allows reading the magnetization state between the two ferromagnetic layers 208 , 212 . Writing (switching the top layer as shown) may be accomplished by the spintronic effect (spin injection-directly-transferring spin information in electrons that are injected into the electrons that reside in the magnetization of the ferromagnet). Additionally, switching of the top layer, as shown in FIG. 2C , 2 D for example, may be performed or aided by a conductor placed in proximity, such as conductors 204 a , 204 d . It should be appreciated that the polarity structure that is used as an input to create spin-polarized electrons may comprise magnetic material, such as Co, Fe, or Ni, or an alloy thereof.
FIG. 3 illustrates one embodiment of an MRC array 300 . The MRC array 300 comprises a plurality of MRC devices 302 , wherein each MRC device 302 includes and upper electrode 304 and a lower electrode. The upper electrode 304 is formed adjacent to an upper portion of the MRC device 302 , and the lower electrode 306 is formed adjacent to a lower portion of the MRC device 302 . In one aspect, the plurality of MRC devices 302 are daisy-chained in a manner so as to conductively interlink the lower electrode 306 of one MRC device 302 to the upper electrode of another MRC device 302 . The MRC array 300 is a series of one or more conductively interconnected MRC devices 302 , which may be utilized to increase the resistance differential between multiple transistors or other circuit elements as needed and if substrate area is available or previously allocated for this purpose. For example, if it is determined that a larger and/or smaller resistance differential is needed in a circuit, such as the inverter circuit 100 in FIG. 1A , then a plurality of MRC devices 302 may be conductively interlinked and positioned between the various circuit elements to increase and/or decrease the resistance differential between the various circuit elements.
Advantageously, integrated GMR-based memory and logic structures, such as the above-mentioned magneto-resistive contacts, provide non-volatility to semiconductor-based memory and logic structures, such as SRAM. In one aspect, the magneto-resistive contact demonstrates integrated latch memory, wherein the source and drain contacts of transistors are electrically interconnected with GMR structures to provide a fully integrated advanced memory cell. Furthermore, another advantage is spin current induced magnetic switching, wherein the point contact CPP structures may be switched by injecting or passing currents from magnetically fixed pinned layers to magnetically programmable soft layers for the purpose of altering the spin polarization of the soft layer relative to the fixed polarized spin of the pinned layer. In one aspect, the proposed switching scheme is significantly selective and highly efficient over conventional switching schemes.
Although the following description exemplifies one embodiment of the present invention, it should be understood that various omissions, substitutions, and changes in the form of the detail of the apparatus, system, and/or method as illustrated as well as the uses thereof, may be made by those skilled in the art, without departing from the spirit of the present invention. Consequently, the scope of the present invention should not be limited to the disclosed embodiments, but should be defined by the appended claims. | The semiconductor industry seeks to replace traditional volatile memory devices with improved non-volatile memory devices. The increased demand for a significantly advanced, efficient, and non-volatile data retention technique has driven the development of integrated Giant-Magneto-resistive (GMR) structures. The present teachings relates to integrated latch memory and logic devices and, in particular, concerns a spin dependent logic device that may be integrated with conventional semiconductor-based logic devices to construct high-speed non-volatile static random access memory (SRAM) cells. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to gaming machine configuration and in particular to a communication protocol for gaming machine analysis and gaming machine configuration.
BACKGROUND OF THE INVENTION
[0002] One aspect of gaming machine operation is proper configuration of the gaming machine. Gaming machine configuration may include the assignment of various gaming machine settings to control aspects of game play. The machine settings may include but are not limited to payout limits, accrued winning amounts before automatic payout, hopper limits, pay tables and pay rates, machine denomination, single winning event jackpot limits and game theme settings. In some jurisdictions certain machine settings are closely regulated and the jurisdiction may require that the machine settings be adjusted depending on various factors such as the location of the machine, the time of day, or the day of the week.
[0003] In the prior art, the appropriate or desired machine settings were logged in hardcopy form in a binder or folio. Using a hardcopy report of the appropriate machine settings a technician would physically locate a machine and manually enter, i.e., set up, the machine settings.
[0004] To enter the data, gaming machines of the prior art often included a touch-screen or other similar user interface for the technician to gain access to the machine and configure the machine settings. Access to the gaming machine, which is a high security issue, may be granted through use of complex technician-entered pass codes or expensive and fragile security chips or hardware. The machine-accessible configuration undesirably creates a necessity for security measures that are complex and expensive to implement.
[0005] As can be understood the process of manually configuring a machine's settings via a touch screen interface are a time consuming and tedious operation. The technician must continually refer to the hardcopy binder that contains the machine settings and enter each setting via a touch screen. If configuration occurs via a touch screen, then a further drawback is that the gaming machine must include a touch screen enabled software interface that allows the technician to control machine settings. In addition, during the time consuming machine setup operation the game is not in play and hence potential gaming revenues are lost. In other embodiments a machine's buttons may be used. This results in configuration becoming a very time consuming operation since there a limited number of buttons on a machine.
[0006] As a result of the above-described drawbacks in gaming machine set-up or configuration, there is a need for an efficient way to establish gaming machine settings. The method and apparatus described herein provides an efficient way to determine current gaming machine settings. Also described herein is a method and apparatus to achieve compatibility between different various gaming platforms, operating systems and network protocols.
SUMMARY OF THE INVENTION
[0007] The invention overcomes the drawbacks of the prior art by providing a communication protocol that provides a standardized communication format and system for determining a gaming machine's settings and modifying a gaming machine's settings. In one embodiment the invention comprises a method for determining settings on a gaming machine via a computerized network comprising generating a machine settings request at a host and converting the settings request using the communication protocol to create a standardized settings request. The standardized settings request may be compatible over two or more computer networks. Thereafter the method transmits the standardized settings request over a computer network to a gaming machine. The gaming machine receives the standardized settings request and performs a variable translation at the gaming machine on the standardized settings request to obtain translated variables. The translated variable are variables that may be understood by the gaming machine. Next, the method retrieves the machine settings from the gaming machine based on the translated variables and transmits a response containing the machine settings to the host machine. The host machine receives the response from the gaming machine and may optionally display or record the response.
[0008] In one embodiment this method may, upon receipt of the standardized settings request at the gaming machine, designate the gaming machine in inactive status. In another embodiment the method further comprises verifying that the gaming machine is not in play prior to retrieving the machine settings at a gaming machine.
[0009] In another embodiment a method for determining the settings of a gaming machine via a computerized network is provided. This method comprises receiving a settings request at a gaming machine and converting the settings request to a gaming machine specific format based on a communication protocol and a translation table. Thereafter, the method polls the gaming machine to obtain the requested gaming machine settings and transmits the gaming machine settings over the computerized network. In one embodiment the method further includes transmitting a machine active message to a host machine if the gaming machine is in play upon receipt of the settings request and if gaming machine is in play then not polling or transmitting the gaming machine settings.
[0010] Another method comprises a method for modifying gaming machine settings from a host computer. This method comprises generating a machine status inquiry at the host computer and sending the machine status inquiry to a gaming machine over a computer network. Thereafter the host machines receives an inquiry response from the gaming machine, the inquiry response indicating if the gaming machine is available. If it is available, the host machine sends a gaming machine setting modification request to the gaming machine if the inquiry response indicates that the gaming machine is available. The gaming machine setting modification request is configured to modify one or more settings of the gaming machine. Next, the method receives, at the host computer, a gaming machine setting modification response from the gaming machine regarding whether gaming machines settings were modified.
[0011] In one embodiment the machine status inquiry comprises an inquiry sent to a gaming machine to determine if the gaming machine is being played by a player. In one embodiment the method may further include providing a message on the host computer that the gaming machine is not available if the inquiry response indicates that the gaming machine is not available. In one embodiment generating comprises obtaining input from a user of the host computer regarding which of one or more gaming machines to send a status inquiry to and formatting the status inquiry into a format for transmission over a computerized network.
[0012] In yet another embodiment the method described herein is a method for modifying settings of a gaming machine which comprises providing data to a computerized device regarding which settings to modify and formatting the data into a setting modification request for use by software on the gaming machine. Then providing the setting modification request to a network interface of the computerized device for transmission to a gaming machine. The gaming machine receives and processes the setting modification request at the gaming machine and seizes control of the gaming machine to prevent play during the modification of the settings. The gaming machine or communication protocol software modifies one or more settings of the gaming machine based on the setting modification request.
[0013] In one embodiment the computerized device comprises a computer. The transmission to the gaming machine may occur over a computerized network. The data may specify which gaming machine is to have its settings modified and the setting modification request may include at least one setting and the at least one setting is represented by a first variable and the method may further include translating the first variable to a second variable, wherein the second variable is utilized by the gaming machine. It is further contemplated that in other embodiments more than one variable sent from the host may be translated into a single variable at the gaming machine or a single variable from the host may be translated into more than one variable at the gaming machine. For example, a pay out limit variable sent to from a host may be translated into a hopper limit variable, credit limit variable, and a bet limit variable at the gaming machine. In one embodiment the method includes sending a setting modification confirmation from the gaming machine to the computerized device to provide confirmation that gaming machine settings were modified.
[0014] A system is also described herein for changing one or more settings of a gaming machine from a remote location. Such a system comprises a host system and a gaming machine. The host system includes a user interface, a first network interface configured to communicate over a computerized network, a processor configured to execute computer program code logic, and a processor readable medium configured to store software code or data. The software code or data may comprise computer program code logic configured to generate a gaming machine settings modification request and computer program code logic configured to receive the gaming machine settings modification request and transmit the gaming machine settings modification request to a gaming machine via the first network interface.
[0015] The gaming machine may comprise a second network interface configured to communicate over a computerized network, a processor configured to execute computer program code logic, a processor readable medium configured to store software code or data. The software code and data may comprise computer program code logic configured to receive the gaming machine settings modification request via the second network interface and computer program code logic configured to process the gaming machine settings modification request to thereby modify one or more settings of the gaming machine. In one embodiment the gaming machine settings modification request is in a format compatible with two or more gaming machine network protocols.
[0016] In one configuration one of the one or more settings of the gaming machine comprise a setting that controls the pay out rate for the gaming machine. The gaming machine described above may further include a processor readable medium storing computer program code logic configured to translate a variable representing a setting to be modified by the gaming machine settings modification request to a format compatible with the gaming machine. The gaming machine may also further include a processor readable medium storing computer program code logic configured to prevent gaming machine play during modification of one or more settings of the gaming machine.
[0017] In yet another embodiment the communication protocol configured to facilitate the modification of one or more settings of a gaming machine from a remote location is provided. The communication protocol may be configured to receive data from a machine settings control module located on a host system such that the data identifies at least one gaming machine to which a settings request is to be sent. The communication protocol also processes the data into a settings request so that the settings request is compatible with gaming machine platforms equipped with the communication protocol and provides the settings request to a communication device associated with the host system for transmission to a gaming machine at a remote location.
[0018] In one embodiment the communication protocol is further configured to receive the settings request from a communication device associated with the gaming machine, process the settings request to determine one or more actions requested in the settings request, and execute the one or more actions. The communication protocol may be further configured to prevent play of the gaming machine when the communication protocol processes the settings request and executes the one or more actions. In addition, the communication protocol may be further configured to translate a variable associated with the communication protocol to a variable associated with the gaming machine and the settings request may comprise a request to determine current settings of a gaming machine.
[0019] In some embodiments the gaming machine comprises a gaming machine on a casino floor. While in other embodiments the communication device comprises a communication device configured to transmit the settings request over a computer network, the computer network consisting of a local area network, a wide area network, a gaming machine network, the Internet, a public switched telephone network, or a wireless network.
DESCRIPTION OF THE DRAWINGS
[0020] [0020]FIG. 1 illustrates a generalized process diagram of an example process for gaming machine setting inquiry.
[0021] [0021]FIG. 2 illustrates a generalized process diagram of an example process for gaming machine setting modification.
[0022] [0022]FIG. 3 illustrates a block diagram of an example embodiment of an exemplary computer network as may be used to facilitate machine setting status inquiries and machine setting modification in a loop configuration.
[0023] [0023]FIG. 4 illustrates a block diagram of an example embodiment of a computerized network configured in a star configuration.
[0024] [0024]FIG. 5 illustrates a block diagram of an exemplary embodiment of a host computer.
[0025] [0025]FIG. 6 illustrates an exemplary translation table.
[0026] [0026]FIG. 7 illustrates a block diagram of an example embodiment of a gaming machine configured to utilize a communication protocol.
[0027] [0027]FIG. 8 illustrates an example compilation of software code or computer program code logic retained on a storage medium.
[0028] [0028]FIG. 9 illustrates an operational flow diagram of an example method of operation of the communication protocol performing a machine setting inquiry.
[0029] [0029]FIG. 10 illustrates an operational flow diagram of an example method of operation of the communication protocol performing a machine setting change request.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The method and apparatus described herein is a communication protocol for machine setting inquiry and modification, a system for communication protocol operation and a method for machine setting inquiry and modification. In the following description, numerous specific details are set forth in order to provide a more thorough description of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without these specific details. In other instances, well-known features have not been described in detail so as not to obscure the invention.
[0031] [0031]FIG. 1 illustrates a generalized process diagram of an example process of gaming machine settings inquiry as described herein. A host machine 100 is designated on the left-hand side of FIG. 1, while a gaming machine 108 is designated on the right-hand side of FIG. 1. Between the gaming machine 108 and host machine 100 , a communication medium 104 is shown. It is contemplated that the host machine 100 communicates with one or more gaming machine 108 via a computer network or other communication system using the communication medium 104 to relay data or signals. In one embodiment the host machine 100 comprises a server computer, the communication medium 104 comprises Ethernet, twisted pair, wireless, or any other suitable channel, and the gaming machine 108 comprise any type of device configured to provide a gaming experience or gaming event to a player.
[0032] To overcome the drawbacks of the prior art, the method and apparatus described herein provides a communication protocol to facilitate configuration of a gaming machine over a gaming network or a computer network. The communication protocol may also be utilized to poll a gaming machine to determine its current settings. The communication protocol described herein is intended to be universally compatible across various hosts and gaming machine platforms. As a result it desirably includes functionality to interface with various host systems and gaming machine platforms and may further include protocol translation tables and data variable tables to gain compatibility with numerous various systems.
[0033] In reference to FIG. 1, at an operation 112 a machine setting data request is generated in an effort to obtain the status or settings of a remote gaming machine. Machine settings may include, but are not limited to, payout limits, accrued winning amounts before automatic payout, hopper limits, pay tables and pay rates, machine denomination, single winning event jackpot limits and game theme settings, peripherals present or disable/enable, tilt settings, machine volume levels, enable/disable of other communication protocols, such as accounting protocols, maximum bet, maximum win, player options, electronic fund options, and jackpot limits.
[0034] At an operation 116 , the host machine activates the commination protocol and thereby performs translation and framing on the machine setting data request. Communication protocol translation and framing 116 comprises activation of a communication protocol, manipulation of the machine setting data request for transmission over a computer network in a format which may be interpreted, received and processed by a remote gaming machine and the providing of the processed machine setting data request to a network input/output device of the host machine. Thereafter at operation 120 the host machine performs input/output (I/O) operations on the machine setting data request, thereby transmitting it over the communication medium 104 to a gaming machine 108 .
[0035] Upon receipt by the gaming machine 108 , the machine setting data request is received in a similar I/O operation at operation 140 . It is contemplated that the I/O operation 140 operate and execute in a manner similar to other communication over the network, thereby allowing the communication protocol described herein to interface and gain the advantages of existing network operations and apparatus. After the I/O operation at operation 140 , the machine setting data request is forwarded to and activates an operation 144 wherein the communication protocol translation occurs at the gaming machine 108 . Communication protocol translation interprets the machine setting data request and transforms the request into a format suitable for interpretation and processing by the gaming machine 108 .
[0036] As it is contemplated that the communication protocol be compatible with various gaming machine platforms, operation 148 occurs to perform data variable translation on the variables that represent the machine settings in the machine setting data request. As is commonly understood, gaming machines often represent gaming machine settings with software variables that are used by the machine software during game play. It is contemplated that these variables may vary depending upon the gaming machine platform to which the machine setting data request was transmitted. Accordingly, operation 148 performs data variable translation to allow the gaming machine 108 obtain the proper information by translating one or more variables utilized by the host machine 100 to a variable set that is understood by the gaming machine 108 . The translation process is described below in greater detail.
[0037] In an operation 152 the gaming machine 108 collects data for its current settings. It is contemplated that this step may occur in a manner previously performed by gaming machine 108 software as a result of the communication protocol translation operation 144 or the data variable translation of operation 148 . After collecting the data regarding the current settings of the gaming machine 108 , the gaming machine performs communication protocol translation and framing at operation 154 to facilitate transfer of the machine settings to the requestor or entity, in this case the host machine 104 . After communication protocol translation and framing at operation 154 the machine settings are subject to an I/O operation 158 . This occurs in a standardized method as would occur with other gaming machine data. Hence the communication protocol described herein is able to take advantage of existing network software routines and apparatus for input and output.
[0038] The I/O operation 158 transmits the current gaming machine settings over the communication medium 104 to a host machine 100 . At the host machine 100 a similar I/O operation 124 occurs to receive the data from the gaming machine 108 . The I/O operation 124 forwards the data to systems that perform operation 132 . Operation 132 comprises communication protocol translation to translate data from the gaming machine out of the format of the standardized communication protocol to a format for use by the host machine 100 . As can be understood, this operation may only be necessary in ceratin systems. In one embodiment the communication protocol for gaming machine configuration serves as an intermediate or background communication protocol to provide a standardized software interface for communication between the host machine and the one or more gaming machines 108 organized under software and hardware platforms.
[0039] At operation 136 the host machine 100 receives the machine setting data request response and may store the machine settings to a file or displaying the machine settings on a display or other user interface. It should be noted that the figure shown in FIG. 1 is a generalized procedure and other variations or procedures are contemplated which do not depart from the scope of the claims. Additional details of various embodiments are described below in greater detail.
[0040] [0040]FIG. 2 illustrates a generalized process diagram of an example process for gaming machine setting modification. As aspects of FIG. 2 are identical to aspects of FIG. 1, like elements are referenced with identical reference numbers. In contrast to FIG. 1, FIG. 2 generally describes the procedures used to modify machine settings using the communication protocol as described herein. The use of the communication protocol allows gaming machine settings to rapidly and efficiently modify gaming machine settings via a computerized network or other means of communication. In operation 212 it is contemplated that the communication protocol be compatible with various gaming machine platforms, operation 248 occurs to perform data variable translation on the variables that represent the machine settings in the machine setting data request. As is commonly understood, gaming machines often represent gaming machine settings with software variables that are used by the machine software during game play. It is contemplated that these variables may vary depending upon the gaming machine platform to which the machine setting data request was transmitted. Accordingly, operation 148 performs data variable translation to allow the gaming machine 108 obtain the proper information by translating one or more variables utilized by the host machine 100 to a variable set that is understood by the gaming machine 108 . The translation process is described below in greater detail.
[0041] In an operation 224 the gaming machine 108 modifies its current settings based on the modification request. After modifying the data regarding the current settings of the gaming machine 108 , the gaming machine performs communication protocol translation and framing at operation 228 to facilitate transfer a confirmation of the modification of the machine settings to the requestor or entity, in this case the host machine 104 . After communication protocol translation and framing at operation 154 the machine settings are subject to an I/O operation 158 . This occurs in a standardized method as would occur with other gaming machine data. Hence the communication protocol described herein is able to take advantage of existing network software routines and apparatus for input and output.
[0042] The I/O operation 158 transmits the current gaming machine settings over the communication medium 104 to a host machine 100 . At the host machine 100 a similar I/O operation 124 occurs to receive the data from the gaming machine 108 . The I/O operation 124 forwards the data to systems that perform operation 132 . Operation 132 comprises communication protocol translation to translate data from the gaming machine out of the format of the standardized communication protocol to a format for use by the host machine 100 . As can be understood, this operation may only be necessary in ceratin systems. In one embodiment the communication protocol for gaming machine configuration serves as an intermediate or background communication protocol to provide a standardized software interface for communication between the host machine and the one or more gaming machines 108 organized under software and hardware platforms.
[0043] At operation 240 the host machine 100 receives the machine setting modification request response and may store and/or display the confirmation of the new machine settings or store the new settings to a file. It should be noted that the figure shown in FIG. 1 is a generalized procedure and other variations or procedures are contemplated which do not depart from the scope of the claims. Additional details of various embodiments are described below in greater detail.
[0044] [0044]FIG. 3A illustrates a block diagram of an example embodiment of an exemplary computer network as may be used to facilitate machine setting status inquiries and machine setting modification using a communication protocol as described herein. The network configuration of FIG. 3A is configured in a daisy chain or loop format. The network includes a host computer 300 linked by one or more communication or network cabling 302 to gaming machines 304 , 308 and 312 . It is contemplated that N number of gaming machines may be configured in this matter up through gaming machine 312 designated a gaming machine N. In operation host machine 300 generates a message having a message address and transmits it over line 302 . The message from the host 300 progresses along the network and is analyzed by each gaming machine 304 , 308 and 312 . Each gaming machine 304 , 308 and 312 analyzes the message address to determine if it should accept and process the message from the host 300 . Messages may be addressed to more than one or a range of gaming machines 304 , 308 and 312 . Any message format may be used and the message may be of any length transmitted as a single message or segmented into smaller messages according to a network protocol.
[0045] [0045]FIG. 3B illustrates a block diagram of an alternative embodiment to the configuration shown in FIG. 3A. Similar elements are labeled with identical reference numbers. Only the aspect of FIG. 3B which differ from FIG. 3A are discussed. As shown a first interface 330 connects to the host 300 . The first interface 330 connects in series to a second interface 334 . The second interface 334 may optionally connect to additional interfaces up to an Nth interface 338 .
[0046] Each interfaces 330 , 334 , 338 connects to a gaming machine 304 , 308 , 312 as shown. In one embodiment the interfaces 330 , 334 , 338 perform communication services for the gaming machines 304 , 308 , 312 . In one embodiment the interfaces 330 , 334 , 338 comprise network interface cards configured to receive, translate, or store data for a gaming machine. Other communication protocol services may be performed by the interfaces 330 , 334 , 338 such as variable translation or machine settings inquiries. In one embodiment the interface comprises a sub-host configured to perform at least partially as the 300 .
[0047] [0047]FIG. 4 illustrates a block diagram of an example embodiment of a computerized network configured in a star configuration. The star network configuration show in FIG. 4 is a host computer 400 connected via several network links 402 A, 402 B, 402 C. The network links 402 connect the host 400 to gaming machines 404 , 408 and 412 . Any number of gaming machines may be connected to the host 400 up to and as shown by Nth gaming machine 412 . It is contemplated that each gaming machine can utilize a separate port (not shown) on the host 400 .
[0048] In this configuration the host machine 400 generates a message such as a machine settings request or a machine setting modification request and forwards it to the particular machine 404 , 408 and 412 , based on the port address of the machine. A message may be provided to multiple ports or a range of ports on the host machine 400 to facilitate multiple machine addressing.
[0049] [0049]FIG. 5 illustrates a block diagram of an exemplary embodiment of a host computer 500 . This is but one exemplary embodiment and it is contemplated that one or ordinary skill in the art may design other embodiments. The host 500 includes a processor 504 in communication with a memory 506 . The host 500 also includes a user interface 508 connected to the processor 504 . The user interface 508 may include one or more input/output systems configured to use one or more input/output buses 512 . The one or more input/output buses 512 facilitate interaction with a human operator or other computer systems.
[0050] As described herein a protocol processing module 520 communicates with a memory 524 and an input/output system 528 . The I/O system 528 connects to one or more other computers via a computer network which may utilizes an input/output bus or communication channels 532 .
[0051] The processor 504 may comprise any type processor or control logic configured to execute software code and oversee operation of a host machine 500 . Examples of the processor 504 include, but are not limited to, a processor or CPU such as an Intel type or AMD type processor, an ASIC type processor, control logic, digital signal processor, or any other devices capable of executing software code or computer program code logic or interfacing with a computer network. Memory 506 , which is in communication with processor 504 , may comprise any type of memory including volatile or nonvolatile memory such as, but not limited to, a hard disk drive, magnetic memory, or flash memory, RAM, either static or dynamic, ROM, or optical memory. The memory 506 may be located internal to the host 500 or external such as on a RAID hard drive system or other external storage medium. The user interface 508 and bus 512 may comprise video display drivers and input/output hardware, keyboard, mouse or other input device, software, drivers and hardware or any other user interface system as may be contemplated by one of ordinary skill in the art.
[0052] A protocol processing module 520 comprises a configuration of hardware or software or both configured to perform processing on the data requests from the processor 504 into a standardized format for transmission over a computer network to be received by one or more gaming machines. In one embodiment the protocol processing module 520 is integrated within the processor 504 . In one embodiment the protocol processing module comprises a one or more processors, an ASIC, control logic or other processing system. The protocol processing module may be incorporated into the processor 504 . The memory 524 may comprise any type of memory. In one embodiment the memory comprises RAM. The protocol processing module 520 may further include variable translation tables, which may be integrated with the protocol processing module 520 or stored in memory 524 . The variable translation table contains data to translate a machine setting variable defined by the processor 504 to a variable as would be understood by the gaming machine platform which eventually receives the machine setting inquiry or request. Hence a first variable may be translated to a second variable. It is further contemplated that a first variable may be expanded into more than one alternate variables. Thus, a single variable sent by a host may be translated into two or more variable that are understood by or used by the gaming machine. The first variable may be expanded into N number of variables where N is any positive integer. It is also contemplated that two or more variable sent by the host may be translated into a reduced number of variables or a single variable at the gaming machine. In addition the protocol processing module 520 in conjunction the I/O system 528 may formulate the communication protocol communications into packets for transmission over a computer network and perform transmission over a network line 532 . The I/O system 528 may be referred to a network interface.
[0053] [0053]FIG. 6 illustrates an example embodiment of a translation table 600 . Although various different types of translation tables may be implemented for use with the communication protocol described herein, the table shown in FIG. 6 includes a communication protocol variable set, in column 1 604 , which in this embodiment is recognized for use in a host computer. It is contemplated that the communication protocol variable shown in column 604 is defined by or understood by the host machine and the communication protocol. Hence these are the variables that would be used by the communication protocol software or a software system or module utilized by a user to request gaming machine status or request a change in gaming machine settings.
[0054] A second column 608 contains a variable set that corresponds to a gaming machine of a first type. A third column 612 contains a variable set corresponding to a gaming machine of a second type. A fourth column 616 contains variable set corresponding to a gaming machine of a forth type. By way of example, a row 620 contains the communication protocol variable representing the pay limit for a gaming machine. In an exemplary communication protocol, the variable the represents the pay out limit is PAYLIMIT as shown in row 620 . Gaming machines and the software executing thereon may not recognize the variable PAYLIMIT as the variable that represents the pay out limit. Utilizing the translation table and the type of gaming machine to which the data request or modification request is being sent, the translation table provides a variable set translation. Based on the information in the second column 608 the variable set for the type one gaming machine or type one platform is defined as a variable PYLIM. Likewise for second column this pay limit variable comprises the variable A while the variable for a third type gaming machine as shown in the fourth column as defined by the variable R. The remaining rows of the translation table illustrate other variables and their potential translation. These variables and their translations are provided by way of example and for purposes of understanding and discussion the present invention is not limited to these variables. Furthermore, any number of rows, columns or translations tables may be utilized as is necessary to achieve the method and apparatus described herein.
[0055] Turning now to FIG. 7, a block diagram of an example embodiment of a gaming machine configured to utilize the communication protocol and methods derived therefrom.
[0056] This is but one exemplary embodiment and it is contemplated that other configuration may be arrived at without departing from the scope of the invention. As shown a gaming machine 700 includes a processor 704 in communication with a memory 712 . The gaming machine 700 also includes a user interface 708 connected to the processor 704 . The user interface 708 may include one or more input/output systems configured to use an input/output bus 740 . The one or more input/output buses 740 facilitate interaction with a human operator or other computer systems.
[0057] As described herein a protocol processing module 716 communicates with a memory 720 and an input/output system 724 . The I/O system 724 connects to one or more other computers or other gaming machines via a computer network which may utilizes input/output bus or communication channels 744 .
[0058] The processor 704 may comprise any type processor or control logic configured to execute software code and oversee operation of a gaming machine 700 . Examples of the processor 704 include, but are not limited to, a processor such as an Intel type or AMD type processor, an ASIC type processor, control logic, digital signal processor, or any other devices capable of forcing a computer network. The memory 712 , which is in communication with processor 704 , may comprise any type of memory including volatile or nonvolatile memory such as, but not limited to, a hard disk drive, magnetic memory, or optical memory. The memory 712 may be located internal to the gaming machine 700 or external such as on a RAID hard drive system or other external storage medium. The user interface 708 and input/output lines 740 may comprise a video display drivers and input/output hardware, keyboard, mouse or other input device, software, drivers and hardware or any other user interface system as may be contemplated by one of ordinary skill in the art.
[0059] The protocol processing module 716 comprises a configuration of hardware or software or both configured to perform processing on the inquiries or modification requests from the processor 504 to thereby transform them into a standardized format for transmission over a computer network and for receipt by one or more gaming machines. In one embodiment the protocol processing module 716 is integrated within the processor 704 . In one embodiment the protocol processing module comprises a one or more processors, ASIC, control logic or other processing system. The memory 720 may comprise any type memory. In one embodiment the memory comprises RAM. The protocol processing module 716 may further include variable translation tables, which may be integrated with the protocol processing module 716 or stored in memory 720 . Either of the host machine or gaming machine or both may contain the translation tables and functionality associated therewith. The variable translation table translates a machine setting variable requested by the host to a variable as would be understood by the gaming machine platform which eventually receives the machine setting request. The protocol processing module 716 in conjunction the I/O system 724 perform input/output processing such as formulation of the request into a packet format for transmission over a network.
[0060] [0060]FIG. 8 illustrates an example compilation of software code such as may be stored on a gaming machine, such at in the one or more memories of the gaming machine shown in FIG. 7. It contemplated that the gaming machine may contain game code 804 , system software 808 and communication protocols 812 . The game code 804 , system software 808 and communication protocols 812 may stored on any type of memory, storage medium, or processor readable medium.
[0061] The game code 804 comprises software configured to provide a game play to a player on the gaming machine. The system software 808 controls operation of the gaming machine, gaming machine peripherals, and use of a computer network to communicate with a host. The system software may also interfaces the game code 804 and the gaming machine. As a subsystem of the system software 804 the communication protocol 812 may comprise one or more software modules for use by this system software. Upon receiving a game setting data request or a request to modify current game settings the system software may activate the communication protocols 812 or utilize the communication protocols to respond to the requests from the host machine. In one embodiment is contemplated communication protocol 812 remain inactive in the background of the system software until receipt of a inquiry or modification request. Then the communication protocol interprets the request for settings modification and performs variable translation as necessary. It is further contemplated that software may be stored on the gaming system other than that shown in FIG. 8. This software facilitates operation of the gaming machine and facilitates communication over a computer network.
[0062] [0062]FIG. 9 illustrates an operational flow diagram of an example method of operation of the communication protocol. The method of operation shown in FIG. 9 is representative of communication between the host machine and one or more gaming machines wherein the host machine is requesting to the current status or configuration of the gaming machine's settings. FIG. 9 also illustrates the interaction between the host machine and the gaming machine in an exemplary method of operation. The steps shown or occurring on the left hand side of FIG. 9 represent activity occurring at the host machine while steps occurring or shown on the right hand side of FIG. 9 represent those at a gaming machine. Communication between the host machine and gaming machine may occur over a computer network or other communication system. It is further contemplated that a method of operation other than exactly shown in FIG. 9 may occur.
[0063] At step 904 the host machine generates a gaming machine setting request. The setting request may be generated as part of a scheduled and standard machine operation or through a specific user request generated especially for determining the settings of a game machine. In one embodiment a software interface is provided for users to efficiently and easily use the machine settings request operation. User interfaces may be provided to selectively specify which machine are subject to the machine setting request. Machines are usually identified by a network address or some other type of machine classification. Any addressing scheme may be adopted for use.
[0064] After the machine settings request is generated by the host machine the communication protocol performs protocol translation. This occurs at a step 908 . Protocol translation comprises activation of the communication protocol and conversion of the machine setting request to the format and that is compatible for transmission over a computer network and/or receipt and processing by a gaming machine. Protocol translation may also include data variable conversion and a machine setting conversion in the host machine. However in the example embodiment of FIG. 9 the communication protocol module of the gaming machine stores the variable translation tables.
[0065] At a step 912 the host machine generates a machine status inquiry. A machine status inquiry comprises a request, to the gaming machine being polled, for its status. A settings request may be distinguished from a status inquiry in that the setting request is a request to determine the current settings of a gaming machine while a status inquiry is a inquiry to determine if the gaming machine is available to process a request, such as a settings request or a modification request. In one embodiment status comprises available and/or unavailable. Another embodiment status may be designated as active or inactive. An available or inactive machine is a machine that is not currently in play by a player while an unavailable or active machine comprises a gaming currently in play. As can be understood it is undesirable to poll machine settings of a game currently in play as this could interrupt game play or risk, although unlikely, a potential malfunction. Accordingly it is desired to collect data regarding gaming machine setting when the gaming machine is not in play. It is contemplated however, that the machine poll operation or the machine configure operation may occur during game play or during a period of game inactivity.
[0066] Thereafter at a step 916 the host machine transmits the machine status inquiry over the network to one of our gaming machines. It is contemplated that adequate network protocols, network addressing and packetizing and framing be incorporated into this step to achieve transmission over a computer network to the one or more gaming machines.
[0067] Turning now to the operation of the gaming machine at step 920 , the gaming machine receives the machine status inquiry and performs analysis as would be understood one or ordinary skill in the art. The present goal is to determine whether the machine is available to respond to a machine status inquiry from a host. At a step 924 a determination is made regarding the machine status. If the machine status is available then the operation advances to step 928 and the gaming machine generates a machine available response for transmission to the host machine. Conversely, if at step 924 the game machine is not available then the gaming machine generates a machine not available response for transmission to the host. It is contemplated that the communication protocol may poll the gaming machine or the software located thereon to determine if the gaming machine is available. Although not shown it is further contemplated that an error code may be generated if a decisive response cannot be provided regarding machine availability.
[0068] Turning now to FIG. 9B, the operation advances to step 938 wherein the communication protocol of the gaming machine performs protocol translation on the response so the response may be transmitted using the communication protocol. The operations of Step 934 may comprise translations from the communication protocol format to a format or message configuration compatible with the gaming machine or network interface. At a step 942 the gaming machine transmits the machine status response over the computer network to the host. This may occur in a manner know in the art such as in a manner compatible with existing or future gaming machine networks or computer networks.
[0069] After translation in a step 942 the host receives the machine status response from the gaming machine. This occurs at step 946 . Thereafter the host may optionally perform communication protocol translation. At step 950 the host machine interprets whether the gaming machine is available based on a response from the gaming machine. If the gaming machine is unavailable the operation advances up to step 954 and the host machine may generate and display or store in memory a message that the gaming machine status is unavailable and hence no machine settings were retrieved.
[0070] In contrast, if at that Step 950 the gaming machine message is interpreted to indicate that the gaming machine is available then the operation advances to the step 958 and protocol translation may occur. Advancing to step 958 occurs if the machine is available to receive and process a machine settings inquiry. At a step 962 the host machine transmits the machine settings request over the computer network to one or more gaming machines.
[0071] Advancing to step 966 the gaming machine receives the machine settings request or inquiry and thereafter at step 972 performs variable translation on the machine settings request. In one embodiment the variable translation translates the variables used and understood by the communication protocol to a set of variables that represent the machine setting variables as used by the gaming machine. It is contemplated that the gaming machine may operate under any number of standards or platforms with various different operating systems. Hence the variable translation occurs to insure that the variable or information identified by the host machine may be properly matched up with or correlated to the variables and data as understood by the gaming machine. As a result, the communication protocol described herein may be compatible across different gaming machine platforms or operating systems. The translation table such as that show in FIG. 6 may be utilized to this end.
[0072] Shown on FIG. 9C the gaming machine operating software polls the machine settings based on the translated variables. This occurs at a step 974 . This occurs in a manner dependant upon the gaming machine platform and operation system of the gaming machine. Thereafter at a step 976 the gaming machine, after having obtained the gaming machine settings from the various apparatus and software of the gaming machine, performs protocol translation on the data to facilitate transmission of the gaming machine setting over the computer. It is further contemplated that this may include compiling the gaming machine settings into a response or performing a re-translation of the gaming machine data back to the original variables so that the requested data may be understood by the host machine and the communication protocol located on the host machine. Packetizing, addressing, and the like may also be performed at step 976 . Thereafter at a step 980 the gaming machine transmits the machine setting response.
[0073] After transmission the operation advances to a step 984 wherein the host machine receives the machine settings response and provides the receives data to the communication protocol. At step 988 the communication protocol performs protocol translation on the data to translate it into a format for use by the host machine. It is contemplated that a software module be running on the host machine for storage of the data or display of the data to the requesting party. Accordingly at a step 992 the host machine records or displays the machine settings. Although not expressly described in FIG. 9 is contemplated that the gaming machine being polled may optionally be placed into an inactive status so as to not interfere with game play. It should be noted however that the polling process is of sufficiently short time duration that a machine reporting an inactive status would likely not enter into active game play before the polling operation is completed.
[0074] [0074]FIG. 10 illustrates an example of an operational flow diagram of an example method of operation of a gaming machine setting modification routine. This is one example method of a operation routine to change a machine setting using the communication protocol described herein. As compared to FIG. 9, FIG. 10 contains similar steps. For purposes of understanding and readability, the entire processes of machine setting modification is described.
[0075] The method of operation shown in FIG. 10 is representative of communication between the host machine and one or more gaming machines wherein the host machine is requesting that the settings of gaming machine be modified. The steps shown or occurring on the left hand side of FIG. 10 represent activity occurring at the host machine while steps occurring or shown on the right hand side of FIG. 10 represent those at a gaming machine. Communication between the host machine and gaming machine may occur over a computer network or other communication system. It is further contemplated that a method of operation other than exactly shown in FIG. 10 may occur.
[0076] At step 904 the host machine generates a gaming machine setting modification request. The modification request may be generated as part of a scheduled and standard machine operation or through a specific user request generated especially for determining the settings of a game machine. In one embodiment a software interface is provided for users to efficiently and easily modify the settings. User interfaces may be provided to selectively specify which machine are subject to the machine setting modification request. Machines are usually identified by a network address or some other type of machine classification. Any addressing scheme may be adopted for use.
[0077] After the machine setting modification request is generated by the host machine the communication protocol performs protocol translation. This occurs at a step 1008 . Protocol translation comprises activation of the communication protocol and conversion of the machine setting request to the format and that is compatible for transmission over a computer network and/or receipt and processing by a gaming machine. Protocol translation may also include data variable conversion and a machine setting conversion in the host machine. However in the example embodiment of FIG. 10 the communication protocol module of the gaming machine stores the variable translation tables.
[0078] At a step 1012 the host machine generates a machine status inquiry. A machine status inquiry comprises a request, to the gaming machine being polled, for its status. In one embodiment status comprises available and/or unavailable. Another embodiment status may be designated as active or inactive. An available or inactive machine is a machine that is not currently in play by a player while an unavailable or active machine comprises a gaming currently in play. As can be understood it is undesirable to modify machine settings of a gaming machine that is currently in play as this could interrupt game play or risk, although unlikely, a potential malfunction. Accordingly it is desired to modify data regarding gaming machine settings when the gaming machine is not in play.
[0079] Thereafter at a step 1016 the host machine transmits the machine status inquiry over the network to one of our gaming machines. It is contemplated that adequate network protocols, network addressing and packetizing and framing be incorporated into this step to achieve transmission over a computer network to the one or more gaming machines.
[0080] Turning now to the operation of the gaming machine at step 1020 , the gaming machine receives the machine status inquiry and performs analysis as would be understood one or ordinary skill in the art. The present goal is to determine whether the machine is available to respond to a machine setting modification request from a host. At a step 1024 a determination is made regarding the machine status. If the machine status is available then the operation advances to step 1028 and the gaming machine generates a machine available response for transmission to the host machine. Conversely, if at step 1024 the game machine is not available then the gaming machine generates a machine not available response for transmission to the host. It is contemplated that the communication protocol may poll the gaming machine or the software located thereon to determine if the gaming machine is available. Although not shown it is further contemplated that an error code may be generated if a decisive response cannot be provided regarding machine availability.
[0081] Turning now to FIG. 10B, the operation advances to step 1038 wherein the communication protocol of the gaming machine performs protocol translation on the response so the response may be transmitted using the communication protocol. The operations of step 1034 may comprise translations from the communication protocol format to a format or message configuration compatible with the gaming machine or network interface. At a step 1042 the gaming machine transmits the machine status response over the computer network to the host. This may occur in a manner know in the art such as in a manner compatible with existing or future gaming machine networks or computer networks.
[0082] After translation in a step 1042 the host receives the machine status response from the gaming machine. This occurs at step 1046 . Thereafter the host may optionally perform communication protocol translation. At step 950 the host machine interprets whether the gaming machine is available based on a response from the gaming machine. If the gaming machine is unavailable the operation advances up to step 1054 and the host machine may generate and display or store in memory a message that the gaming machine status is unavailable and hence no machine settings were retrieved.
[0083] In contrast, if at that Step 1050 the gaming machine message is interpreted to indicate that the gaming machine is available then the operation advances to the step 1058 and protocol translation may occur. Protocol translation of step 1058 may occur before or after a determination is made regarding whether the machine is available. At a step 1062 the host machine transmits the machine settings modification request over the computer network to one or more gaming machines.
[0084] Advancing to step 1066 the gaming machine receives the machine settings modification request and thereafter, at step 1072 , designates the machine as inactive. Designating the gaming machine as inactive prevents the gaming machine from entering into play during the settings modification process. The modification process is anticipated to be brief and hence the short period of inactive status will not significantly lower a gaming machines profit potential.
[0085] As shown on FIG. 10C, and at step 1074 , the operation performs variable translation on the machine settings modification request. In one embodiment the variable translation translates the variables used and understood by the communication protocol to a set of variables that represent the machine setting variables as used by the gaming machine. It is contemplated that the gaming machine may operate under any number of standards or platforms with various different operating systems. Hence the variable translation occurs to insure that the variable or information identified by the host machine may be properly matched up with or correlated to the variables and data as understood by the gaming machine. As a result, the communication protocol described herein may be compatible across different gaming machine platforms or operating systems. The translation table such as that show in FIG. 6 may be utilized to this end.
[0086] Next, the gaming machine, based on the received modification request, modifies the settings of the gaming machine at step 1076 . The modification may occur in a manner dictated by the gaming machine and as may be known in the art. Thereafter, at step 1078 , the gaming machine, communication protocol, or other software executing on the gaming machine polls the machine settings based on the translated variables. This occurs in a manner dependant upon the gaming machine platform and operation system of the gaming machine. At a step 1080 , the gaming machine, after having obtained the gaming machine settings from the various apparatus and software of the gaming machine, performs protocol translation on the data to facilitate transmission of the gaming machine setting over the computer. It is further contemplated that this may include compiling the gaming machine settings into a response or performing a re-translation of the gaming machine data back to the original variables so that the requested data may be understood by the host machine and the communication protocol located on the host machine. In one embodiment the response of step 1078 serves as a confirmation to the host machine that the settings were modified in the manner requested. Packetization, addressing, and the like may also be performed at step 1076 . Thereafter at a step 1082 the gaming machine transmits the machine setting response to the host or any other system, device, or entity that requested the gaming machine setting modification.
[0087] After transmission the operation advances to a step 1094 and 1084 . At step 1094 the gaming machine is restored to active status to game play or operation may occur using the modified settings. At step 1084 the host machine receives the machine settings modification response and provides the receives data to the communication protocol. At step 1086 the communication protocol performs protocol translation on the data to translate it into a format for use by the host machine. It is contemplated that a software module be running on the host machine for storage of the data or display of the data to the requesting party. Accordingly at a step 1092 the host machine records or displays the machine settings. Although not expressly described in FIG. 10 is contemplated that the gaming machine having its settings modified need not be placed into inactive status.
[0088] In is further contemplated that in one embodiment a gaming machine may serve as a host for purposes of configuring other gaming machines. Thus it is contemplated that the communication protocol and the associated software to facilitate configuring other gaming machines may be located on a gaming machine. In such an embodiment a technician may access a gaming machine to thereby configure other gaming machines. Such an embodiment may be desired in gaming machine networks that lack a host or when a host configuration process is unavailable or undesirable. The gaming machine configured to configure other gaming machine using the protocol described herein may include software to facilitate interface by a technician.
[0089] In operation a technician may configure a first gaming machine in any manner possible. Thereafter, the technician may activate the communication protocol described herein to configure gaming machines other than the first gaming machine in the manner described herein. A configuration identical to or different from the first gaming machine may be selected for other gaming machines. It is further contemplated that adjacent gaming machines, gaming machines in a gaming machine bank or any other gaming machine may be configured. Configuring from a gaming machine provides the same benefits over the prior art described above by providing a more rapid and efficient means to configure gaming machines. The advantages are available after setting up a first gaming machine in a known manner and in a location wherein other gaming machines to be configured may be readily identified.
[0090] In one embodiment the configuration occurs using a device other than a gaming machine or a host. It is contemplated that configuration may occur from a laptop computer, personal digital assistant, handheld computing device, or any other wireless or hardwired communication or computing device. In such an embodiment, a technician may connect to the one or more gaming machines to be configured and perform processing in the manner described above to facilitate a configuration change or query. Either a wireless, optical, or hardwired connection may occur. It is further contemplated that such a device may have pre-stored thereon the desired gaming machine settings or connect to a gaming machine or other source to obtain the desired machine settings. These machine settings would be stored in a memory located in the device for transfer to one or more other gaming machines. Machine updates may occur at different properties from common configuration file(s).
[0091] It will be understood that the above described arrangements of apparatus and the method therefrom are merely illustrative of applications of the principles of this invention and many other embodiments and modifications may be made without departing from the spirit and scope of the invention as defined in the claims. | A method and apparatus for communicating gaming machine settings is disclosed. In one embodiment a universal configuration communication protocol is provided for retrieving or modifying, over a network, current gaming machine setting of a remotely located gaming machine. A translation table may be implemented with the communication protocol to achieve variable translation between different gaming machine platforms. In one embodiment the gaming machine status is requested prior to activating the communication protocol to prevent interruption of game play. In one embodiment activation of the communication protocol may result in the gaming machine momentarily entering an inactive status. | 7 |
FIELD OF THE INVENTION
The invention generally relates to a system for offering, purchasing, and generating tickets, such as for live events.
BACKGROUND ART
The advent and acceptance of electronic tickets, or e-tickets, has simplified the process for spectators and event attendees, allowing them to receive tickets by e-mail and print a proof of purchase from their computer. In addition, new systems have allowed users to use an electronic ticket's bar code, or similar authentication mark, to enter an event.
Although these advancements have alleviated a spectator's need to maintain paper tickets, they also have robbed spectators of a valuable part of the ticketing process. Unique paper tickets are a valuable keepsake by which a spectator can remember their attendance at a particular event. In addition, paper tickets can have value among sports memorabilia collectors or have sentimental value. Electronic tickets or “e-tickets,” in general, do not have the same look and feel or quality as an actual ticket printed for the event.
Systems for generating tickets are known for use with respect to events such as concerts and sports matches, but none are intended, for example, to provide replica tickets alongside electronic tickets, to compensate for the void created by the electronic ticketing process.
SUMMARY OF THE INVENTION
Methods and apparatus for generating offering, purchasing, and replica tickets for an event such as a concert or sports match are provided. The replica tickets are designed to have the exact look and feel of the paper tickets issued for the event. One method includes software which provides the ticket purchaser the option to receive a replica ticket via e-mail and print it from a local computer. In an alternative embodiment, software provides the ticket purchaser with the option to receive a replica ticket in the mail. In additional embodiments, the software will notify the event coordinator that only the electronic ticket will be valid for entry, thus ensuring that the ticket purchaser cannot use both their electronic ticket and replica ticket. In further embodiments, both the electronic ticket and replica ticket may be used for entry to the event, but the event coordinator uses software to ensure that only one is used to gain entry. Finally, if the replica tickets are issued alongside electronic tickets, they may be given authentication numbers. Users can query a website using this authentication number to determine if the replica ticket is valid for entry to the event, or intended solely for the purpose of memorabilia. Online e-ticket customers can be presented with an interactive option (e.g., via an interface) when they are purchasing an e-ticket for attending an event. The option, for example, offers the customer a replica ticket to purchase as an “add-on” item to purchasing a corresponding e-ticket. The physical replica ticket can be delivered by physical delivery (e.g., a shipping service, at the event, etc.) or electronically (e.g., the purchaser prints a physical replica ticket).
BRIEF DESCRIPTION OF THE DRAWINGS
Other aspects, purposes, and advantages of the invention will become clear after reading the following detailed description with reference to the attached drawings, in which:
FIG. 1 illustrates a conventional paper ticket for an event such as a concert or sports match;
FIG. 1 a . illustrates the existing technology in which an electronic ticket, or e-ticket, is received by a user at their computer;
FIG. 2 illustrates a conventional electronic ticket as is known in the art;
FIG. 3 illustrates an embodiment of the present invention in which the user, alongside the purchase of an electronic ticket, is given the option to receive a replica ticket;
FIG. 4 is a flow chart illustrating a process for purchasing a replica ticket in accordance with embodiments of the present invention;
FIG. 4A is a flow chart illustrating a process for offering, selling, providing, and authenticating a replica ticket in accordance with embodiments of the present invention;
FIG. 5 illustrates an embodiment of the present invention, including the process by which a ticket purchaser is prompted to purchase a replica ticket;
FIG. 6 illustrates the system used to provide for the exchange of data and facilitate the purchase of a replica ticket in accordance with one embodiment of the present invention;
FIG. 7 illustrates a replica ticket in accordance with one embodiment of the present invention;
FIG. 8 illustrates an embodiment of the present invention, in which a prospective replica ticket purchaser may authenticate a replica ticket using the system of the present invention; and
FIG. 9 illustrates an example concept view of a display screen for purchasing an e-ticket and a replica ticket in accordance with embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a conventional paper ticket 10 . Such tickets have been commonly used to facilitate a reservation for events such as concerts, plays and sports matches and are typically professionally printed (e.g., using card stock). Ticket 10 contains event information regularly included on such tickets, including event name 20 , event date 30 , event location 40 , and section, seat and row assignment 50 . In addition, many modern day tickets include a bar code 60 , which can be scanned by ushers at the event to guarantee authenticity. Such tickets typically include graphics (e.g., in color) such as logos or images (e.g., image of a stadium or the entertainer) and can include one or more authenticity protections (e.g., a bar code). Tickets such as these have largely been replaced by electronic tickets, or e-tickets.
FIG. 2 illustrates an existing system by which a ticket purchaser can obtain an electronic ticket. This method requires a computer 110 , or other similar device that can access the Internet, and software, such as an Internet browser 120 , that can be used to access the ticket vendor's website and make a purchase. The ticket purchase is confirmed by either providing an electronic ticket in the browser, or sending it to the ticket purchaser's e-mail address. After the ticket purchaser has received the ticket, they may print it out on printer 130 . This printout can be used to gain access to the event. In the alternative, the ticket purchaser may access their electronic ticket on a portable computer or smart phone, and present the electronic version to gain entry to the event.
FIG. 2 a illustrates an example of an electronic ticket 210 . The electronic ticket includes event information similar to conventional paper tickets, including the event name 220 , event date 230 , event location 240 , section, seat and row assignment 250 , as well as a bar code 260 to guarantee authenticity. Such electronic tickets have simplified the process for spectators and event attendees, alleviating the need to wait for tickets in the mail, or reserve tickets at will call. Rather, ticket purchasers can receive tickets and proof of purchase via e-mail and print them from their home computers. Due to the convenience of this method of ticketing, electronic tickets have largely replaced conventional paper tickets. As a result, event attendees have been robbed of the conventional paper ticket, which can serve as a valuable piece of memorabilia for a given event.
With reference now to FIG. 3 , a ticket purchaser can use a computer, or another device capable of accessing the Internet, to connect to the ticket vendor's website 310 . The ticket vendor can preferably be an online hub for purchasing tickets for a wide range of events and venues, such as “Stubhub.com.” The ticketing site can be an aggregator or reseller. The site can also be dedicated to one venue, team, type of event, or series of events. While purchasing an electronic ticket for the event, the website provides the option to purchase a replica ticket 320 . This option can come in a myriad of forms, including a webpage during the purchasing sequence, or a prompt to open a related webpage. The option can be displayed on the same page or display that a ticket for an event is offered for purchase. The option can be displayed after the user purchases an e-ticket. A feature can also be added that permits an e-ticket purchase a limited time period after the purchase of an e-ticket to purchaser a corresponding replica ticket. The feature may be offered at a fee to e-ticket purchasers (e.g., pay a small fee to have the right to buy the replica ticket after the event). Another feature can allow an e-ticket purchaser to buy the replica tickets that only corresponding to the purchased e-tickets (cannot buy replica tickets carrying seat or admittance specific information for e-tickets purchased by someone else). If the ticket purchaser chooses to purchase a replica ticket, they can then choose how to receive the replica. The replica can either be mailed to the ticket purchaser, or sent by electronic means such as e-mail. In one embodiment, the event coordinator eliminates the risk that replicas are used to gain entry to the event by ensuring that all replicas are mailed after the event has occurred. In the alternative, the replica can be e-mailed to the ticket purchaser, and printed on printer 330 .
FIG. 4 provides a flowchart detailing the system which facilitates the purchase of a replica ticket. At step 410 , the user goes online to purchase a ticket for an event. At step 420 , the user is given the choice of purchasing an electronic ticket. If the user purchases a conventional paper ticket, they are sent the ticket by mail, or it is left at will call. If the user purchases an electronic ticket, they are sent an electronic ticket by e-mail, and prompted to purchase a replica ticket 430 . This prompt can come by way of an on-screen advertisement, a click button, a pop-up window or any other manner that the opportunity to purchase a replica ticket may be brought to the ticket purchaser's attention. If the user chooses to purchase a replica ticket 440 , the system obtains the attributes for the replica ticket. This can be done by accessing a database 450 which contains necessary data fields and corresponding data (e.g., for each event, venue, team, league, entertainer, etc.). The database contains logos relevant to sporting events and performances, such as the logos for professional sports leagues, teams, bands, and venues. This information is collected through collaboration with various organizations. The system uses the event information such as event name, event date, and venue, to determine which attributes to pull from the database. For example, tickets to a New York Mets game may require the logos of Major League Baseball, the New York Mets, and their home stadium, CitiField. This type of event information can be determined either from the information entered during purchase of the electronic ticket, or by prompting the ticket purchaser to re-enter the information. The system then obtains payment from the ticket purchaser 460 , and determines whether the replica ticket is to be mailed, or e-mailed 470 .
Various implementations are contemplated. For example, with reference now to FIG. 4A , certain steps of a process are identified. The steps in this FIG. 4A (or as otherwise described) can be combined in a different order or steps can be removed or added in accordance with embodiments of the present invention. At step 412 , an interactive interface can be displayed that permits a user to buy an e-ticket for an event and replica ticket for the same event. The interactive interface may be provided by using a webpage or website. The interface may include an application such as an applet (e.g., an application on a mobile device). The interface can offer the user the opportunity to select to attend a list of events, which, for example, can be different types of events or venues. An interactive option can be displayed that would permit the user to purchase one or more tickets for rights to attend an event in person (e.g., a specific seat reservation). The interface may provide the user the option to purchase an e-ticket or a physical ticket. In response, to selecting to purchase an e-ticket, the interface may display to the user the option to buy a replica ticket in addition to the e-ticket. The option can be provided on the same page or screen as the option to buy an e-ticket for an event (e.g., simultaneously). Or some other relationship in time can be implemented if desired. The replica ticket option can also be presented at the same time as option to buy a ticket to an event is provided (e.g., as an element that can be added to a cart). Typically, the replica ticket would be the same ticket that the user would receive if the user chose to buy a physical ticket to attend the event (as opposed to the e-ticket). Therefore, the replica ticket would preferably be the same or would have the characteristics as if the user had purchased a physical ticket to attend the event. Buying both an e-ticket and a corresponding replica ticket would not provide the purchaser with two tickets to attend the event, but rather only one would be for receiving entry to the event (e.g., only the e-ticket). The replica ticket preferably would not have associated rights to permit the purchaser to use it to enter an event. In some embodiments, some variations can be made to the physical characteristics or material printed on the replica ticket for purposes such as authentication. In other words, a replica ticket does not have to be an exact duplicate of the physical ticket that could be purchased as opposed to an e-ticket. In response to being presented with the options or interface, the user can make selections that cause its computer or device to transmit messages that inform the ticket provider (e.g., seller, distributor, vendor, venue, ticket hub, etc.) of the user's selections.
At step 414 , in response to user selections, equipment of the ticket provider generates a message. The generated message provides instructions that the replica ticket be produced or delivered to the e-ticket purchaser. The message can be an internal message within a computer or network of the ticket provider or can be a message sent over a communication network of a replica ticket provider (e.g., a vendor of physical tickets). The provider equipment would be configured to be able to automatically generate these messages and send to many different replica ticket providers (dynamically) so as to be able to handle a wide array of replica tickets (e.g., venues, event types, geographic locations, etc.). If an internal message is generated, the message is used in conjunction with a database to automatically generate or produce the replica ticket. As such, step 414 can include the step of the ticket provider producing the replica ticket themselves based on stored attribute information (as opposed to relying on sending instructions to a third party).
At step 416 , the replica ticket or e-ticket can be delivered to a purchaser. The e-ticket and replica ticket can be delivered at different times. The replica ticket can be physically delivered by mail or electronically delivered, e.g., using the examples given herein. At step 418 , security measures printed on the replica ticket are used to verify the replica ticket or to verify authenticity of the replica ticket. Such a step can be part of making sure the replica ticket is not being used as an additional right to attend an event. Such steps can be taken after the user receives the replica ticket.
An event can be a live event involving attendance in person, but can also include other types of events such as those held electronically over the Internet.
If desired, the option to buy a replica ticket can be combined with another option such as the option to buy a replica ticket. For example, the system can automatically provide replica tickets with e-tickets. In such a case, only a single interactive option would be needed to offer the user the opportunity to buy an e-ticket and a replica ticket.
If desired, a replica ticket may include one or more pieces of ticket information common with an e-ticket that corresponds to that particular e-ticket. For example, information unique to that e-ticket can be included on the replica ticket.
A provided database can be used to pull information and used as part of the e-ticket and the replica ticket.
If desired, an interactive option can be displayed by the interface that permits the user to select to return to the website at a later date after purchasing the e-ticket to purchase the replica ticket. There may be a fee associated with selecting that option. If desired, this feature may also always be available and the user may be informed while on the site that they have a certain number of days to return to purchase the replica ticket.
FIG. 5 depicts a manner by which a ticket purchaser may be prompted to purchase a replica ticket. A ticket purchaser may visit a website to purchase an electronic ticket 510 . Upon completion of the purchase, there may be a prompt asking the ticket purchaser if they wish to purchase a replica ticket 520 . In one embodiment, this link may lead the purchaser to another webpage hosted by the ticket vendor, or a webpage hosted by a third party that produces replica tickets. In one embodiment, the same site that is selling the e-ticket can display an interactive option to purchase a replica ticket (e.g., on the same page, through the same interface). The option to have the right to buy the replica ticket can also be offered to be sold to others using an interactive option in connection with purchase of an e-ticket. The ticket purchaser may, for example, then be asked whether they wish to use the details of their recent purchase to obtain the attributes for their replica ticket, or whether they wish to re-enter the information 530 . Billing information can be taken, and the ticket purchaser can also be asked whether they wish to receive their replica ticket by mail or e-mail 540 .
FIG. 6 depicts the system used to provide replica tickets to the ticket purchaser. The Internet 610 provides the mode of communication for the system. The ticket purchaser 620 uses a computer 630 to access the Internet and to connect to a webpage 640 that connects to Ticket Vendor Server 650 . After completing the purchase of an electronic ticket, the ticket purchaser is prompted to connect to webpage 660 , which is connected to the Replica Ticket Vendor Server 670 . The Ticket Vendor Server and the Replica Ticket Vendor Server can communicate through the Internet or through a separate communications path. The replica ticket vendor and ticket vendor may be the same entity, in which case they may share a server. When the ticket purchaser chooses to purchase a replica ticket, the replica ticket vendor server must obtain the attributes necessary to draw the ticket from Ticket Attribute Database 680 . These attributes are compiled by Replica Ticket Vendor Server 670 . They are then printed on a ticket and mailed to the ticket purchaser, or e-mailed to the ticket purchaser. In addition, a Replica Ticket Authentication Database 690 can be accessed by the Replica Ticket Server 670 to authenticate replica tickets, as discussed below. If desired, in response to a user purchasing a replica ticket in connection with an e-ticket, a message or signal can be sent, e.g., over the Internet or other communications network, that instructs one of many different vendors (e.g., each for a different team, venue, league, etc.) to print the replica ticket, ship the replica ticket, or otherwise provide the replica ticket (in response to the message or signal).
FIG. 7 depicts an embodiment of the replica ticket 710 of the present invention. The replica ticket preferably contains all of the information regularly included on such tickets, including event name 720 , event date 730 , event location 740 , and section, seat and row assignment 750 . In one embodiment, the replica ticket includes all of the features and marks of the electronic tickets, or conventional paper tickets being issued for the same event. In one particular embodiment, the replica ticket may include a fake bar code 760 , or fake seat attributes, such that it cannot be used to gain access to the event.
In a particular embodiment, the bar code on the replica will be genuine, such that the ticket is identical to the conventional paper tickets issued for the event. In this case, the ticket purchaser may use either their electronic ticket or the replica to attend the event. If the purchaser chooses to include a genuine bar code on their replica, the website from which the replica was purchased will notify the event coordinators. The event coordinators can then use software to ensure that this bar code can be used a single time, and prevent both the electronic ticket and replica from being used for entry to the event.
FIG. 8 illustrates an embodiment in which the replica ticket is given a genuine and functional bar code. In such a case, the replica ticket 810 can receive an authentication number 820 . Since such a replica ticket may be resold, a potential purchaser will need a method by which to determine that the replica will provide event access. To accomplish this goal, all of the authentication numbers can be stored in a database by the event coordinator or ticket vendor. The potential purchaser can use a computer 830 , or any other device which can access the Internet, to query the database. Such a query could be conducted using a webpage, or similar tool, hosted by the event coordinator or ticket vendor. The query can tell the potential purchaser whether the replica will provide access to the event, and whether the replica should be purchased for this purpose. In addition, replicas which could provide access to an event could have more value as memorabilia than replicas which could not provide such access. Collectors of such memorabilia could query the database, using the described method, to determine whether the replica has such additional value.
FIG. 9 illustrates a display screen that can be displayed to a user. Display screen 902 can for example, be displayed on a user computer or mobile device. The screen can include information identifying live event 904 . It can also include buy option 906 using which the user can use to buy a ticket (e.g., an e-ticket) to the event. Option 908 for selecting a number of attending is also displayed. Add-replica ticket 910 can be displayed on the same page to provide the user with the option to purchase a replica ticket in conjunction with the buy a ticket to attend the event. Other replica ticket related options or features can be displayed on this screen or other related screens or pages.
A replica ticket object can be sent electronically to a purchaser. The object can be one or more images or it can be a combination of images and other software such as an executable app. The object can have the necessary characteristics to have a replica ticket printed by an e-ticket purchase (e.g., a consumer) at a level of quality or appearance that is similar, or at the same level, as if it was provided by a professional vendor. The object can be stored and used (e.g., printed) at some later time (e.g., definite or indefinite term). The object could also be given electronically to a retail vendor by the purchase to have the vendor generate the replica ticket.
Processes or steps described above can be implemented using equipment and networks also described above such as by implementing one or more processes on one or more computer readable medium that stores computer readable instructions for execution by a processing system that performs the process.
Several embodiments of the present invention are specifically illustrated and/or described herein. However, it will be appreciated that modifications and variations of the present invention are covered by the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention. | Methods and apparatus for issuing tickets for events are disclosed. In an embodiment, a method includes providing a ticket purchaser with both an electronic ticket and a duplicate replica ticket. The replica ticket provides the user a piece of memorabilia, without presenting the issue of having multiple tickets capable of being used for entry. In an additional embodiment, the replica ticket can also be used to gain access to the event. | 6 |
[0001] The present invention relates to a method and device for visualizing human or animal brain segments in order to aid a stimulation or manipulation of the brain.
BACKGROUND OF THE INVENTION
[0002] Functional connectivity analysis of resting-state fMRI data (fcrs-fMRI) of a human or animal brain has been shown to be a robust non-invasive method for localization of functional networks without using specific tasks, and to be promising for presurgical planning. Results of functional connectivity analysis of resting-state fMRI data is described in detail in the literature (Biswal B, Yetkin F Z, Haughton V M, Hyde J S (1995) “Functional connectivity in the motor cortex of resting human brain using echo-planar MRI”, Magn Reson Med 34:537-541; De Luca M, Beckmann C, De Stefano N, Matthews P, Smith S (2006) “fMRI resting state networks define distinct modes of long-distance interactions in the human brain”, NeuroImage 29:1359-1367; Di Martino A, Scheres A, Margulies D, Kelly A, Uddin L, Shehzad Z, Biswal B, Walters J, Castellanos F, Milham M (2008) “Functional Connectivity of Human Striatum: A Resting State fMRI Study”, Cereb. Cortex 18:2735-2747).
[0003] Many available data, such as the described resting-state fMRI data, have not yet been transferred to clinical everyday practice, nor made easily accessible to neurosurgeons. As such, visualization methods, visualization devices and stimulating or manipulating devices are needed that allow better access to the existing data.
OBJECTIVE OF THE PRESENT INVENTION
[0004] An objective of the present invention is to provide a method of visualizing at least one human or animal brain segment in order to aid a stimulation or manipulation of the brain.
[0005] A further objective of the present invention is to provide a visualization device for visualizing at least one human or animal brain segment in order to aid a stimulation or manipulation of the brain.
[0006] A further objective of the present invention is to provide a stimulating or manipulating device allowing a stimulation or manipulation of the brain.
BRIEF SUMMARY OF THE INVENTION
[0007] An embodiment of the invention relates to a method for visualizing at least one human or animal brain segment in order to aid a stimulation or manipulation of the brain, said method comprising the steps of:
predicting the localization of where a stimulation or manipulation effect is or would be, if and when initiated, and determining at least one target brain segment which is or would be stimulated or manipulated; evaluating whether at least one brain segment is functionally correlated to the at least one target brain segment; providing image data which visualize the at least one target brain segment, and/or at least one of the functionally correlated brain segments; and displaying the image data.
[0012] Preferably, a brain segment is treated as a functionally correlated brain segment if its brain activity currently shows or has previously shown an identical or at least a similar brain activity compared to the at least one target brain segment. For instance, a brain segment may be treated as a functionally correlated brain segment if its metabolic activity over time currently shows or has previously shown an identical or at least a similar metabolic activity over time compared to the at least one target brain segment.
[0013] According to a preferred embodiment, a brain segment is treated as a functionally correlated brain segment if its oxygen and/or glucose consumption over time currently shows or has previously shown an identical or at least a similar oxygen and/or glucose consumption over time compared to the at least one target brain segment.
[0014] Further, a correlation value may be calculated for each brain segment out of a predefined plurality of brain segments, wherein each correlation value describes the correlation between the brain activity of the respective brain segment and the brain activity of the target brain segment. The image data may visualize the functional correlation values of said plurality of brain segments.
[0015] The correlated brain segments may be determined using a three dimensional brain activity data set. The brain activity data set may describe the local brain activity for each location inside the brain and may have been generated for the brain currently or potentially stimulated or manipulated.
[0016] Preferably, the three dimensional brain activity data set comprises functional magnetic resonance imaging, fMRI, data provided by a functional magnetic resonance imaging, fMRI, device. The functional magnetic resonance imaging data may be task-based fMRI data and/or resting-state fMRI data.
[0017] The method may further comprise the steps of:
generating a first image showing the brain's anatomy or a portion thereof based on an anatomy image data set, generating a second image showing the at least one potentially stimulated or manipulated brain segment and/or at least one of the correlated brain segments, and superimposing or overlaying the first image and the second image and displaying the superimposed or overlaid images.
[0021] The anatomy image data set may comprise or consist of tomograms generated by a MRI tomography.
[0022] The at least one potentially stimulated or manipulated target brain segment and/or at least one of the correlated brain segments is preferably visualized in real-time during change of the localization of the device's stimulation or manipulation effect.
[0023] A further embodiment of the present invention relates to a visualization device capable of visualizing the current or future stimulating or manipulating of at least one human or animal target brain segment, said device comprising:
a first unit capable of predicting the localization of the device's stimulation or manipulation effect, and determining the at least one target brain segment being currently or potentially stimulated or manipulated; a second unit capable of evaluating whether at least one brain segment is functionally correlated to the at least one target brain segment, and a third unit adapted to provide image data which visualize the at least one target brain segment and/or at least one of the functionally correlated brain segments; and a display unit adapted to display the image data.
[0028] The second unit may be adapted to determine functionally correlated brain segments by using a three dimensional brain activity data set which describes the local brain activity for each location inside the brain and which has been generated for the brain currently stimulated or manipulated.
[0029] The three dimensional brain activity data set may have been generated based on data provided by a functional magnetic resonance imaging, fMRI, device.
[0030] The third unit may be adapted to generate a first image showing the at least one target brain segment and/or at least one of the functionally correlated brain segments which are identified by the second unit. The fourth unit may be adapted to generate a second image showing the brain's anatomy or a portion thereof based on an anatomy image data set, which visualizes the brain's anatomy. The fifth unit may be adapted to superimpose or overlay the first image and the second image to provide superimposed or overlaid images for visualization by the display.
[0031] The visualization device is preferably adapted to visualize the at least one target brain segment and/or at least one of the functionally correlated brain segments in real-time during change of the localization of the stimulation or manipulation effect.
[0032] The visualization device may comprise a processor and a memory, wherein the first, second, third, and fourth units may be software modules stored in the memory and being run by the processor.
[0033] A further embodiment of the present invention relates to a stimulating or manipulating device comprising a visualization device as described above and a stimulation and/or manipulation unit capable of stimulating and/or manipulating at least one human or animal brain segment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] In order that the manner in which the above-recited and other advantages of the invention are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended figures. Understanding that these figures depict only typical embodiments of the invention and are therefore not to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail by the use of the accompanying drawings in which
[0035] FIG. 1 shows an exemplary embodiment of a visualization device according to the present invention,
[0036] FIG. 2 shows an exemplary embodiment of a stimulating or manipulating device according to the present invention, and
[0037] FIG. 3 an example of two superimposed images shown by a display of the visualization device according to FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0038] The preferred embodiments of the present invention will be best understood by reference to the drawings, wherein identical or comparable parts are designated by the same reference signs throughout.
[0039] It will be readily understood that the present invention, as generally described herein, could vary in a wide range. Thus, the following more detailed description of the exemplary embodiments of the present invention, is not intended to limit the scope of the invention, as claimed, but is merely representative of presently preferred embodiments of the invention.
[0040] The outcome of neurosurgical interventions benefits from knowledge about the location of specific functional areas in the brain. For example, pre-surgical identification of circumscribed functional regions in relation to a tumor can be a substantial advantage in surgical planning. The gold-standard method for such functional localization, intraoperative electrical stimulation mapping, is invasive and limited to the localization of a few main cortical functional areas accessible during intracranial interventions. In contrast, a non-invasive imaging technique, “task-based” functional magnetic resonance imaging (fMRI), is capable of non-invasively showing the location of a diverse array of functional regions by using task paradigms to identify the implicated areas (Vlieger E, Majoie C B, Leenstra S, den Heeten G J (2004) “Functional magnetic resonance imaging for neurosurgical planning in neurooncology”, European Radiology 14:1143-1153).
[0041] Although seemingly of great promise for clinical application, task-based fMRI has seen limited integration into the technical repertoire of neurosurgical planning due to several practical constraints: special experimental setup, relatively long measuring time, high demand on patients for cooperation, and the substantial training and expertise required for processing the data. Furthermore, localization of each functional area using task-based fMRI requires a specialized task.
[0042] A novel technique in functional neuroimaging termed “resting-state fMRI”, in contrast to traditional task-based fMRI, measures changes in BOLD (Blood-oxygen-level dependence) signal without the patient being subjected to any task (i.e. spontaneous fluctuations). A formidable body of research in brain and neurological science over the past years has demonstrated the feasibility of using spontaneous fluctuations in fMRI data to map functional systems.
[0043] Various functional areas and networks throughout the entire brain can be mapped using a single resting-state fMRI scan: The basic underlying observation is that even in a task-independent state, the brain shows spontaneous fluctuations in fMRI activity which are far from random. The correlation between spontaneous fluctuations across different regions reflects areas that are functionally relevant to each other, and can be described as “functionally connected” (Fox M D, Raichle M E (2007) Spontaneous fluctuations in brain activity observed with functional magnetic resonance imaging. Nat Rev Neurosci 8:700-711). The resulting methodology is termed “functional connectivity analysis of resting-state fMRI” (fcrs-fMRI). The classic method for the analysis of functional connectivity may be based on taking the signal from a region-of-interest (ROI) and assessing its correlation with all other regions of the brain (termed: “seed-based” functional connectivity).
[0044] Exemplary embodiments of the invention as described hereinafter relate to a novel interactive visualization tool allowing the exploration of task-based and/or resting-state fMRI data (and/or other data) for neurosurgical use.
[0045] FIG. 1 shows an exemplary embodiment of a visualization device 10 according to the present invention. The visualization device 10 comprises a first unit 20 , second unit 30 , a third unit 40 , a fourth unit 50 , a fifth unit 60 , and a display unit 70 .
[0046] The visualization device 10 further comprises an interface 80 which allows to enter anatomy data ANA of an anatomy data set 90 , brain activity data BAD of a three dimensional brain activity data set 100 , and a target signal S.
[0047] The three dimensional brain activity data set 100 describes the local brain activity for each location inside the brain and is currently or has previously been generated. The three dimensional brain activity data set 100 is preferably generated based on data provided by a functional magnetic resonance imaging, fMRI, device. The three dimensional brain activity data are preferably resting-state functional MRI data.
[0048] The local brain activity data may indicate the metabolic activity of the brain segments. The metabolic activity of the brain segments may be determined by measuring the oxygen consumption and/or the blood oxygen saturation of the brain segments over time.
[0049] The anatomy data ANA of the anatomy data set 90 may comprise or consist of tomograms generated by MRI tomography.
[0050] The target signal S may be generated by an external stimulation and/or manipulation unit 110 , or by an external simulation unit 120 which simulates the functionality of an external stimulation and/or manipulation unit.
[0051] The visualization device 10 may operate as follows:
[0052] First, a target signal S is generated which defines three dimensional coordinates of a given location. The given location corresponds to a measured or estimated location of a stimulation and/or manipulation effect which is currently provided by the stimulation and/or manipulation unit 110 or which could be provided by the stimulation and/or manipulation unit 110 at a later stage.
[0053] The target signal S is entered via the interface 80 and reaches the first unit 20 . The first unit 20 may be a prediction unit which predicts the localization of the device's stimulation or manipulation effect in the human or animal brain, and determines at least one target brain segment which is or would be stimulated or manipulated if/when a stimulation or manipulation is or would be carried out at said given location defined by the target signal S. Said at least one brain segment is referred to as target volumetric element Vt hereinafter. The first unit 20 provides the target volumetric element Vt to the second unit 30 .
[0054] The second unit 30 may be a correlation unit which analyzes the brain activity data BAD of the three dimensional brain activity data set 100 with reference to the target volumetric element Vt. During this analysis, the second unit 30 evaluates whether brain segments are functionally correlated to the target brain segment, and determines all or at least a few of the functionally correlated brain segments that show identical or at least similar brain activity compared to the target volumetric element Vt. The related brain segments are referred to as correlated or related volumetric elements Vr hereinafter.
[0055] The second unit 30 provides the target volumetric element Vt and the correlated volumetric elements Vr to the third unit 40 .
[0056] The third unit 40 may be a first visualization unit which generates a first image I 1 showing the target and the correlated volumetric elements Vt and Vr.
[0057] The fourth unit 50 may be a second visualization unit which analyzes the target signal S and the anatomy data ANA of the anatomy data set 90 . As a result, the fourth unit 50 generates a second image I 2 showing the brain's anatomy or a portion thereof, including the target volumetric element Vt, based on the anatomy image data set 90 .
[0058] The first image I 1 and the second image I 2 are sent to the fifth unit 60 which is preferably formed by a superimposing unit.
[0059] The fifth unit 60 superimposes or overlays the first image I 1 and the second image I 2 , and provides a superimposed image I 1 +I 2 for visualization by the display 70 .
[0060] An example of two superimposed images I 1 +I 2 is shown in FIG. 3 . The anatomy of the brain is shown in two orthogonal cross sections. The targeted volumetric element Vt and the correlated volumetric elements Vr are indicated in an exemplary fashion.
[0061] The first, second, third and fourth units may be realized by software modules stored in a memory and being run by a processor.
[0062] FIG. 2 shows an exemplary embodiment of a stimulating or manipulating device 200 according to the present invention. The stimulating or manipulating device 200 comprises a visualization device 10 comprising a first unit 20 , a second unit 30 , a third unit 40 , a fourth unit 50 , a fifth unit 60 , and a display unit 70 . The visualization device 10 may be similar or identical to the visualization device 10 as described in detail above with reference to FIG. 1 .
[0063] The stimulating or manipulating device 200 further comprises a stimulation or manipulation unit 210 capable of stimulating or manipulating at least one human or animal brain segment. For stimulation and/or manipulation, the stimulation or manipulation unit 210 preferably generates a focused electrical or magnetical field inside the brain. To this end, the stimulation or manipulation unit 210 may comprise at least one magnetic coil, which may be placed outside the brain, to generate a magnetic field inside the brain. Additionally or alternatively, the stimulation or manipulation unit 210 may comprise at least one electrode, which may be placed inside or outside the brain, to generate an electric field inside the brain.
[0064] The stimulation or manipulation unit 210 further comprises a control unit 211 which allows a user to change the location of the stimulation or manipulation effect. The control unit 211 preferably generates a target signal S defining three dimensional coordinates of the location where the stimulation and/or manipulation effect is currently concentrated.
[0065] Moreover, the stimulating or manipulating device 200 may comprise an interface 220 for entering anatomy data ANA of an anatomy data set 90 , and brain activity data BAD of a three dimensional brain activity data set 100 .
[0066] The stimulating or manipulating device 200 may operate as follows:
[0067] During stimulation or manipulation, the visualization device 10 evaluates the target signal S of the stimulation or manipulation unit 210 , and predicts the current localization of the device's stimulation or manipulation effect in the human or animal brain. Then, it generates a superimposed image I 1 +I 2 for visualization by its display 70 . The superimposed image I 1 +I 2 shows the anatomy of the brain, the current targeted brain segment, and correlated brain segments that have identical or at least similar brain activity compared to the currently targeted brain segment. An example of two superimposed images I 1 and I 2 as displayed by display 70 is depicted in FIG. 3 .
[0068] The embodiments as described above with reference to FIGS. 1-3 may be implemented based on LIPSIA, a freely available MRI data processing suite. LIPSIA already implements certain precomputation steps, as well as the masking-out of voxels (volumetric elements) in order to optimize correlation computation. In order to implement real-time interaction a further restriction of correlation computation may be applied to only three visible slices present in the standard LIPSIA triplanar visualization. The combination of these approaches yields re-draw rates of approximately 0.1 seconds during a shift of the seed region-of-interest, which is sufficiently fast for fluent interaction.
[0069] AFNI recently introduced interactive functional connectivity visualization as part of its standard distribution. Using highly optimized computational methods, “InstaCorr” (afni.nimh.nih.gov/pub/dist/doc/misc/instacorr.pdf) achieves comparable speed of calculation while conducting correlation across the whole brain.
[0070] The embodiments as described above with reference to FIGS. 1-3 may integrate the process of seed selection and the visualization of correlation results. Instead of picking a seed point according to anatomical data, and then calculating the result, both may be done seemingly simultaneously.
[0071] Correlation of time-series from volumetric data using a seed region-of-interest (ideal time-series) is computationally a time consuming problem for real-time applications. For every voxel in the volume (approximately 200,000), the respective time-series (with approximately 200 time points) have to be correlated with the ideal time-series, typically requiring several hundreds of millions of operations. The following options, which reduce the number of real-time computations in various ways, can be employed to make display feasible at interactive frame rates (typically less than 0.1 seconds between successive frames):
1. Reduce the Resolution:
[0072] After interacting in real-time with lowered resolution, which is less computationally demanding due to fewer voxels, the chosen seed regions-of-interest can be reanalyzed at full-resolution. However, this option is the least advantageous due to loss of anatomical specificity.
[0000] 2. Restrict the Tissue Type for which Correlation has to be Computed:
[0073] A mask of voxels located within the brain reduces the computational demands tremendously. Excluding “non-grey matter” voxels from analysis may further accelerate the computation. For example, one could exclude white matter and ventricles using tissue segmentation, and limit data analysis only to grey matter, or one could only analyze a specific region-of-interest.
3. Restrict the Computation to the Visible Areas:
[0074] Rather than restrict tissue types, it is possible to only compute the information necessary for the current display (in our case, the three two-dimensional orthogonal slices in a standard tri-planar view).
4. Precomputation:
[0075] This approach does not reduce the number of required computations, but rather conducts them in advance. Correlation, as implemented in functional connectivity analysis, consists of two terms, one of which is independent from the ideal time-series. This term can be calculated and stored before interaction. With sufficient memory, it is also possible to completely precompute the correlation between every pair of voxels in the measured volume. Such a correlation matrix takes typically an hour to compute, and several Gigabytes of RAM.
[0076] The same precomputation could also be conducted for smaller regions of interest, reducing the required time and memory drastically.
[0077] For providing the images as described above with reference to FIGS. 1-3 , MR scanner systems may be used. The following parameters may be established to optimize the measurements results: On a GE 3-Tesla scanner equipped with an 8-channel head coil, fMRI may be acquired using a standard echo-planar imaging sequence (repetition time=2500 ms, echo time=30, flip angle=83°, voxel dimensions=1.71873×1.71873×4 mm). High resolution “anatomical” images may be obtained using a T1-weighted pulse sequence (MPRAGE, TR=7224 s; TE=3.1 ms; TI=900 ms; flip angle=8; 154 slices, FOV=240 mm). On a Siemens 3-Tesla Tim Trio scanner equipped with a 12-channel head coil, fMRI may be acquired using a standard echo-planar imaging sequence (repetition time=2300 ms, echo time=30, flip angle=90°, voxel dimensions=3×3×4 mm). Anatomical scans may be obtained using a T1 weighted pulse sequence (MPRAGE, TR=1900/2300 ms; TE=2.52/2.98 ms; TI=900 ms; flip angle=9; 192/176 slices, FOV=256 mm).
[0078] The data may be preprocessed using a combination of Free-surfer (http://surfer.nmr.mgh.harvard.edu/), AFNI (http://afni.nimh.nih.gov/), and FSL (http://www.fmrib.ox.ac.uk/fsl/), all freely available standard data analysis packages. Preprocessing for the functional data, which has been described previously may include: slice-timing correction for interleaved slice acquisition and motion correction in six degrees-of-freedom (AFNI). The six motion components and a “global” signal (extracted from the average signal over the entire brain) may be used as covariates in a general linear model. The residual data may then be bandpass filtered between 0.02-0.08 Hz and spatially smoothed using a 6 mm full-width half-maximum Gaussian kernel (AFNI).
[0079] Typically, the functional measurements consist of isotropic samplings on a voxel grid with 3-4 mm voxel size, using a standard BOLD-sensitive EPI sequence for rapid volumetric coverage of the whole brain (typ. 17×14×10 cm field of view). The measurements are sensitive to changes in blood oxygenation, and typically a complete volume is acquired every 1-4 seconds. Recent advances have made resolutions in the sub-millimeter range and much shorter acquisition times with multiple volumes per second possible. Further improvements can be expected. It is also possible to increase spatial and temporal resolution by restricting the sampling to a sub-region of the brain. Therefore, achievable resolution ranges from a few millimeters down to 0.1 mm and even lower, depending on sampling and other parameters. Other modalities like Positron Emission Tomography (PET), Magnetoencephalography (MEG), and Electroencephalography (EEG) may result in similar functional datasets of localized changes in brain function over time. While using single voxels as seed-regions of interest is possible, typically collections of neighboring voxels are taken into account in order to increase the signal to noise ratio, e.g. spherical regions with a 5 mm radius, or a neighborhood of voxels with similar radius along the cortical gray matter after a segmentation of the different tissue types.
[0080] The anatomical volume may be skull stripped using the standard Freesurfer processing path. A single functional volume may then be registered to the skull-stripped anatomical volume using FSL's linear registration tool, and the resulting transformation matrix may be applied to the entire functional data set.
[0081] To detect the sensorimotor network, a mouse cursor, which defines the location of the stimulation or manipulation effect and thus decides about the targeted voxel, may be placed on the lateral motor cortex, anterior to the central sulcus, and the region of interest shifted until a symmetrical network appeared across pre- and post-central gyri, as well as supplementary motor area. For the language network, the mouse cursor may be placed in the left inferior frontal gyrus, adjacent to the precentral sulcus, which corresponds to Broca's area (anterior operculum). By shifting the location slightly, it is possible to detect functional connectivity in the sagittal plane to the posterior portion of the superior temporal gyrus (Wernicke's area) and adjacent inferior parietal cortex. For the dorsal-attention network, the cursor may be placed in the superior frontal gyrus and shifted until functional connectivity in the axial slice is visible bilaterally in both frontal regions and the intraparietal sulcus. The default-mode network may be identified with the cursor placed in the posterior cingulate. Functional connectivity from this region is visible in the medial prefrontal cortex along the sagittal plane, as well as bilateral inferior parietal cortex visible in the coronal plane.
[0082] Using the procedure described above, an experienced fcrs-fMRI researcher needed less than two minutes to identify the described four networks per case, less than 30 seconds on average per network.
[0083] Summarizing, the embodiments of the present invention as described above with respect to FIGS. 1-3 , enable the analysis and visualization of functional connectivity using “resting-state fMRI” data at a speed that allows for real-time exploration of regions of interest.
REFERENCE SIGNS
[0000]
10 visualization device
20 first unit
30 second unit
40 third unit
50 fourth unit
60 fifth unit
70 display unit
80 interface
90 anatomy data set
100 brain activity data set
110 external stimulation and/or manipulation unit
120 simulation unit
200 stimulating or manipulating device
210 stimulation or manipulation unit
211 control unit
220 interface
ANA anatomy data
BAD brain activity data
I 1 first image
I 2 second image
S target signal
Vr related volumetric element
Vt target volumetric element | An embodiment of the present invention relates to a method for visualizing at least one human or animal brain segment in order to aid a stimulation or manipulation of the brain, said method comprising the steps of:
(a) predicting the localization of where a stimulation or manipulation effect is or would be, if and when initiated, and determining at least one target brain segment which is or would be stimulated or manipulated; (b) evaluating whether at least one brain segment is functionally correlated to said at least one target brain segment; (c) providing image data which visualize the at least one target brain segment and/or at least one of the correlated brain segments as evaluated in step (b); and (d) displaying the image data. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of U.S. patent application Ser. No. 11/823,214 filed Jun. 27, 2007.
FIELD
[0002] The present invention relates to MEMS memory devices, and more particularly, to seek-scan-probe memory storage devices.
BACKGROUND
[0003] FIG. 1 illustrates a prior art, conventional MEMS (Micro-Electro-Mechanical System) seek-scan-probe (SSP) memory device, where various components are labeled by their typical names. For simplicity, only two cantilevers are shown in FIG. 1 , but in practice there is an array of cantilevers. The storage media comprises a Chalcogenide. However, other media may be used for storage, such as ferroelectric material. Electrical energy (heat) converts a Chalcogenide between its crystalline (conductive) and amorphous (resistive) phases, so that information may be stored, and read by sensing current through the storage media. The cantilever array is on a stage mover. The cantilever array may be moved laterally so that a data bit may be stored or read spatially. Each cantilever covers a specific region of the storage media to perform read, write, and erase operations over the specific region.
[0004] To perform a read, write, or erase operation, the tip of the active cantilever needs to contact the storage media so that current can flow between the tip and the media electrode underneath the storage media for resistance sensing (read operation) or electrical current passing (write and erase operations). The read, write, or erase action is performed with a pulse voltage, e.g., ground to 8 volts, applied on the media electrode with a typical duration of about 20 nano-seconds (ns). The cantilever mechanical response is insensitive to such a fast electrical pulse. The tip contact with the storage media is mainly achieved by the cantilever's bending from internal stress.
[0005] Due to process variation on the wafer, the stress-induced bending may vary significantly from cantilever to cantilever, resulting in situations in which some cantilevers are in contact with the storage media while some have inadequate bending to reach the storage media surface. In order to make sure that all cantilevers are contacting the storage media, the gap between the mover and storage media surface is usually reduced to obtain adequate contact force on the least-bent cantilevers. However, this may damage the cantilever tips.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 illustrates a prior art scan-seek-probe memory device.
[0007] FIG. 2 illustrates a scan-seek-probe memory device according to an embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0008] In the description that follows, the scope of the term “some embodiments” is not to be so limited as to mean more than one embodiment, but rather, the scope may include one embodiment, more than one embodiment, or perhaps all embodiments.
[0009] FIG. 2 illustrates in simplified form a side-view of an embodiment. For simplicity, only two cantilevers are shown, but in practice an array of cantilevers are used to store, read, and erase bits on the storage media. Each cantilever is sandwiched by two actuation electrodes, a media electrode and another electrode on the mover, which is referred to as a pull electrode in FIG. 2 . Each media electrode and its corresponding pull electrode are separated by an air gap. A pull electrode is located at the backside of its corresponding cantilever, and allows the cantilever to be actuated upwards. The media electrode serves as the front actuation electrode of its corresponding cantilever to increase contact force with the storage media. For some embodiments, when the electrodes are powered off (no actuation), the cantilevers contact the storage media with forces ranging from about 0 to 25 nN.
[0010] For some embodiments, the cantilevers comprise a relatively compliant beam to allow acceptable force variation caused by process variation. For example, for a cantilever beam of compliance (spring constant) k=0.05N and for a variation in the vertical dimension of Δz=0.5 μm, the force variation is ΔF=kΔz=25 nN. For such embodiments, this relatively small force range is not expected to damage the cantilever tips after a wafer is bonded.
[0011] When powered up, the cantilevers are actuated into two groups: a non-active group and an active group. Cantilevers in the non-active group do not perform R/W/E (Read/Write/Erase) actions. The cantilevers in the active group have their tips in contact with the storage media for data access. For a non-active cantilever, a high voltage may be applied on the pull electrode. For example, for some embodiments a voltage of 30V may be applied on the pull electrode, resulting in a pulling force of between 0.1 to 0.2 μN for an assumed gap of 4 μm to 5 μm. For such embodiments, the force is expected to move the tip of a cantilever upwards by 0.5 μm to 2 μm, slightly above the storage media surface, and the applied voltage is expected to produce an electrostatic force in balance with the cantilever spring, but not so large as to cause pull-in of the cantilever onto the pull electrode. In this way, the cantilever is suspended between the over and media wafer. Because the tips are only slightly above the storage media, the non-active cantilevers may be made active and contact the storage media surface when the pull voltage is removed.
[0012] For active cantilevers, no voltage need be applied on the pull electrode. For some embodiments, the active cantilevers contact the storage media surface with a force in the range of 0 nN to 25 nN, depending on the initial bending due to process variation. For cantilevers with close to zero spring contact force, an additional actuation may be used to boost the contact force. For example, a low voltage may be applied on the media electrode to produce an additional attracting force between the cantilever tip and the storage media. For example, for a 0.3 μm tip height, an electrostatic force of about 50 nN to 100 nN may be produced by applying 2V on the media electrode. This low voltage on the media electrode is essentially invisible to the phase change storage media, which usually requires a voltage larger than 7V to cause a phase change. Typically, the storage media has a very high resistance, in the neighborhood of 100 kΩ between the tip and media electrode, so that a low actuation voltage may be maintained if needed.
[0013] The total contact force is the sum of the spring force and electrostatic force from the media electrode. By adjusting the voltage on the media electrode, the tip contact force may be modulated, for example, from 25 nN to more than 100 nN. The R/W/E action with a short electrical pulse (V s >7V and less than 100 ns in duration) may be performed when the desired contact force is achieved. The very short pulse from the R/W/E action should have minimum effect on the cantilever. When a cantilever completes a data access, the media electrode voltage is removed and a high voltage is applied on the pull electrode to open the cantilevers, that is, pull the tip upwards so that the cantilever is in a non-active mode.
[0014] Because only the active cantilevers are contacting with the storage media during data access, it is expected that tip and storage media wear should be reduced for the non-active cantilevers. It is also expected that this may improve reliability and lifetime of the device.
[0015] Various modifications may be made to the described embodiments without departing from the scope of the invention as claimed below. For example, the spring constant need not be uniform throughout a cantilever. For example, some embodiments may have cantilevers such that over their length closest to the mover, the spring constant is higher than for a portion of their length closest to the storage media. | A seek-scan-probe memory device, utilizing a media electrode to allow active cantilevers to contact the storage media, and a pull electrode to pull up cantilevers away from the storage media when in an inactive mode. Other embodiments are described and claimed. | 6 |
This is a continuation of application Ser. No. 575,773, filed May 9, 1975, now abandoned.
BACKGROUND
Rubber linings in abrasive-material handling equipment such as centrifugal pumps for dredging sand, mud and for pumping slurry are old. The use of such liners is normally for purpose of economy and to enable quick replacement when worn beyond a certain point. Formerly, either no liners were used for dredging or pumping the foregoing materials or cast alloy iron or steel liners were used. Rubber was found to be much more economical, when pumping clean, abrasive sand. However, where the material being pumped or dredged included sharp rocks, broken glass, tin cans, pieces of metal and other sharp hard particles found in trash as may accumulate in the beds of canals, rivers, harbors and other bodies of water, the use of rubber wear components in the centrifugal dredges has been found to be valueless, because the sharp objects remove large pieces of the rubber.
Also, heretofore, rubber liners have been used as impact receiving wear components in hoppers, chutes, and the like to resist the wear due to rocks and the like that are handled, but such liners are not used where the angle of impact is less than forty degrees and the rate of movement of the material thereover is greater than twenty feet per second, due to greatly accelerated wear where these limits are exceeded. Such liners are specially formed to present surfaces having angles of impact as close to ninety degrees as possible to enable the resiliency of the relatively soft rubber to absorb much of the shock free from the shearing effect of a low angle of impact.
Liners in centrifugal dredge and slurry pumps have heretofore been manufactured to provide continuous volute portions circumferentially around the impeller, and continuous door or side walls, although they and the casing may be split in the plane of the volute for insertion and removal of the liners. In either instance the wear is not uniform but occurs in different areas. To extend the life of the costly metal liners, an expensive and time consuming expedient is adopted for building up the worn areas with welding, and applying hard faced welding surfaces. Otherwise the liners are replaced, although extensive areas of the wear surfaces show little wear.
The side or door liners show wear in many instances between the runner-shrouds or discs and the liners adjacent thereto due to movement of the water and abrasive material from the volute portion across the faces of said liners and the inlet under the influence of the high pressure differential between said portion and the inlet portion, the pressure at the latter being negative. This wear across the liners progressively reduces the efficiency of the pump as the wear increases, with a resultant rise in the operation costs. Here again, in the case of the metal liners, resort is made to building up the worn areas with welding.
In the liners hereinafter shown and described, each comprises a layer of rubber or rubber-like material in which the wear surface is smooth. When used hereafter in this application, the term "rubber" shall mean any natural or synthetic, resilient, rubber-like material. Embedded in the rubber layer is one or more sheets of high carbon steel wire mesh material or other tough, abrasive resistant mesh, the wire of which is substantially inseparably bonded or vulcanized to the rubber. This sheet, or sheets where more than one is used, is or are parallel with said wear surface, and in the latter instance the sheets are spaced apart.
The size of the wire and the mesh openings are such as to resist breakage from the impact and abrasion of the materials being dredged, such as hard rocks, broken glass including glass bottles, tin cans, wire, pieces of metal etc. The wire defining the mesh openings protects the rubber therein and prevents the deepening of any areas worn to the sheet and also checks the expansion of such areas. Thus, the mesh sheets provide abrasion resistant wear surfaces.
Where the liners are in hoppers, chutes and the like that take the impact of rocks, aggregate and the like, fed thereto and over which such material is moved, the liners are not necessarily in sections in each installation, and they usually are fairly accessible for installation, removal and replacement. The wear surfaces are smooth thereby offering no unusual resistance to fast movement of the materials thereover, and the angle of impact may be thirty degrees and less to expedite such movement. The liners are of rubber, have the wire mesh sheet or sheets embedded therein and bonded thereto, to provide a lining material having the long wear characteristic of hard alloy metals but at a fraction of the cost.
SUMMARY OF THE INVENTION
One of the objects of the invention is the provision of improved rubber liners for use in abrasive handling equipment in positions to receive the impact and wear from the abrasive material handled and the initial and operating costs of which are a small fraction of the initial and operating costs of conventional hard high alloy steel liners in the same positions in the same equipment handling the same materials under the same conditions.
Another object of the invention is the provision of rubber linings in and for centrifugal dredge and slurry pumps in sections that are selectively removable and replaceable in different areas within the pumps subject to wear from impact with and movement of the abrasive material through the pumps.
Another object of the invention is the provision of a rubber liner in a conventional centrifugal dredge or slurry pump having the long wear characteristics of hard, high alloy steel.
A still further object of the invention is the provision of rubber liners for use in conventional abrasive handling equipment providing wear surfaces therein in engagement with the abrasive material handled by said equipment, and which liners have the long wearing characteristics of conventional hard alloy steels and are suitable for use in handling such materials as hard sharp rocks, broken glass, metal pieces, tin cans, wire and the like.
Other objects and advantages will appear in the drawings and description.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is side elevational view of a liner for a centrifugal type dredge pump, a portion of the outer case being shown in elevation.
FIG. 2 is an enlarged, fragmentary view along line 2--2 of FIG. 1.
FIG. 3 is an enlarged view of one of the liner sections of the volute portions thereof.
FIG. 4 is an enlarged fragmentary cross sectional view through a portion of the liner showing the wire cloth or wire mesh material therein.
FIG. 5 is a side elevational view of a portion of a bladder type liner separate from the outer case.
FIG. 6 is an elevational view of the liner portion of FIG. 5 as seen from the discharge side.
FIG. 7 is an enlarged cross sectional view along line 7--7 of FIG. 6 in which part of the conventional outer case is shown in broken line, except at the liner-attaching bolt, which is in section.
FIG. 8 is a semi-diagrammatic sectional view showing the impact receiving liners in a chute, hopper and conduit.
DETAILED DESCRIPTION
One conventional form of pump housing, generally designated 1, includes a weldment comprising a side 3 (FIG. 2) rigid with a volute shaped periphery 4. A door 5 is removably secured by bolts (not shown) to the weldment in opposed relation to side 3. A central opening 6 (FIG. 1) in said door is for a suction pipe, and an opening in the side 3 coaxial with opening 6 is for the impeller shaft. This structure is old.
The side liner, generally designated 7 extends across the inner surface of side 3, while the volute portion of the liner is formed in sections 8 to 13, the sections 8, 13 defining two of the opposite sides of the outlet. In addition, a nose section 14 is at the acute juncture between sections 12, 13 (FIG. 1). While sections 8, 13 are straight extensions of the volute, they will be called volute sections. A door liner 7' extends across the inner surface of the door 5.
The side and door liner and the volute liners extend completely over the internal surfaces of the pump housing.
Each of the volute sections of the liner comprises a backing plate 15 and a wear liner 16, the latter facing the impeller chamber. The wear liner and backing plate of each section are correspondingly curved, except sections 8, 13 which are straight, and their concavely curved sides face radially inwardly toward the axis of the impeller which is coaxial with opening 6.
The wear liner 16 of each volute section, is of rubber, and is vulcanized to its backing plate. Nuts 17 on stud bolts 18, that, in turn are secured to the backing plate of each volute section, secure the liners rigidly in their positions within the housing 1. Said bolts 18 extend from the backing plates through the volute portion of the housing for releasably holding the sections against spacers 19 that are along the volute periphery 4.
The side liner 7 and the door liner 7' are respectively secured to the side and door by bolts and nuts corresponding to bolts 18 and nuts 1 as indicated in FIG. 1 by the same numbers.
The wear liners 16 in each volute section in a dredge pump, as illustrated, having a 24 × 24 inch outlet, are of uniform thickness of approximately two inches, while the side and door wear liners are a quarter of an inch less in thickness. These wear liners are of rubber in which several sheets or layers 23, 24, 25 of high carbon steel industrial wire cloth of 0.105 inches diameter and with 1/4 inch openings are embedded in the rubber before vulcanizing, said layers being parallel with the wearing surface of each liner. The sheet or layer 23 may be 3/8 inch from said surface, with the sheet 24 spaced 1/2 inch from sheet 23 and from inner layer 25. The layer of rubber 16 is vulcanized after the steel wire mesh or wire cloth is embedded therein and the backing plate is against the back of layer 16, whereby the wire cloth and the backing plate 15 are substantially inseparably bonded to the rubber. The rubber is preferably cured to approximately 60 Shore durometer hardness, and the same procedure is followed with respect to the door and side liners, both of which may be called side liners.
The adjacent ends of the adjacent pairs of volute sections are complementarily bevelled to engage each other when the volute sections are bolted to the volute portion of the outer case, and the inclination of the bevels at opposite ends of each section are in the same direction so that any one of the volute sections may be removed and replaced independently of the others.
The structure enabling the selective removal and replacement of the volute portions of the liner is important because the wear on the liners is not uniform around the volute. Certain sections may wear thin while others show little wear. Also the selective replacement of sections enables lining the pump with the best combination of lining material for the particular job undertaken.
As an alternative to the form of pump liner arrangement shown in FIGS. 1, 2 and 3, the invention may take the form of a bladder type rubber liner, an embodiment of which is illustrated in FIGS. 5-7.
Conventional bladder type liners have taken the form of unitary cast alloy iron or steel liners, and also rubber liners that may or may not be split in one or more planes of the volute.
In the present instance the rubber liner used to line a bladder pump is generally designated 28, and is divided into segments along lines 29 (FIG. 5) that extend radially relative to the axis of the impeller (not shown), but which is coaxial with the rings 30. Each segment includes a portion of the volute 31 and side walls 32 (FIG. 7).
The outlet portion 33 of the liner is preferably divided into portions 34, 35 along line 36 (FIG. 5), and the segment 38 that adjoins one of the ends of sections 34, 35 has parallel end edges 39, whereby said segment 38 provides the key segment that may be removed to free any of the others for replacement. Each of the segments, being of U-shape cross sectional contour has a U-shaped backing plate 40 with the rubber wear liner on the inside and vulcanized thereto, and each liner has U-shaped sheets 42 of high carbon industrial wire cloth embedded in the rubber 41 of the liner in parallel spaced relation to each other and to the inner wear surface of each segment thereby providing liners having the same wear characteristics as the liners in FIGS. 1-4. Bolts 43 (FIG. 7) are adapted to releasably secure the segments within the pump housing shown in phantom as 26 in the same manner as bolts 18.
Most bladder type pumps incorporate side wall or door liners that are bolted to the associated wall or door, and the liner of this invention can be configured to serve as side wall and door liners in the bladder type pump.
While the foregoing structures are preferable, the rubber liner is not to be limited to any particular type of pump case. Also while natural rubber has been found to be preferable in combination with the wire cloth to which it is bonded, it is to be understood that any rubber-like material exhibiting the characteristics of natural rubber with respect to resistance to wear and adherence to metal, may be utilized.
Referring to FIG. 8, the abrasive material handling equipment comprises a hopper 50, a feed chute 51 feeding abrasive material such as rocks or aggregate 52 into the hopper, and a second feed chute 53 feeding similar material into a vertically extending conduit 54 having an angularly downwardly extending extension at its lower end. Liner 55 in chute 51; liner 56 in hopper 50; liner 57 in chute 53 and liner 58 at the lower end of conduit at the juncture between the extension 59 and the vertical portion of the conduit are each of the same rubber and wire mesh structure as the layer 16 in that each contains at least one sheet of the wire mesh material.
FIG. 8 is intended to be illustrative of several different places where the liner is adapted to be used. The angles at which the wear liners positioned relative to horizontal are such as to promote a relatively high velocity of the sharp rocks, etc., thereover, both conditions being considered as detrimental to the lining material whether of metal or rubber, and particularly as to rubber.
In actual use in dredging operations, or in abrasive-material handling apparatus, a sharp object such as a sharp rock, a broken bottle or a piece of iron and the like may mutilate the wear surface of the liner to some extent, but the mutilation will stop at the steel mesh and the rubber will not strip away from the sheet. Ultimately the rubber will be worn to the wire cloth in different places but the wear will not continue to the rubber beyond the wire mesh until the latter is worn through. The wire of the mesh protects the rubber within the mesh openings and the rubber within the openings protects the wire.
Due to the greater wear that occurs in certain areas of the liners, only those that are worn through need be replaced, hence many of the sections will remain unchanged thereby further contributing to the extremely low cost per yard of material dredged or handled. | Wear liners in abrasive material handling apparatus or equipment in positions to receive the impact and scouring by hard materials such as sharp rocks, broken glass, tin cans, metal pieces and other hard particles at all impact angles including acute angles and at high velocities. Such liners comprise a layer of vulcanized rubber or equivalent material having an impact receiving surface that is smooth and continuous, with one or more sheets of abrasive resistant wire mesh embedded in said layer parallel with and spaced below said surface, and with said sheets, when more than one, spaced from each other and parallel. The rubber or rubber-like material is substantially inseparably vulcanized or bonded to the wires of said sheet or sheets and is of approximately 60 Shore durometer hardness. | 1 |
RELATED APPLICATION
This application is a continuation-in-part of my prior U.S. Patent Application Ser. No. 6-182224, filed Aug. 28, 1980 and assigned to the same assignee as the instant application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates generally to cutting element, or insert, retention or clamping arrangements. More specifically, the invention pertains to apparatus for locating and clamping each of a plurality of metal cutting inserts in a slotting cutter.
2. Description of the Prior Art
For machining slots ov various widths in workpieces, prior art cutters are known having a disk-like body with disposable cutting inserts protruding radially from the disc periphery. For efficient machining, such inserts must be solidly and accurately supported. This requirement has heretofore led to use of relatively bulky insert wedging elements, or inserts of relatively complex shape, along with a minimum cutter body width capable of supporting the prior art insert mounting arrangements. This minimum cutter body width, in turn, defines the minimum width slot capable of being formed by such rotating slotting cutters. For slots narrower than such minimum, integral high speed steel saw blades or cutters utilizing brazed cutting tips had to be used.
Examples of pertinent prior art cutters of the type described are shown in U.S. pat. Nos. 867,275-Hunter, 1,618,782-Rottler, 1,700,333-Pond, 3,590,893-Burkiewicz, and 3,887,975-Sorice et al.
The Hunter, Rottler, and Burkiewicz disclosures teach insert clamping via flexible portions of the cutter body. Such flexibility is allegedly obtained by providing additional saw cuts or slit-like apertures in the body positioned between cutting blade pockets.
The Pond and Sorice et al. patents set forth arrangements utilizing camming members which bear against appropriately shaped portions of the cutting inserts to achieve clamping. In such arrangements, the cutting forces exerted on the insert are transmitted directly onto the cam surfaces, which can lead to damaging cam wear. This condition also necessitates a greater body thickness surrounding the camming member. An additional disadvantage of such an approach arises from the necessity of fashioning inserts with the requisite complicated surfaces which must cooperate with the camming member.
In my above-identified prior application, relatively narrow cut-off and grooving inserts are retained in a narrow insert support blade in a novel manner. By further investigation of the approach disclosed in the prior application, I have discovered a novel approach to insert retention in a rotating slotting cutter having a body width which may be as narrow as the support blades used with cut-off inserts in single point, non-rotating cut-off and grooving tools.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide insert retention in a slotting cutter enabling positive location and rigid clamping of each insert in cutter bodies that may virtually be as narrow as a conventional cut-off or grooving tool insert cutting edge while avoiding the above deficiencies of prior art slotting cutter designs.
In accordance with such an object, a slotting cutter includes a plurality of disposable cutting inserts placed in a corresponding plurality of pockets circumferentially spaced about the periphery of the disc-shaped cutter body, each insert having cutting edges of length substantially equal to the width of the desired slot to be cut. In addition to a portion of an insert, each pocket houses a flexible, substantially planar clamping element lying within the plane of cutter body rotation. Adjacent to each pocket is disposed actuating means rotatable in the plane of cutter body rotation, positioned such that, upon rotative movement thereof, the actuating means causes the clamping element to secure the insert in operative cutting position.
DRAWING
The objects and features of the invention will become apparent from a reading of a detailed description of an embodiment of the invention taken in conjunction with the drawing in which:
FIG. 1 is a plan view taken along the axis of rotation of a slotting cutter arranged in accordance with the principles of the invention;
FIG. 2 is a view of the cutter of FIG. 1 taken normal to the axis of rotation of the cutter body;
FIG. 3 is a more detailed view of the insert retention or clamping apparatus utilized in each insert retention pocket of the cutter of FIG. 1; and
FIG. 4 is an axial view of a camming member utilized in conjunction with the inssert retention apparatus depicted in the cutter of FIG. 1.
DETAILED DESCRIPTION
With reference to FIGS. 1-4 of the drawing, the same reference numerals are used for the same component or portion of the apparatus depicted in the various figures.
Referring to FIGS. 1 and 2, a slotting cutter capable of using cut-off and grooving tool inserts is set forth. One such insert that may be used with the disclosed embodiment is described in more detail in the above referenced prior application Serial Number 6-182224, which is hereby incorporated by reference. As seen from FIGS. 1 and 2, each insert 500 has a cutting edge 501 extending substantially parallel to the cutter body axis of rotation for a distance at least as wide as the width of the cutter body.
Slotting cutter 100 comprises a disc-shaped body portion of relatively narrow axial thickness defined by first and second lateral surfaces 101. The outer disc-shaped portion terminates centrally of the body in an enlarged hub region 110, in which is placed an axially centered bore 120 for receipt of a support shaft of a driving machine spindle (not shown). Rotative motion is imparted to the cutter via a drive key (also not shown) which mates with drive keyway 130.
Peripherally spaced at substantially equal angular positions about the cutter body are substantially rectangular recesses, or clamp and insert receiving pockets, 140, each having substantially parallel top and bottom surfaces, 143 and 142, respectively, joined by a rear surface 141, and opening radially outwardly for mating receipt of an insert 500. The radially outermost portion of each pocket is partially terminated by a lip portion 190 of cutter body material. Each surface 41, 42, 43 extends axially from one lateral surface 101 to the other. A portion 180 of bottom surface 142 of each pocket is generally V-shaped to conform to the bottom surface of each insert 500.
Referring to FIG. 1 in conjunction with FIG. 3, in addition to housing an insert 500, each pocket 140 additionally contains a substantially planar insert retention or clamping blade 300, having a rear surface 332 abutting the rear pocket surface 141, a top surface 308 abutting the top pocket surface 143, a clamping surface 305 in overhanging engagement with a portion of a top surface of an insert 500, a bottom surface 331 abutting a portion of bottom pocket surface 142 radially inward from insert 500, and an insert positioning surface 304 for providing a positive stop for a corresponding rear surface of insert 500. As shown, each blade 300 lies in the plane of cutter body rotation between lateral surfaces 101.
Each retention element 300 further includes an aperture in the form of a sawcut or slit 302 extending from an opening at the juncture of surfaces 304 and 305 and extending radially inwardly (when viewed as mounted in a cutter body pocket) towards rear surface 332 and terminating, for example, at an undercut 306. To assist in achieving proper insert seating location, undercut 307 is provided at surface 308. Sawcut 302 is positioned such that a moveable clamping portion 301 of blade 300 is provided, capable of flexing movement about blade portion 330. In a preferred form, sawcut 302 forms a relatively small angle 320 with the surface 308, on the order of, for example, eight degrees.
Bottom surface 331 is additionally provided with substantially semicircular tack hole or depression 303 at a position where blade 300 is to be tack-welded to cutter body 100. This tack weld is shown at 170 of FIG. 1.
Referring now to FIGS. 1 and 4, mounted adjacent to each top pocket surface 143 in a mating cavity 150 is a clamp actuator or camming member 400, rotatable in its mating cavity about an axis substantially parallel to the axis of cutter body rotation and having a plane of rotation identical to the cutter body plane of rotation. As seen from FIG. 4, each camming member 400 has a circular peripheral portion 402 subtended in a cord-like fashion by flattened peripheral portion 401. Additionally, each member 400 is provided on at least one lateral face with a hexagonal socket 403 for engagement with a standard hexagonal wrench for imparting rotational movement to the camming member. Each camming member is substantially permanently mounted in its respective cavity 150 by peening the lateral surfaces 101 of the cutter body around theperiphery of cavity 150.
As shown in FIG. 1, each projecting cutting insert 500 is preceded in a direction of cutter body rotation by a suitably shaped chip gullet 160.
In a non-clamping condition, camming member 400 has its flattened portion 401 positioned in cavity 150 such that portion 401 is parallel and coextensive to top pocket surface 143. Under this condition, an insert 500 can be slideably inserted or removed at the pocket opening. On insertion, the insert slides back until a rear insert surface abuts insert locating surface 304 of blade 300 to positively position the radial extent of insert cutting edge 501. Upon rotation in either direction of camming member 400 in the cutter body plane of rotation, camming member surface 402 will urge moveable clamping portion 301 of blade 300 in a direction tending to clamp insert 500 between blade clamping surface 305 and bottom pocket surface portion 180.
Hence each insert 500 may be positively positioned and clamped via a means no wider than the narrowest portion of cutter body 100. Therefore, slots of much narrower width may be formed with slotting cutters of this invention than could heretofore be formed with prior art slotting cutters utilizing disposably mounted cutting inserts. Slots as narrow as on the order of 1/8" have been fashioned with cutters designed in accordance with the principles of the invention. One typical range of widths that appears commercially feasible is on the order of 1/8" to 3/16". Such dimensions are, of course, presented for the sake of example only and are not intended to place implied limitations on the scope of this invention. It will be apparent to those skilled in the relevant cutting tool art, that the minimum width of slots formed by use of this invention is limited only by the width of the cutting edge of the inserts employed, and not by the size of the novel insert clamping apparatus set forth hereinabove.
It should be noted that the invention described herein has been illustrated with reference to a particular embodiment. It is to be understood that many details used to facilitate the description of such a particular embodiment are chosen for convenience only and without limitation on the scope of the invention. Many other embodiments may be devised by those skilled in the art without departing from the scope and spirit of the invention. For example, the planar insert clamping blade 300 could be formed as an integral portion of the cutter body, by milling out appropriately positioned slits to define a flexible clamping portion of body material positioned between each camming member snd one surface of a corresponding insert pocket. Accordingly, the invention is intended to be limited only by the scope and spirit of the appended claims. | Improved apparatus is disclosed for positively locating and retaining disposable inserts of a slotting cutter. The apparatus is arranged such that inserts normally used in non-rotating cut-off, parting or grooving tools can be mounted in a relatively narrow substantially circular rotating cutter body, thereby permitting narrower slot formations than heretofore possible with such tools. | 8 |
BACKGROUND OF THE INVENTION
TECHNICAL FIELD
The present invention relates to the field of tubing manufacturing and in particular to the field of fuel and vapor transmission tubes for internal combustion engine vehicles. It further relates to laminated structures having flexibility, impact resistance and hydrocarbon impermeability suited for use as a fuel and/or vapor conducting tubing and to a process for making the same.
BACKGROUND OF THE INVENTION
It has been known in recent times to use a multilayered or laminated rubber structure serving as a fuel transporting hose for an automotive fuel feed line into a vehicle reservoir. The conduit wall may have three layers; a heat and gasoline-resistant inner tube; a weather-resistant outer tube and a reinforcing fiber matrix or layer interposed and integrated between the other two. Even so, partly oxidized, or "sour" gasoline and oxygenated fuel adversely affect a fuel hose life so that enhanced gasoline-resistant features are needed. The fluoropolymers FKM, a terpolymer of tetrafluoroethylene, hexafluoropropylene and vinylidine chloride, hereinafter, respectively, TFE, HFE, and VF 2 , has exhibited satisfactory performance characteristics as a fuel resistant material. See, for example, U.S. Pat. No. 5,093,166, issued Mar. 3, 1992. However, it has proved difficult to bond an FKM layer to other rubbers. Further, FKM layers are not by themselves sufficiently impermeable to hydrocarbon vapors to enable automobile manufacturers to meet U.S. EPA standards for automotive vehicle emissions for 1995.
Thin layer THV, also a terpolymer of TFE, HFE, and VF 2 , has been used as a hydrocarbon barrier lamina in tubular hoses. These hoses have been made by spirally wrapping a THV tape on a mandrel to form a tube, spirally wrapping a metal reinforcement around the tube, and spirally wrapping a chloroprene tape around the reinforcement. The resulting tubular hose is heated to fuse the THV layers together and to vulcanize the rubber layer. This process is cumbersome and relatively expensive.
As to the automotive fuel filler tubes, some are presently made of relatively thick-walled nylon plastic, which provides the desired resistance to the usual hydrocarbon fuels, like gasoline, diesel oil, and even liquid paraffins, for example, ethanol. However, thick-walled nylon plastic tubing does not have sufficient flexibility and impact resistance to withstand automobile collisions without fuel line rupture. Flexibility and resilience of the tubing is also required to route the tubing through a tortuous path in the vehicle.
Vapor tubes which are used to recycle fuel vapors (for pollution control) must be resistant to the combustion vapors as well as the fuel itself. One of the more recent tubular construction is a coextruded formed tubing, which involves an inner core of NBR rubber and an outer core of a chlorosulphonated polyethylene plastic (Hypalon from the DuPont Co.). But with the currently used laminated fuel tubular conduits, there is still a persistent hydrocarbon pollution problem, due in part to the relatively high gas vapor permeability of presently used polymeric materials. In order to acceptably be used as fuel filler tubes, the conduits of these materials require at least surface modifications that will essentially block or markedly reduce unused HC vapor transmission to the environment from the fuel tank.
For example, the available Nitrile/Hypalon-based tubing has an HC permeation resistance rating of about 600 g/m 2 per day vapor loss measurement using ASTM Reference Fuel C, while the federal EPA wants to reduce permeability emissions to about 2 g per day for the entire vehicle. To that end, the auto industry currently seeks to reduce permeability for the gasoline filler tube and other fuel lines, vapor lines and vent hoses essentially to zero, a goal that is addressed by the present invention.
SUMMARY OF THE INVENTION
According to the invention, a laminated rubbery structure includes the cooperative use of two fluoropolymeric materials having complementary physical properties and incorporating an adjacent layer of a rubbery polymer such as an epichlorohydrin elastomer used as an amorphous copolymer with ethylene oxide (ECO), all of which can be extruded in a continuous process to provide a resilient and bendable tubular article of very low hydrocarbon permeability, and is further well adapted for transport of volatile fuels.
The tubular sidewall comprises a core layer of an FKM fluoroelastomer, exhibiting the properties of a rubber, a second layer of THV fluoroplastic exhibiting the properties of a thermoplastic layer, these layers being relatively thin layers, and an external layer of a rubbery polymer such as an epichlorohydrin monomer (EC) copolymerized with ethylene oxide (EO) to form an epichlorohydrin polymer (ECO). This ECO layer is the relatively thicker layer in the laminate.
Preferably, the core layer of FKM includes a measurable amount of an electroconductive filler material, like carbon black, useful to confer the desired core layer with conductivity for discharge of static electricity.
In a preferred embodiment, a binder layer of an amine or an acrylic compound is coated onto the THV layer to bond the THV layer to the ECO layer.
The present laminated polymeric structures, when fabricated into fuel conduits, provide for bendability when forming is needed, permit some compression without rupture, and will also tolerate moderate elongation without rupture. The laminated sidewalls demonstrate very low hydrocarbon permeability, both as to liquids, like gasoline, and to hydrocarbon vapors. Conductivity of the laminate inner layer inhibits the build-up of static electricity in the fuel reservoir. Finally, this somewhat resilient laminated sidewall shows the ability to mechanically seal itself and elongate, in the event of sidewall breach incidental to a vehicle collision.
In another aspect of the invention, fuel filler or a vapor line tubing has an extruded inner layer of a THV fluoroplastic that can or cannot be conductive and an extruded outer layer of a rubbery polymer. A binder layer of an amine compound is preferably coated onto the THV layer to promote bonding between the THV layer and the rubbery polymer layer.
In accordance with still another embodiment of the invention, a laminate of the invention is made by coextruding the FKM and THV layers under pressure to mechanically bond these two layers together and then crosshead extruding the external rubbery polymer layer onto the THV layer. A primer or binder coating is preferably applied to the THV layer between the coextrusion and crosshead extrusion steps. During the extrusion process, the temperature of the FKM fluoroelastomer is maintained below about 300° F., preferably about 270° F., while the temperature of the THV fluoroplastic is maintained above 400° F., preferably about 450° F.
After the extrusion process, the tubing is cut to lengths and heated for a time and at a temperature which gives the tubing lengths a partial vulcanization to promote cross-linking between the THV fluoroplastic layer and the outer elastomer layer while it is in a straight condition. Thereafter, the length of tubing is bent into a desired configuration and heated for a time and at a temperature to give the shaped tubing a full vulcanization.
The aspects and advantages of the present invention will be better understood by reference to the detailed description of preferred embodiments and associated features but the invention is not intended to be limited thereto.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective end view of a tube according to the invention;
FIG. 2 is a sectional view of the tube shown in FIG. 1, taken along lines 2--2 of FIG. 1;
FIG. 3 is a schematic representation of a process according to the invention for making the tube shown in FIGS. 1 and 2;
FIG. 4 is a sectional view, like FIG. 2, of a second embodiment of the invention;
FIG. 5 is a graph of plotted performance data for a laminated sidewall evaluated against gasoline vapor permeation according to a prior art construction; and
FIG. 6 is a graph of plotted performance data for a laminated sidewall evaluated against gasoline vapor permeation for a laminate according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, and to FIGS. 1 and 2 in particular, there is shown a tubular structure according to the invention. Preferably, the tube is used as an automotive fuel filler tube for gasoline and has a high degree of permeability. The tube has inner layer 14 of an FKM fluoropolymer, an intermediate layer 16 of a THV fluoropolymer, a relatively thick layer 18 of an elastomer and a thin binder coating 20 between the THV layer 16 and the elastomer layer 18.
The FKM fluoropolymers which can be used according to the invention have been available for some time. For example, the FLUOREL brand of fluoroelastomers, introduced by the 3M Company of Minnesota in the early 1960s, are suitable for use in this invention. These fluoroelastomers are TFE/HFP/VF 2 terpolymeric compositions, which are melt processable fluoro-plastics, providing a useful combination of performance and processing advantages without the need for organic additives. They are characterized by low processing temperature range (100° C. to 175° C.), co-processability with temperature-sensitive substrates, like non-fluorinated plastics, and elastomers, like ECO. They also are essentially amorphous and have the characteristics of elastomers, i.e., they are thermosetting compounds which exhibit a 100% stretch without deformation. Typically, the fluoroelastomers contain about 65-71% fluorine by weight. They also show excellent flexibility/elongation features with low flexural modulus, good flex fatigue life, and avoidance of stress cracking. They evince versatile bondability (hot melt adhesive) and a broad temperature service range.
These fluoroelastomers can have a relatively wide range of monomer ratios. These fluoroelastomers are generally described in U.S. Pat. No. 2,833,752, issued May 5, 1958 and U.S. Pat. No. 5,208,305, issued May 4, 1993, both of which patents are incorporated herein by reference. Generally, the TFE component can be present in the range of 0 to 70 weight parts, the HFP component can have a range of 20 to 50 weight parts and the VF 2 component can have a range of 20 to 80, based on 100 weight parts of FKM. The preferred fluoroelastomer is a fluoroelastomer sold by 3M Company under the designation FE5830Q. This polymer has about 33% VF 2 , 24% TFE and 43% HFP, by weight.
Suitable FKM polymers are obtained, for example, by polymerizing a mixture of monomers consisting of 40 mol percent of TFE, 30 mol percent of HFP and 30 mol percent of VF 2 , with the monomer mixture also containing up to 5 weight parts of a bisphenol cross-linking agent per 100 parts, by weight, of the three monomers and 1-20 parts of a basic metal oxide. This FKM composition is suited to a well-known extrusion process for forming the FKM layer 14.
The FKM polymer is compounded with various additives, such as carbon black, cross-linking agents and plasticizers for processability and for conductivity. FKM layer 12 is preferably conductive, as the result of additives such as carbon black. Other compounding ingredients include magnesium oxide, calcium hydroxide and carnauba wax.
The THV fluoropolymer used in the invention is a fluoroplastic terpolymer which is described in U.S. Pat. No. 5,055,539, issued Oct. 8, 1991. This patent is incorporated herein by reference. The terpolymer component of the THV layer comprises tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidine fluoride (VF 2 ). The THV fluoroplastic polymers comprise the following polymerized units: (a) 20-50% by weight of VF 2 ; (b) 35-70% by weight of TFE; and (c) 10-30% by weight of HFP, with the proviso that the quantities of VF 2 , TFE and HFP make up 100% by weight of the polymer component of the THV layer. The THV fluoroplastic polymer used in the invention is used without any further adjuvant compounds.
The THV fluoropolymer should be partially crystalline, that is, it should contain 10 to 70% by weight of crystalline components and have a crystalline melting point of 100-240 ° C., measured by differential thermal analysis. Polymers having a melting point of below 100° C. are generally too soft for the intended application. Polymers having a melting point above 240° C. are more difficult to process in the intended application. THV 500 grade sold by 3M Company is the preferred compound used in the invention, although the THV 200, 350 and 400 grades can also be used. These THV fluoropolymers are thermoplastic in nature, i.e., they melt when heated and are subject to elastic deformation at 100% elongation.
The THV fluoroplastic polymers typically have specific gravity ranges from 1.95 to 1.98 g./cc ASTM 792), melting range from 115° C. to 180° C. (DSC), a melt flow index from 5-25 (265C/5 kg.)(ASTM 1238) in powder and pellet form and 35-60 (265C/5 kg.) (ASTM 1238) in aqueous dispersions. THVs have a tensile stress at break of 20 N/mm (ASTM 638) and elongation at break 500-600 percent (ASTM 638), a limiting oxygen index of 75 (ASTM 2863) and flammability rating of V0 (UL 94).
The employment of THV 500G grade fluoroplastic, in the form of granules (pelleted is the preferred material), is suitable for melt processing into a coextruded formed article with FKM and ECO polymers. The lower melting point of the THV polymers provides for a more complete and uniform fusing of the THV to itself and to the adjacent FKM polymer layer.
The THV fluoroplastic polymers have the advantage of being an easily extrudable material which is flexible and crystalline. Further, they are bondable to the other substrates and have relatively low temperature processability. They are non-corrosive and have relatively high elongation properties.
The elastomeric compound should have one or more of the following properties: ozone and weather resistance, fuel resistance, flame resistance and it must adhere to the fluoroplastic polymer. The elastomeric compound used as layer 18 can be selected from various vulcanizable elastomeric compounds of any known natural rubber or synthetic rubber stock and including, without limitation, epichlorohydrin elastomers including ECO copolymer, styrene-butadiene rubber (SBR), of both high and low durometer grades and oil-extended types; neoprene (G and W types); ethylene-propylene copolymer and terpolymer rubbers; butyl rubber; acrylonitrile-butadiene rubber; chlorosulfonated polyethylene rubber; fluorinated polyethylene; CSM; CPE and NBR/PVC. Preferably, the elastomeric compound is an ECO copolymer. The elastomeric rubber is compounded with the usual compounding ingredients, such as cross-linking agents, carbon black, plasticizers, and the like.
Copolymers with 40% EO (the equimolar amount) are useful rubbers for elastomer layer 18, having excellent resistance to oils and ozone and low gas permeability. The polymers are vulcanized by well known methods employing the use of thioureas and basic metallic oxides. The resulting copolymer is primarily amorphous, with only a small degree of crystallinity. The good gasoline resistance of ECO and its low-temperature flexibility, make it especially useful for inclusion in the automotive parts articles of the present invention.
The binder layer 20 can be any suitable binder material to promote the adhesion of the FKM layer 16 to the elastomer layer 18. Preferably these compounds are amine compounds or acrylic compounds. An example of a suitable binder is Dynamar FC 5155 sold by the 3M Company of St. Paul, Minn. Examples of suitable amine compounds include 1,2-ethanediamine, N 3-(trimethoxysilyl)propyl!-methane amine, N-methyl-. An example of a suitable acrylic binder compound is an ethylene acrylic elastomer compound. The ethylene acrylic elastomer is sold by the du Pont company under the trade name of Vamac.
The FKM layer 14 can vary somewhat but is generally kept relatively thin. Generally, the FKM layer 14 is in the range of 0.25 to 1.00 mm, preferably in the range of 0.50 to 0.75 mm thick.
The THV layer 16 can also vary widely but is selected to give the appropriate barrier to hydrocarbons in conjunction with the FKM layer 14. Generally, the THV layer will be in the range of 0.10 to 0.50 mm, preferably in the range of 0.20 to 0.25 mm.
The elastomer layer 18 is relatively thick, and forms the bulk of the tubing wall. The thickness of the elastomeric layer 18 can vary over a wide range but typically will fall in the range of 1.5 to 5.0 mm thick, preferably in the range of 3.0 to 3.5 mm. The binder layer 20 is relatively thin, and is in the nature of a coating.
Referring now to FIG. 3, there is shown in schematic form a process for producing tubing according to the invention. A rubber extruder 24 and a plastic extruder 26 have extrusion openings connected to a dual extrusion die 28 for extruding a two-layer tube. The extruders 24 and 26 heat the FKM and THV to suitable processing temperatures and coextrude the two under pressure through the dual extrusion die 28 to form a tubing having an inner layer of FKM and an outer layer of THV. The temperature of the FKM is controlled in the extruder so that it does not overheat due to the relatively elevated temperature of the THV. The temperature of the THV is kept above about 400° F., preferably about 450° F., while the temperature of the FKM is kept below 300° F., preferably about 270° F., during the coextrusion process. The tubing 30 is pulled from the die 28 and is passed through an air cooler 34 and a binder coater 36 wherein a binder coating is uniformly applied to the outer layer of THV. The tubing 32 is then passed through a crosshead extruder 38 which extrudes an elastomer layer 18 onto the coated tubing 32. To this end, the crosshead extruder 38 has a rubber extruder for feeding an elastomeric compound such as ECO into a crosshead extrusion die through which the coated tubing passes. The rubber extruder heats the elastomeric compound to a processing temperature at which it can be extruded onto the coated tubing 32. A puller 40 pulls the composite tubing 42 from the crosshead extruder 38. The tubing 42 is then cut to lengths 48 with a knife 46 in a well known operation. The length of tubing is given a relatively light vulcanization treatment in a partial vulcanization chamber 50 by heating the tubing lengths in straight condition to a temperature in the range of 200° F. to 300° F. for a period of about 30 to 180 minutes. This partial vulcanization step is carried out while the tubing is straight to cross-link the outer elastomer layer 18 to the THV fluoroplastic layer 16. The length of tubing 48 is then placed onto a shaping device 52, for example, having a mandrel 54 to give a shape to the tubing. The shaped tubing is then vulcanized in a vulcanizing oven 56 to vulcanize the elastomeric composition in the layer 18 as well as the FKM layer 14. The vulcanization takes place in a well known process. After vulcanization, the shaped and vulcanized tubing 58 is removed from the shaping device 52 and subsequently cooled.
Conceivably, the binder coating step can be eliminated and the crosshead extruder 38 can be positioned at the dual extrusion die 28 to make a three-layer extrusion. A triple extrusion die can be used for this purpose.
The laminated resilient structure of this invention is adaptable to be formed into various shapes such as the tubular article of FIG. 1, shown after extrusion by the method of the invention, but seen prior to its shaping and vulcanization to adapt to a particular auto fuel filler tube. The resulting resilient articles of variable lengths, and of differing configurations (due to the internal geometry of the autos), present an organic chemical and weather-resistant fluid conduit, permitting only negligible escape of volatile HC vapors, due to enhanced sidewall gas impermeability.
Referring now to FIG. 4, there is shown a second embodiment of the invention wherein like numerals have been used to describe like parts. In this embodiment of the invention, the FKM fluoroelastomer layer 14 has been eliminated. A tubing formed with the construction shown in FIG. 4 includes an inner layer of THV thermoplastic 16, an elastomeric layer 18 and a binder coating 20 between the elastomeric layer 18 and the THV fluoroplastic layer 16. A tubing according to this construction can be used for fuel filler neck hoses or vapor tube applications.
The tubing made in accordance in FIG. 4 can be made in a process similar to that illustrated in FIG. 3 and described above with the exception that the rubber extruder 24 is eliminated. Otherwise, the process can be the same. Alternatively, the THV thermoplastic layer 16 and the elastomeric layer 18 can be extruded in a dual extrusion process with or without the application of the binder coating 20.
EXAMPLE
Flexible tubular articles fabricated according to the present invention were produced in the following manner:
Hose Construction #1
Inner Layer: Formulated FKM 1
Barrier Layer: THV 500G
Binder Layer: Dynamar FC5155
Outer Layer: Formulated ECO 2
Process
1. Mix FKM
2. Mix ECO
3. Co-extrude FKM & THV
4. Cool
5. Apply binder layer
6. Cross-head extrude ECO over FKM & THV
7. Cool
8. Cut to length
9. Pre-vulcanize
10. Load on shaping mandrels
11. Vulcanize
12. Remove from mandrels
13. Cool
14. Trim
Hose Fabrication #2
Barrier Layer: THV 500G
Binder Layer: Dynamar FC5155
Outer Layer: Formulated ECO
Process
1. Mix ECO
2. Extrude THV
3. Cool
4. Apply binder layer
5. Cross-head extrude ECO over THV
6. Cool
7. Cut to length
8. Load on shaping mandrels
9. Vulcanize
10. Remove from mandrels
11. Cool
12. Trim
______________________________________Constituent Content (Parts per 100 Rubber)______________________________________Formulated FKM.sup.1FKM Polymer 100.00Carbon Black 20.00Plasticizer 5.00Carnauba Wax 0.50Calcium Hydroxide 3.00Magnesium Oxide 9.00Calcuim Oxide 7.00Formulated ECO.sup.2ECO Polymer 100.00Hydrocarbon Resin 15.00Stearic Acid 1.25Antioxidant 1.00Calcium Oxide 10.00Antimony Oxide 5.00Carbon Black 75.00Plasticizer 5.00Vulcanizing Agent 1.0Accelerator 1.75______________________________________
The various layers of the hose construction exhibited the properties listed below:
______________________________________PHYSICAL PROPERTIESMaterial Properties FKM ECO THV______________________________________Original PhysicalsHardness, Shore A 82 69 95Modulus @ 100% Elongation, MPa 4.8 4.5 7.0Tensile Strength, MPa 11.0 12.5 14.5Elongation, % 294 267 520After Oven Aging 168 hours @ 125° C.Hardness Change, points +8 +10 0Tensile Strength Change, % +14 +4 -31Elongation Change, % -35 -34 -3After Oven Aging 168 hours @ 125° C.Hardness Change, points +12 -7 -13Tensile Strength Change, % -26 -41 -5Elongation Change, %After ASTM Fuel C Immersion, 70 hours @ 23° C.Hardness Change, points -2 -5Tensile Strength Change, % -15 -18Elongation Change, % -16 -8Volume Change, % +3 +10After 75% ASTM Fuel C + 25% MethanolImmersion, 70 hours @ 23° C.Hardness Change, points -11 0Tensile Strength Change, % -27 -22Elongation Change, % -25 -8Volume Change, % +13 +24After ASTM #3 Oil Immersion, 70 hr @ 125° C.Hardness Change, points +2Tensile Strength Change, % +4Elongation Change, % -15Volume Change, % +3Permeation - SAE J30 28 days @ 23° C.,g/sq.m./24 hrsASTM Fuel C 275% ASTM Fuel C + 25% Methanol 4 After 42 days After 42 daysBurst Strength, Mpa Original Filled with Fuel C Filled with M2519 mm ID 1.03 0.97 0.9628 mm ID 0.76 0.76 0.7338 mm ID 0.48 0.43 0.4548 mm ID 0.40 0.35 0.37Electrical Conductivity, megaohms 1Adhesion, kN/mOriginal Stock tear; cannot separateAfter 42 days Filled with Fuel C Stock tear; cannot separateAfter 42 days Filled with M25 Stock tear; cannot separateFlexibility after 8 days @ 150° C. No CracksOzone Resistance, 70 hours @ 100 PPHM, No Cracks40° C.Low Temperature Flexibility @ -40° C. No CracksAfter 70 hr Filled with Fuel C, Fuel Drained,then aged 70 hr @ -40° C.______________________________________
A brief cataloging of the several figure graphs is provided to better relate them to the laminate compositions of the prior art and to the disclosed embodiments of the present invention.
FIG. 5 reflects permeation test results for a FKM fluoropolymer/ECO elastomer laminate of the prior art evaluated for its gasoline resistance under SAE J-30 standards. Fuel resistance of the laminate (FKM layer surface) is measured by gasoline permeation in grams/M 2 /24 hrs.
FIG. 6 reflects test results for an FKM/THV/ECO polymeric laminate (hose construction #1) made according to the invention. This laminate was evaluated under SAE J-30 standards for gasoline permeation by M25 fuel (fuel C) under the same temperature and time parameters as in data represented in FIG. 5.
The graph of FIG. 5 displays substantial daily weight loss of test gasoline from the receiver over fourteen days, from 110 down to 45 grams/M 2 . The laminate of FIG. 6 is appreciably superior in permeation resistance to that of FIG. 5, even over a 42-day period.
The present invention (FIG. 6) reveals excellent, extended levels of permeation resistance (SAE J-30) up through 42 days, which is appreciably better than the prior art laminate of FIG. 5.
When contrasting the performance data of the prior art laminate depicted in FIG. 5 to that of the invention shown in FIG. 6, the degree of improvement approaches an order of magnitude, as measured by weight loss from the formed container per unit area over extended time periods. These challenging test conditions exaggerate those experienced in auto industrial uses wherein the gasoline only intermittently (upon tank filling) contacts the laminated conduit. The filling tube does, however, continuously experience gasoline vapor pressure from the fuel tank throughout vehicle use.
Thus, it may be fairly concluded that a laminated fluoroplastic/rubber structure, fabricated in accord with the present invention, performs a superior function as measured by the markedly reduced permeability to volatile hydrocarbons.
In addition, the dual fluoropolymer use will permit a reduced thickness so as to improve the resiliency of the laminated conduit with attendant savings in the need for these costly, special purpose elastomeric systems.
Tubing according to the invention can be used in automotive applications for fuel lines, vapor lines, fuel filter and vent hoses. The tubing according to the invention is advantageously made by extrusion processes which determine the internal and external diameter of the tubing. The processes for making the tubing are economical.
Whereas the invention has been described with reference to a single elastomeric layer 18, the invention can also be used to make reinforced tubing. The same process as described above can be carried out to make the reinforced tubing except that there would be the additional steps of applying a reinforcement to the outer surface of the elastomeric layer 18, coating a second binder layer onto the reinforcement and crosshead extruding an additional elastomeric layer 18 over the reinforcement. The reinforcing layer can be a conventional reinforcing material, including natural and synthetic woven and knitted fabrics and metal wires. The elastomeric outer layer can be applied in a conventional crosshead extruding process in the same way as described above with respect to the application of the elastomeric layer 18.
While the present invention has been described in an illustrative manner, it is to be understood that the invention may be embodied with various changes, modifications and improvements, that may occur to those skilled in the art reading the specification, without departing from the spirit and scope of the invention as defined in the appended claims. | Automotive filler tubes require resistance to usual hydrocarbon fuel and mechanical properties to withstand collision forces. Tubes are fabricated from laminated rubbery structure reflecting the cooperative use of selected fluoropolymeric materials laminated with a rubbery copolymer like an epichlorohydrin elastomer to provide a flexible tubular article permitting only negligible escape of confined volatile hydrocarbons. A FKM rubbery polymer forms a relatively thin inner layer in the tube, a THV polymer forms a relatively thin intermediate layer and a relatively thick elastomeric polymer, e.g., ECO, forms a cover layer. In an alternative embodiment, a tube is formed from an inner layer of a THV fluoroplastic polymer and a cover layer of a relatively thick elastomeric polymer. The tubing is made by coextruding the FKM rubbery polymer and the THV fluoroplastic polymer, coating the THV fluoroplastic polymer layer with a binder, crosshead extruding the elastomeric polymer layer and cutting the tubing to lengths. The lengths are given a partial cure in straight condition to cross-link the THV fluoroplastic layer to the FKM rubber polymer layer and to the elastomeric layer. The partially cured lengths of tubing are shaped and then fully cured. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
The entire content of Polish Patent Application No. P.407002, filed on Jan. 30, 2014 in which the priority right of the present patent application is claimed is herein incorporated by reference.
TECHNICAL FIELD
The subject of the invention is a device for closing sliding doors, designed for use in the furniture industry, built-ins and interior arrangement.
BACKGROUND
Sliding door closing devices prevent the door from closing too fast and hitting against an external frame, side wall or frame. They prevent the hand from being crushed or damage to the door structure.
From patent description US2013167444A1, a sliding door arrangement is known, in which the force of a rapidly closing door is dampened by a gas shock absorber mounted in a guide rail. A pin is attached to the door, which, while closing, engages with a gripper attached at the end of the shock absorber.
From Polish utility model application W.120907, a sliding door closing device is known, which comprises three systems for shock absorbing and gripping, spring tension adjustment and an adjustable device mounting inside the guide rail. While sliding (opening) the door, the shock absorbing and gripping system is tensioned by the spring tension adjustment system, and an engagement pin is released from a driver, and the door continues sliding freely. While closing, the rapidly closing door with the engagement pin hits its driver, the shock absorbing and gripping system is released, the door is braked and energy is dissipated, and the door continues closing slowly, controlled by the spring tension adjustment system, until it closes completely.
Solutions known from the above descriptions are able to brake rapidly closing doors, yet they are difficult to open since, until the shock absorber is released, the resistance of the shock absorbing system has to be overcome. This is particularly difficult for doors without handles or strips intended for opening.
The purpose of the invention is to develop a sliding door closing device that will brake a rapidly sliding door leaf and close it to make contact with a side edge, but would allow easy and effortless opening at the same time.
The door closing device, according to the invention, has a body. The body, in its upper part, has longitudinal holes in the side walls, located in the vicinity of the body ends. In the lower part of the body, there is a longitudinal component located in parallel to the base, which serves as a pusher, and—in the upper part of the body—above the pusher, there is a slider with lateral holes at the ends.
Inside the slider, there are two chambers. In one of them, there is a spring and a choke of the closing device, and in the other chamber, the gripper of the closing device is fixed slidably, connected with the closing device choke and which remains in contact with the closing device spring. The end part of the slider, at the side of the spring and choke, is terminated with a hooked attachment. To one of the external walls of the body, the spring and—on the opposite side—the choke of the opening device is mounted. The ends of the spring and choke of the opening device are permanently attached to the body wall and—on the other side—connected with a lateral joiner placed through holes in the body and in the slider. On one of the ends, the body is fitted with the rotary and spring mounted slider gripper, which remains in contact with the pusher, and is provided with an attachment that fits to the one at the end of the slider. On the opposite side of the body, there is a permanently fixed housing in which there are two rollers arranged in parallel to the body base, whereby one roller is movable and one is stationary. The movable roller is fitted in a support that is spring-mounted to the housing, and its side surface remains in contact with the pusher end.
Preferably, the closing device body has the shape of a channel bar, which, in the cross section, is narrower in the lower part than in the upper part.
The sliding door closing device, according to the invention, features an easy door opening function with an opening system comprising a slider with an attachment and gripper on one side, properly shaped support of the moving roller on the other side, and a pusher contacting the roller support with a slider gripper, the opening device spring, and the choke. The opening system allows for opening of the door by pushing the door on a vertical strip or on the edge. Pushing on the door moves the support on the moving roller and simultaneously moves the pusher on the support wedge and releases the pusher from the gripper. In one variant of the door closing device, according to the invention, the pusher releases the slider from the gripper by a pushing movement, and in the other variant, it does so by a pulling movement. By opening the opened door, tension is placed on the closing device spring with the gripper of the closing device moving inside the slider. The stroke of the slider is determined by the length of longitudinal holes in the body. Preferably, the length of the holes is approx. 25 mm. When tension is placed on the spring, the gripper is locked, and the door moves freely on the guide rails. While closing, the closing device gripper is released by the door guide gripper, and the door is closed by placing tension on the opening spring and moving the slider in the body and locking it with the slider gripper at the same time. The closing spring pulls the door to the inner side of the cabinet.
The closing device, according to the invention, is provided with components with the additional function of releasing the door closing system, thanks to which, at first, the door is much easier to open, and activating the opening mechanisms requires only a slight push on the door or on a vertical profile in which the door is fixed.
BRIEF DESCRIPTION OF THE DRAWINGS
The sliding door closing device, according to the invention, is presented in a sample embodiment in a drawing, in which:
FIG. 1 presents a simplified diagram of the first variant of the device with the door closed,
FIG. 2 presents a simplified diagram of the second variant of the device with the door closed,
FIG. 3 presents a simplified diagram of the first variant of the device with the door opened,
FIG. 4 presents a simplified diagram of the first variant of the device with the door slid out,
FIG. 5 presents an exploded view of the closing device components in its first variant, and
FIG. 6 presents three views of the closing device mounting in the upper track.
DETAILED DESCRIPTION OF THE EMBODIMENTS
A sample embodiment of the first variant of the sliding door closing device according to the invention is presented in the drawing, which has a metallic body 1 in the shape of a channel bar, which, in the cross section, is narrower in the lower part than in the upper part. At the ends of the body 1 , there is a starting attachment 7 and an end attachment 9 . The starting and end attachments are profiled so as to fit to the inner side of the horizontal door profile. The body 1 has four 25 mm long holes 23 a and 23 b in the side walls of the upper part. In the lower part of the body 1 , there is a longitudinal component 13 , which serves as a pusher, and—in the upper, wider part of the body—above the pusher 13 , there is a slider 2 with holes 24 a and 24 b at the ends. The slider 2 can travel in the body at the distance of 25 mm, since it is held with pins 19 and 21 placed in the holes 24 a and 24 b , moving in the holes 23 a and 23 b of the body 1 . Inside the slider 2 , there are two chambers. In one of them, there is a spring 15 and a choke 11 of the closing device, and in the other chamber, a gripper 6 of the closing device is fixed slidably, connected with the closing device choke 11 by a pin 22 and which remains in contact with the closing device spring 15 . The end part of the slider, at the side of the spring 15 and choke 11 , is terminated with a hooked attachment 25 . To one of the external walls of the body 1 , a spring 14 and—on the opposite side—a choke 12 of the opening device is mounted. The ends of the spring 14 and choke 12 of the opening device are permanently attached to the body 1 wall on one side and—on the other side—connected with the pin 21 placed through the holes 23 a in the body and through the holes 24 a in the slider. At the end part of the body 1 , at the end attachment 9 , there is a rotary and spring mounted slider gripper 8 , which remains in contact with the pusher 13 , which is provided with an attachment 26 that fits to the attachment 25 at the end of the slider. The gripper 8 is connected to the body with a pin 20 , and a spring 17 holds the slider gripper in the correct position. On the opposite side of the body 1 , there is a permanently fixed housing comprising of a top cover 3 and bottom cover 4 . Inside the housing, there are two rollers 10 a and 10 b arranged in parallel to the base of the body 1 , whereby the roller 10 a is movable, and the roller 10 b is stationary. The movable roller 10 a is placed in a support 5 with a pin 18 on which it rotates. The support 5 of the roller 10 a is held in position by a spring 16 . The side surface of the support 5 remains in contact with the end of the pusher 13 .
In the second variant, shown in the drawing in FIG. 2 , the pusher 13 remains in contact with the opposite side of the support 5 , which is a mirror reflection of the support 5 of the first variant. The other end of the pusher 13 remains in contact with the slider gripper 8 , which is connected to the body with the pin 20 . Since, in this variant, the pusher 13 is pulled by the roller support 5 , its end remains in contact with the outer side of the slider gripper 8 .
In the initial state, the door rests against the cabinet or wall edge, the closing device spring 15 is released, and tension is created on the opening device spring 14 , i.e. it is ready to open the door. Pushing on the side edge of the door or on the profile moves the door leaf in relation to the guide rail. This causes a simultaneous movement of the roller 10 a , moves the roller support 5 and pusher 13 , whose opposite side interacts with the gripper 8 . Simultaneously, the slider gripper 8 turns in an axis perpendicular to the base of the body, thus releasing the slider 2 . The released slider 2 moves in the holes cut in the body over a distance of 25 mm thanks to the release of the opening device spring 14 . This movement is cushioned with the opening device choke 12 . Along with the slider 2 movement, the door is moved away from the framing. When continuing to open the door, the closing device slider gripper 6 is moved, allowing to reload and create tension on the closing device spring 15 at the same time. Moving along a proper trajectory within the channel in the slider 2 , thanks to guides cut (guiding channels) in the slider 2 , the closing device gripper 6 , when it creates tension on the closing device spring 15 and the choke 11 , is locked, and the door continues to open freely. While closing the door, the closing device gripper 6 is released in the slider 2 by the guide attachment 25 or 26 or end attachment 9 mounted in the door rail. The slider 2 moves back in the body 1 and creates tension on the opening device spring 14 and the choke 12 . At the same time, the locked closing device gripper 6 in the slider gripper moves inside the slider 2 , being pulled by the closing device spring 15 . This causes a pulling of the door to the framing edge. This movement is cushioned by the closing device choke 11 connected with the closing device gripper 6 . When the door is pulled, the slider 2 is locked by the slider gripper. The door is ready to open. Roller support 5 is capable of moving from the position shown in FIG. 1 to the position in FIG. 3 which activates the pusher 13 when the user lightly pushes the door in a perpendicular direction to the motion of the slider and the gripper 6 .
In the second variant of the device, the movement of the roller 10 a , while pushing, moves the support 5 which pulls the pusher 13 . The pusher, being pulled and remaining in contact with the slider gripper, simultaneously causes the gripper 8 to rotate on a perpendicular axis to the body base, but in the opposite location as compared to the first variant. The slider gripper 8 has a hooked attachment on the opposite side as compared to the first variant. Its rotary movement releases the gripper. | A sliding door closing device having an easy door opening function with an opening system. The closing device provides a slider with an attachment and gripper on one side of the device, and a properly shaped support of a moving roller on the other side of the device. A pusher contacts a roller support of the roller with a slider gripper and an opening spring and choke. The opening system allows for the opening of a door by pushing the door on vertical strip or on the edge. | 4 |
Certain aspects of the present invention were supported by the National Science Foundation-Grants DMR-82-16718 and DMR-80-22870 and the Office of Naval Research. Certain righes have been retained by the United States Government in respect to this invention.
This is a continuation of application Ser. No. 757,884, filed Jul. 23, 1985 now abandoned.
FIELD OF THE INVENTION
This invention is directed to improved eolectrodes for use in batteries, fuel cells, sensors and other electrochemical devices. The electrodes are particularly adapted for use in aprotic electrolytes. High capacity electrodes are formed from polyaniline and related materials which permit electrochemical devices such as batteries to be prepared having capacities and efficiencies close to the theoretical maximum for such materals. Methods for energy storage are also comprehended.
BACKGROUND OF THE INVENTION
There has recently been an increased interest in electrochenistry and electrochemical phenomena of polymeric systems. See, in this regard, U.S. Pat. Nos. 4,222,903 and 4,204,216-- Heeger et al. and 4,321,114 and 4,442,187-- MacDiarmid et al. which are directed to the electrochemistry of certain conjugated polymers having extended conjugation in at least one backbone chain thereof. Each of the foregoing are incorporated herein by reference.
In U.S. patent application Ser. No. 620,446 filed Jun. 14, 1984, assigned to the assignee of this invention and incorporated herein by reference, certain electrochemical systems employing polyanilines as electrodes materials are described. Each of these systems have aqueous or otherwise protic electrolytes. Work in that area prior to the foregoing invention did not meet with successful development of secondary batteries, fuel cells, or substantially reversible electrochemical methods, however.
Jozefowicz et al., have undertaken certain electrochemical studies of certain forms of polyaniline as an anode and cathode in aqueous solution. See, for example, French Patent No. 1,519,729; French Patent of Addition No. 94,536; U.K. Patent No. 1,216,549; "Direct Current Conductivity of Polyaniline Sulfates", M. Diromedoff, F. Hautiere-Cristofini, R. DeSurville, M. Jozefowicz, L-T. Yu and R. Buvet. J. Chim. Phys., Physicoshim. Biol., 68, 1055 (1971); "Continuous Current Conductivity of Macromolecular Materials", L-T. Yu, M. Jozefowicz, and R. Buvet, Chim. Macromol. 1, 469 (1970); "Polyaniline-Based Filmogenic Organic-Conductor Polymers", d. LaBarre and M. Jozefowicz, C. R. Acad. Sci., Ser. C, 269, 964 (1969); "Recently Discovered Properties of Semiconducting Polymers", M. Jozefowicz, L-T. Y, J. Perichon and R. Buvet. J. Polym. Sci., Part C, 22, 1187 (1967); "Electrochemical Properties of Polyaniline Sulfates", F. Cristofini, R. DeSurville and M. Jozefowicz, C. R. Acad. Sci., Ser. C, 268, 1346 (1969); "Electrochemical Cells Using Protolytic Organic Semiconductors", R. DeSurville, M. Jozefowicz, L-T. Yu, J. Perichon and R. Buvet, Electrochim. Acta, 13, 1451 (1968); "Oligomers and Polymers Produced by Oxidation of Aromatic Amines", R. DeSurville, M. Jozefowicz and R. Buvet, Ann. Chim. (Paris), 2, 5 (1967); "Experimental Study of the Direct Current Conductivity of Macromolecular Compounds", L-T. Yu, M. Borredon, M. Jozefowicz, G. Belorgey and R. Buvet, J. Polym. Sci., Polym. Symp., 16, 2931 (1967); "Conductivity and Chemical Properties of Oligomeric Polyanilines", M. Jozefowicz, L-T. Yu, G. Belorgey and R. Buvet, J. Polym. Sci., Polym. Symp., 16, 2934 (1967); "Products of the Catalytic Oxidation of Aromatic Amines", R. DeSurville, M. Jozefowicz and R. Buvet, Ann. Chim. (Paris), 2, 149 (1967); "Conductivity and Chemical Composition of Macromolecular Semiconductors", L-T. Yu and M. Jozefowicz, Rev. Gen. Electr., 75, 1014 (1966); "Relation Between the Chemical and Electrochemical Properties of Macromolecular Semiconductors", M. Jozefowicz and L-T. Yu, Rev. Gen. Electr., 75, 1008 (1966); "Preparation, Chemical Properties, and Electrical Conductivity of Poly-N-Alkylanilines in the Solid State", D. Muller and M. Jozefowicz, Bull. Soc. Chim. Fr., 4087 (1972). Jozefowicz et al. employed a reduced form and an oxidized form of polyaniline, neither of which was analyzed or characterized in any way as to their chemical composition, as the anode and cathode respectively in one normal sulphuric acid (pH-O). They observed that such an electrochemical cell could be charged and discharged for two consecutive cycles.
Repetition of the disclosures of Jozefowicz has shown that the methods of Jozefowicz do not lead to substantial reversibility of electrochemistry involving polyaniline or to electrochemical cells having sufficient reversibility as to provide practical utility for secondary battery use.
Several papers have been published describing the use of "polyaniline" as a cathode in rechargeable battery cells in conjunction with a lithium anode in non-aqueous electrolytes.
In "Electrochemical Study of Polyaniline in Aqueous and Organic Medium. Redox and Kinetic Properties", E. M. Genies, A. A. Syed and C. Tsintavis, Mol. Cryst. Liq. Cryst., 121, 181 (1985), polyaniline film was synthesized in concentrated (presumably aqueous) HF solution. Charge density and other properties were determined in the HF solution. It is stated that it was very important "that the process retains some acidity in the polymer. If the polymer is completely neutralized, it becomes almost electroinactive and an insultator. In organic solvent, the residual acidity of the PANI remains in the polymer."
In "Secondary Batteries Using Polyaniline", 24th Battery Symposium in Japan, Osaka, Japan, 1983, p. 197, A. Kitani, M. Kaya and K. Sasaki report on certain lithium/polyaniline battery structures. No final oxidizing potential or information leading to a knowledge of the degree of protonation of the polyaniline film used in the Li/LiClO 4 propylene carbonate/polyaniline battery is given, however. It is only stated that a potential of 0.8 V (versus a standard calomel electrode) in a 1 M aniline/12 M HClO 4 solution was used in synthesizing the polyaniline. It has now been determined that this potential, in the presence of aniline, produces a green film, not a blue-purple (highly oxidized) film of the type formed if no aniline is present. In the presence of aniline at this potential the polyaniline is constantly being synthesized. In the absence of aniline, the only electrochemical reaction is the more extensive oxidation of the polyaniline. Kitani et al. state that they washed the film with water. This would cause an unknown and uncontrolled amount of deprotonation of the polyaniline salt, depending on the washing conditions.
In "Studies on Organic Polymers Synthesized by Electrolytic Method (II) Secondary Battery Using Polyaniline", A. Kitani, Y. Hiromoto and K. Sasaki, 50th Meeting of the Electrochemical Society of Japan, 1983, p. 123, it is stated that polyaniline film was synthesized by repeated potential cycling between --0.2 V and 0.8 V (no reference electrode is reported) in 0.1 M aniline/0.2 M HClO 4 . No reference is made as to the final potential at which the film was oxidized before it was used in a Li/LiClO 4 (PC)/polyaniline cell. Also no mention is made as to how the product was washed. A pellet of polyaniline which was electrochemically synthesized in a powder form at 1.2 V "was also tested". This was apparently used only in aqueous electrolytes.
"Polyaniline as the Positive Electrode of Storage Batteries", M. Kaya, A. Kitani and K. Sasaki, 51st Meeting of the Electrochemical Society of Japan, Fukuoka, Japan, Apr. 28, 1984, P. 847, deals only with polyaniline in aqueous electrolytes, although in Table I electrochemical properties of a cell employing a Li anode are reported for comparative purposes.
Studies in aqueous electrolytes are described in "Secondary Battery Using Polyaniline", A. Kitani, M. Kaya, and K. Sasaki, 51st Meeting of the Electrochemical Society of Japan, Fukuoka, Japan, Apr. 28, 1984, p. 847.
OBJECTS OF THE INVENTION
It is an object of this invention to provide electrochemical electrodes employing polyaniline species which are capable of very high capacity and efficiency.
Another object is to provide batteries, fuel cells, sensors and the like employing these improved electrodes.
A further object is to prepare such electrodes, batteries, fuel cells and other electrochemical articles.
Yet another object is to attain methods for energy storage employing the foregoing batteries.
These and other objects will become apparent from a review of the present specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 depict structures of some aniline polymer species.
FIG. 3 illustrates possible resonance structures of an emeraldine salt.
FIG. 4 is a cyclic voltammogram for a polyaniline powder.
FIG. 5 depicts deprotonation of a salt form of a partially oxidized polyaniline.
SUMMARY OF THE INVENTION
It has now been found that electrochemical cells can now be prepared having greatly improved capacities and efficiencies. Such cells comprise anode active means, cathode active means, and aprotic electrolyte. At least one of the anode and cathode means is caused to consist essentially of a polyaniline species wherein each nitrogen of the polymer chain of the polyaniline species is associated with one, but only one, hydrogen atom. The foregoing electrochemical cells may be particularly adapted into secondary batteries, fuel cells, sensors and the like. In accordance with preferred practice, the polyaniline specie comprises a cathode of a secondary battery or fuel cell while the preferred anode in such systems is an alkaline metal or alkaline earth metal such as lithium.
In accordance with certain preferred embodiments of the invention, the electrochemical cells function by reversible oxidation and reduction of the polyaniline species forming the electrode. Thus, it is preferred that the polyaniline electrode species be reversibly transformable from an oxidized species having the formula: ##STR1## to a reduced species having the formula:
[--(C.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H)--]
wherein A - is a counterion, preferably from the electrolyte. It has been found that when electrochemical cells are prepared having polyaniline species electrodes which are capable of undergoing the foregoing, reversible transition, that high capacities and efficiencies result. This is in counter distinction to electrochemical cells formed from other forms of polyaniline. In accordance with another embodiment of the invention, methods for reversible energy storage such as in a secondary battery are comprehended which rely upon the cyclical oxidation and reduction of the foregoing electrodes in an aprotic electrolyte.
DETAILED DESCRIPTION OF THE INVENTION
The term "polyaniline" has been used for many years to describe a number of ill-defined materials resulting from the chemical or electrochemical oxidative polymerization of aniline, C 6 H 5 NH 2 . The invention described herein is based in part on the concept that polyaniline polymers may be described as a combination, in any desired relative amounts, of certain of the following idealized repeat units, depending on the experimental conditions to which the polyaniline is exposed. ##STR2## Both "lA" and "2B" units may, under appropriate experimental conditions, be partly or completely protonated to give the corresponding "salt" repeat units. ##STR3##
In the present context the repeat units represented by the terms 1A, 2A, 1S', 1S", 2S' and 2S" should not be regarded as necessarily excluding various isomeric units such as: ##STR4## or their protonated derivatives or branched chain units such as: ##STR5## or their oxidized and/or protonated derivatives which, as will be recognized by those persons skilled in the art, may also be formed to some extent during the synthesis of polyaniline.
Green and Woodhead claimed to have isolated octomers approximating the empirical compositions below. A. G. Green and A. E. Woodhead, J. Chem. Soc., 97, p. 2388 (1910); 101, p. 1117 (1912). The empirical compositions do not necessarily represent the actual structural formulas of the materials; indeed, it might be expected that different repreat units would be distributed more or less uniformly throughout a given polymer chain. Terminal (C 6 H 5 ), --NH 2 ═NH, OH, etc. groups were postulated. While we believe the materials are polymers, we retain, for convenience, the old nomenclature to represent the composition of the octomeric repeat units.
"Leuco-emeraldine" Base (i.e. 1A repeat units only)
[--(C.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H)--].sub.x
"Proto-emeraldine" Base (1A and 2A repeat units)
[[--(C.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H)].sub.3 --](C.sub.6 H.sub.4)--N═(C.sub.6 H.sub.4 ═N--]].sub.x
Emeraldine Base (1A and 2A repeat units)
[[--(c.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H).sub.2 ]--[(C.sub.6 H.sub.4)--N═(C.sub.6 H.sub.4)═N--].sub.2 ].sub.x
Nigraniline Base (1A and 2A repeat units)
[[--(C.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H)]--[(C.sub.6 H.sub.4)--N═(C.sub.6 H.sub.4)═N--].sub.3 ].sub.x
Pernigraniline (2a units only)
[--(C.sub.6 H.sub.4) --N═(C.sub.6 H.sub.4)═N--].sub.x
The smallest number of (C 6 H 4 )--N moieties which can be used in a repeat unit as suggested above which will permit interconversion between the above five compositions is eight. Possible combinations of "1A" and "2A" base units are depicted diagrammatically in FIG. 1. No attention is paid to bond angles, etc., in this representation.
Each of the repeat units in the foregoing polymer structures can also be converted to one or the other of its salt forms under appropriate conditions. By treatment with an appropriate acid the five base forms of polyaniline depicted in FIG. 1 can, in principle, be converted to the corresponding five "salt" forms given in FIG. 2. In principle, the extent of protonation can be greater or less than that shown in FIG. 2, depending on the experimental conditions employed in the protonation reactions. IT will be obvious to one skilled in the art that it is possible to formulate many combinations other than those depicted in FIGS. 1 and 2. The combinations given are to be considered as exemplary rather than exhaustive.
A semi-structural depiction of an emeraldine salt is given in FIG. 3. It is believed that an A - ion may be shared by more than one (NH) bond. In FIG. 3, for example, each (NH) unit may be considered as being associated with 0.5 positive charge. This emeraldine salt, if it consists of equal contributions from each of the four reasonance forms, would exhibit partial benzenoid/quinoid character as to each of the C 6 H 4 groups, and partial double bond character as to all of the C--N bonds. Since imine N atoms are expected to be less basic than amine N atoms, it is expected that the amine N atoms in a polymer containing both 1A and 2A repeat units would be preferentially protonated, e.g.: ##STR6## However, the emeraldine salt given in FIG. 3 has been postulated as containing protonated imine N atoms, viz.: ##STR7## This is believed to result from the delocalization of charge and accompanying equilization of bond lengths accompanying a structure derived from resonance forms suggested in FIG. 3. This is believed to predominate over the expected imine and amine base strengths as observed in simple molecules. The same general effect is believed also to apply when the number of 1A and 2A groups of a polymer chain are not equal. However, as the relative number of imine N atoms increases (relative to the number of amine N atoms) their ease of protonation will decrease since the protonation of an imine nitrogen is assisted by the presence of an adjacent amine nitrogen group.
This is shown clearly by the cyclic voltammogram of FIG. 4 where the potential of No. 1 and No. 1' peak is insensitive to pH in the range from approximately 1 to approximately 4(during the short time during which the cyclic voltammogram is taken) while the potential of No. 2 and No. 2' peak is sensitive to the pH in the same pH range from approximately 1 to approximately 4. The sensitivity of peak No. 2 in FIG. 4 shows that HA dissocaites readily from the polymer in its more highly oxidized state while no such dissociation is experimentally observable for the less highly oxidized polymer charactertized by peak No. 1.
The emeraldine salt presented in structural detail in FIG. 3, may be synthesized in at least two different ways. The salt (but not the compounds from which it is derived) shows metallic conductivity (σ=approximately 5S/cm). Thus, the emeraldine salt may be synthesized by protonic acid treatment of emeraldine base (Example 3). It may also be made through electro-chemical oxidation of leuco-emeraldine base (Example 1).
The colors of the polyaniline bases and salts changes continuously and smoothly according to the number of oxidized and reduced polyaniline groups present in the polymer. This is illustrated by the cyclic voltammogram of chemically-synthesized polyaniline powder (in 1 M aqueous HCl) given in FIG. 4. It can be seen that in this electrolyte the color becomes increasingly more violet with increasing degree of oxidation. The approximate compositions corresponding to a given color as reported by Green, et. al. are given in that figure. It should be noted that, because of the absence in 1A, 1S' and 1S" of repeat units of chromophoric groups related to conjugated quinoid-type segments, polyaniline can act in certain ways as its own "redox indicator". Thus a pale yellow (colorless in thin films) material is characteristic of the reduced 1A, 1S' and 1S" repeat units; green-blue-violet colors are indicative of the presence of 2A, 2S', 2S" groups.
The present invention relies upon the fact that the discharge of a battery cell consisting of a polyaniline cathode and, a metal electrode such as lithium in an aprotic electrolyte such as, for example, a LiClO 4 /propylene carbonate (PC) electrolyte, the fundamental electrochemical reaction occuring at the polyaniline cathode involves the reduction of a ##STR8## The reaction occuring at the Li anode is: ##STR9## The charge reactions are the reverse of the foregoing equations. Charge and discharge reactions between a completely reducted form of polyaniline consisting entirely of 1A repeat units and a completely oxidized form of polyaniline consisting of completely oxidized 2S" repeat units would then be: ##STR10## Such reactions would involve maximum utilization of the electrochemical capacity of the polyaniline, one electron per (C 6 H 5 )--N unit. The polyaniline electrode initially placed in the cell could consist of either the completely oxidized or completely reduced forms shown above.
It was not previously known that in order to obtain full use of the electrochemical capacity of a polyaniline electrode in a non-protic electrolyte it is necessary to control both the degree of oxidation and the degree of protonation of the polyaniline electrode.
A necessary distinction must be made between the different types of nitrogen-associated hydrogen atoms in polyaniline. A nitrogen atom attached to a hydrogen atom which is itself not associated with an A - counterion is said to be a "hydrogenated" nitrogen atom, as in, for example, a 1A repeat unit:
[--C.sub.6 H.sub.4)N(H)--C.sub.6 H.sub.4)--N(H)--].sub.x.
A nitrogen atom attached to a hydrogen atom which is associated with an A - counterion is added to be "protonated", as is, for example, a 2S' repeat unit: ##STR11## In certain instances, as in, for example, a 1S" unit, the nitrogen atoms will be both hydrogenated and protonated: ##STR12##
Full capacity of the polyaniline could also be realized if the polyaniline electrode placed in the cell had, for example, the composition: ##STR13## since after one initial electrochemical reduction it would have the composition:
[(C.sub.6 H.sub.4)--N(H)--C.sub.6 H.sub.4)--N(H)--].sub.(a+b)x
or after one initial electrochemical oxidation it would have the composition: ##STR14## Subsequent charge/discharge reactions would then utilize the full capacity of the polyaniline.
If, however, the polyaniline electrode initially placed in the battery did not have all the N atoms either hydrogentated or protonated, as in, for example:
[[--(C.sub.6 H.sub.4)--N(H)--(C.sub.6 H.sub.4)--N(H)]--[(C.sub.6 H.sub.4)--N═(C.sub.6 H.sub.4)═N--].sub.b ].sub.x
then complete oxidative/reductive, i.e. charge/discharge cycling between ##STR15## would not be possible since there would be no way in which the necessary (2b)x hydrogen atoms would be supplied to the 2A repeat units. If, for example, a=b, i.e. emeraldine base, then only 50% of the maximum capacity could be obtained, at best.
No clear description of the electrochemical processes which occur during the charge or discharge cycles of polyaniline has been described heretofore. Moreover, it has not been previously recognized that only certain chemical forms of polyaniline may be used in the construction of polyaniline electrodes if maximal electrochemical capacity of the polyaniline (based on its weight) is to be realized when it is used in a battery. It has now been discovered that only certain forms of polyaniline can be employed in constructing polyaniline electrodes for use in a battery or other electrochemical cell employing a non-protic electrolyte if the full electrochemical capacity of the polyaniline is substantially to be realized. It has been discovered that the electrochemical capacity of a given electrochemically-grown polyaniline film can be drastically modified simply by converting it to different chemical forms prior to its use in an electrochemical cell employing a non-protic electrolyte. The electrochemical reactions occuring during the charge/discharge processes in cells of the above type are now also known.
In view of the foregoing, it has now been found that in order to obtain preferred, maximum utilization of capacity of a polyaniline electrode in a battery comprising a non-protic electrolyte, the polyaniline electrode placed in the battery must satisfy the condition that each nitrogen atom in the polymer chain have one and only one hydrogen atom associated with it.
Less ideally, but still within the scope of this invention, it is possible to use a form of polyaniline where there are two hydrogen species attached to the same N atom as in, for example, a 1S' repeat unit. During the first charge (oxidation) cycle, HA will be liberated: ##STR16## The oxidized 2S" repeat unit of polyaniline so formed can function satisfactorily during subsequent charge and discharge cycles, but the HA liberated may ultimately diffuse to the Li anode and react chemically with it. This may likely be avoided as an operating problem, however, through careful construction of the battery.
The experiments hereinafter demonstrate the criticality of these criteria and are in excellent agreement with expected values. It should be stressed that the compositions of the "starting" forms of polyaniline given in FIG. I are formal and approximate since it is not yet precisely known what potential is necessary to synthesize a polymer corresponding exactly to the chemical composition of any particular form such as an emeraldine base or an emeraldine salt. The potentials necessary to synthesize a given composition will vary according to the pH (if synthesized in aqueous solution) or the nature of the electrolyte (if synthesized in a non-protic electrolyte). Also the time needed to obtain uniform macroscopic composition by diffusion through an electrochemically grown film has not yet been determined with precision. It is believed, however, that persons of ordinary skill in the art will have no difficulty in understanding and repeating the example.
It is believed that the polyaniline electrode need not necessarily be oxidized to its maximum extent when the battery is being charged. For example, if the composition of the polyaniline electrode placed in the battery were: ##STR17## the 2A repeat units i.e. the "b" segments would still be electrochemically inactive even if the 1A repeat units i.e. the "a" segments are only partially utilized electrochemically. Any electrochemically inactive form of polyaniline adds to the "dead wright" of the polyaniline electrode and reduces its electrochemical capacity per unit weight, however, and is therefore less preferred.
It should also be noted that polyaniline salt forms can also be deprotonated readily such as by washing in solutions of certain pH's greater than the pH of the solution in which the salt was synthesized. For example, electrochemically synthesized polyaniline was held at 0.42 V (vs. a standard calomel electrode, SCE) in an aqueous 1 M HCl solution (pH approximately 0) to produce a polymer having a composition approximating an emeraldine salt. The polymer was then placed in dilute aqueous HCl solutions of pH=1.0, 2.0, 3.0, 4.0 and 5.0 and its V oc was measured (vs. SCE) at intervals. The results are given in FIG. 5 and show the rapid deprotonation of the polymer. The rate of deprotonation increases with increasing pH. This is interpreted as deprotonation of N atoms in the polymer. For example: ##STR18## The reduction potential of the polyaniline electrode, based on the reduction reaction ##STR19## is given by the Nernst equation: ##EQU1## Since the potential becomes smaller as the pH increases, the ratio of the 2S" to 1A units must become smaller, as will, i.e. 2S" are being deprotonated to less highly protonated or nonprotonated units, depending on the pH of the solution.
If spontaneous deprotonation of some of the N atoms of the more highly oxidized forms of the polyaniline should occur in non-protic electrolytes, e.g.: ##STR20## then this spontaneous deprotonation may be inhibited by using an electrolyte having a different acid strength from propylene carbonate, by adding controlled amounts of protic solvents to the non-protic solvent used in the electrolyte, by using a polymeric or oligomeric anion as A - , by choosing an A - such that HA is insoluble in the electrolyte, by adding to the polymer a proton-releasing or absorbing species, such as, for example, an amine NR 3 (of appropriate base strength) and/or (HNR 3 ) + A - which would control or eliminate deprotonation.
The polyaniline species useful in the practice of this invention include all polymeric species containing backbone chains having repeating units ##STR21## and thus include alkyl, aryl, alkaryl and aralkyl substituted aniline polymers as well as other modifications. While such materials have not yet been examined, it is believed that species having subunits such as ##STR22## may also be useful. Heteroatomic substituents are also possibly useful.
The particular forms of the foregoing polyanilines and modified polyanilines which are preferred for the preparation of electrochemical electrodes in accordance with the invention are those wherein each nitrogen of the polymer chain has one but only one hydrogen atom associated with it. Such association may be either hydrogenation or protonation or combinations of both overall in the polymer. Accordingly, polymers formed from 1A and 2S" units are preferred.
Polymers wherein more than one hydrogen atom is associated with some or all of the polymer chain nitrogens can likely also be useful but are less preferred. This is due to the need to eliminate hydrogen species upon oxidation as discussed above.
It will be understood that a description of the molecular structure and formula of an individual polymer is necessarily imprecise since it is difficult to control the precise stoichiometry of redox and protonation reactions. Notwithstanding this, it is believed that those of ordinary skill in the art will understand that the requirement that the chain nitrogen atoms of a polyaniline have one but not more than one hydrogen atom is clear in a practical and preparative sense. That is, such definition permits a small percentage of polymer chain nitrogens to have more or less than one hydrogen atom providing the polymer species functions in accordance with the present invention. The effect of increasing percentages of nonconformance with the chain nitrogen to hydrogen ratio is to decrease electrochemical performance or to produce unwanted hydrogen species in the electrolyte; neither effect is desirable although neither is necessarily harmful in practice when evidenced in minor degree.
In view of the foregoing, the requirement that each chain nitrogen have one hydrogen atom in association and that the electrode active materials "consist essentially of" such form is to be interpreted in accordance with practical considerations attending electrochemical cell manufacture. In general, if less than about 10%, preferably less than about 5% and even more preferably less than about 2% of the chain nitrogen atoms have more or less than one hydrogen atom in association, then the polymer will be considered to meet the foregoing requirement.
When a polyaniline is employed as a cathode active material suitable anodes include polyaniline itself, separately or in a unitary mass, together with many other materials. Such anode materials must be stable in the cell environment, must be ionizable within the context of the electrochemical reaction and must have a reduction potential more negative than the cathode, for polyaniline, generally less than +0.64 volts. Such materials may be found, inter alia, from review of the Handbook of Chemistry and Physics, CRC Co., 52nd ed. at p. D-111 et seq. Exemplary materials include Cd, Pb, Zn, Mn, Ni, Sm, Ti, Mg and materials such as hydrazine.
When the polyaniline is used as an anode, polymers may serve as cathode including p-doped polyacetylene and polyparaphenylene, organics such as benzoquinone, O 2 , H 2 O 2 and metal oxides having, generally, positive reduction potentials (greater than the polyaniline anode). Of course the materials must be stable but ionizable within the context of the cell. Such metal oxides include MnO 2 , PbO 2 , Ni 2 O 3 and others.
A wide variety of electrolytes may be employed which have effective stability, mobility and activity in the electrochemical cells of the invention. Selection of suitable electrolytes including solvent and solvent components is within the skill of the routineer who will be able to select such materials to be compatible with the electrodes and the aprotic cell environment. Preferred electrolytes include alkali metal salts in propylene carbonate and other aprotic solvents.
The employment of electrochemical electrodes in secondary batteries, fuel cells, sensors and other electrochemical cells is well within the level of skill in the art from a review of this specification. A number of uses for such electrodes are found in Handbook of Batteries and Fuel Cells, Linden ed., McGraw-Hill (1984) which is incorporated herein by reference.
The present invention is illustrated by the following examples which are not intended to be limiting.
EXAMPLE 1
Synthesis of Polyaniline Films Polymerized on Platinum Substrates
A standard 3-electrode configuration was used to prepare polyaniline films. An SCE was used as the reference electrode, Pt foil was used as the counterelectrode (total area=1 cm 2 ), and Pt foil was adopted as the working electrode (total area=1 cm 2 ) in 20 ml of 1M HClO 4 . The working electrode was fixed 0.5 cm from the counterelectrode. One mililiter of distilled aniline was added to the electrolyte and stirred until the aniline was dissolved (pH approximately 0). Potential limits were set at -0.20 V and +0.75 V vs. SCE and potential scanning at 50 mvs -1 between the two limits was begun. Scanning was stopped when the film reached the desired thickness (approximately 45 scans, i.e. 30 minutes). The last scan was stopped at 0.4 V on the oxidation cycle. The resulting film was green to the eye at a potential of 0.4 V, corresponding to the approximate composition of an emeraldine salt form of polyaniline.
EXAMPLE 2
Preparation of Electrolyte
An electrolyte solution of 1M LiClO 4 in propylene carbonate was prepared. Anhydrous lithium perchlorate (LiClO 4 ) (Alfa- Ventron, Danvers, Mass.) was purified by weighing out 31.92 gm in a dry box and transferring it to a 500 ml round bottomed flask. The flask was then removed from the dry box and attached to a vacuum line (pressure approximately 2 microns). The flask was heated gently under dynamic vacuum until the LiClO 4 melted. After cooling to room temperature (approximately 10 min) the LiClO 4 was melted two more times under identical conditions. Propylene carbonate (C 4 H 6 O 3 ) (Aldrich Chemical, Milwaukee, Wis.) was purified by spinning band vacuum distillation. A typical distillation involved approximately 300 ml of propylene carbonate in a one meter nickel spinning band column (Nester-Faust) equipped with a variable ratio reflux head (set to a two to one ratio). After evacuating the system the temperature was increased to 100° C. The first 50 ml of propylene carbonate collected were discarded. The next 200 ml were collected and stored for use in an evacuated bulb. The propylene carbonate and the flask containing the LiClO 4 were transferred to the dry box. The electrolyte was then prepared by dissolving the LiClO 4 in 300 ml of propylene carbonate under dry box conditions.
EXAMPLE 3
Pre-Treating and Electrochemical Conditioning of Polyaniline Electrode
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
Polyaniline film on a Pt substrate was synthesized as described in Example 1. The film was then immersed in 1M HClO 4 for 12 hours in air to ensure that the polyaniline was homogeneously in a salt form. After 48 hours of pumping in dynamic vacuum, a 3-electrode electrochemical cell was constructed in the dry box. Both reference and counter electrodes were Li metal. Li was scraped with a knife in the dry box prior to use to remove any oxides from its surface. The working electrode was polyaniline film on the Pt foil. The three electrodes were immersed in a 20 ml beaker containing 10-15 ml of 1M LiClO 4 /propylene carbonate electrolyte. The distance between the polyaniline electrode and the counter electrode was approximately 1 cm. The open circuit potential, V oc , of the polyaniline immediately after construction was 3.51 V vs. Li/Li + .
(B) Electrochemical Conditioning of the Polyaniline Electrode
The polyaniline electrode was pre-conditioned. The film was first reduced by applying a constant potential of 2.5 V vs. Li/Li + (approximately -0.79 V vs. SCE) for 10 min. The potential limits were then set at 2.0 V and 3.2 V. A 50 m V/s scan rate was next applied to the cell, i.e. 48 sec for one complete oxidation/reduction cycle. The upper limite was successively increased to 4.0 V by 0.2 V increments (2-3 cycles at each voltage increment). The cyclic voltammogram obtained was completely reversible for each of these cycles.
Color changes were evidenced from essentially colorless (approximately 2.5 V vs. Li/Li + ) to green (approximately 3.1 V vs. Li/Li + ) to blue (approximately 3.7 V vs. Li/Li + ) in the anodic (oxidative) scan.
EXAMPLE 4
Polyaniline (1A Form) Synthesized Electrochemically in a Propylene Carbonate Electrolyte
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
The polyaniline film from Example 3 was reduced in the dry box by applying a potential of 2.5 V vs. Li/Li + (approximatly -0.79 V vs. SCE) to the film for one hour. This resulted in the production of an essentially colorless polyaniline believed to comprise 1A forms. The film was then rinsed in 0.1M NH 4 OH for 5 hours in an argon filled glove bag to ensure removal of all traces of HClO 4 from the film and its conversion to pure 1A form. After 48 hours of pumping in a dynamic vacuum, a three electrode electrochemical cell was constructed in the dry box as described in Example 3. The open circuit potential of the polyaniline electrode was 2.90 V vs. Li/Li + (approximately -0.39 V vs. SCE).
(B) Electrochemical Properties of the Electrode
First, an initial potential of 2.5 V vs. Li/Li + was applied to the polyaniline electrode to ensure it was in the completely reduced form 1A. A potential scan of 50 m V/s was then applied between 2.5 V and 3.2 V. Two complete cycles were performed. The upper limit was then increased to 4.0 V by increments of 0.2 V. The amount of charge in and out during oxidation and reduction between 2.5 V and 4.0 V was obtained by integrating the I-V curve using the "cut and weigh" method. During the anodic (oxidative) scan, the color changed from essentially colorless and transparent (at 2.5 V) to green (at 3.1 V) to blue (at 3.7 V). 5.44×10 -3 coulombs were passed during the oxidation cycle. 5.21×10 -3 coulombs were passed during the reduction cycle. The coulombic efficiency was therefore 95.8%.
EXAMPLE 5
Polyaniline (Approximate Emeraldine Salt Form) (Synthesized Electrochemically and Chemically)
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
The polyaniline film from Example 4 was oxidized in the propylene carbonate (PC)/LiClO 4 electrolyte by applying a potential of 3.30 V* vs. Li/Li + to the polymer electrode for 5 minutes to convert it to an approximate composition corresponding to a green emeraldine salt form. The film was then rinsed with 1M HClO 4 , in which PC is soluble, and was then washed with 150 ml of fresh 1M HClO 4 for 12 hours (with no exclusion of air) to ensure that it was in a homogeneously protonated salt form. After 48 hours pumping in dynamic vacuum, it was placed in the PC/LiClO 4 /Li cell and the open circuit potential of the polyaniline electrode was found to be 3.50 V. The increase in potential from 3.30 V to 3.50 V is believed to be due to partial oxidation of the polyaniline during the HClO 4 /air treatment.
(B) Electrochemical Properties of the Electrode
The cell was recylced using the same procedure described in Example 4. 5.81×10 -3 coulombs was passed during the oxidation cycle. 5.43×10 3 coulombs was passed during the reduction cycle. The coulombic efficiency was therefore 93.5%.
EXAMPLE 6
Polyaniline 1A Form Synthesized Electrochemically in an Aqueous Electrolyte
100 ml of 1M ZnCl 2 solution and 100 ml of distilled water were both deaerated by passing argon through the solutions for 45 minutes. The polyaniline electrode from Example 5 was first washed with approximately 10 ml of the ZnCl 2 electrolyte to remove the PC electrolyte. It was then placed in 100 ml of fresh equeous ZnCl 2 and reduced by applying a potential of 0.7 V vs. Zn/Zn 2+ (i.e. approximately 2.98 V vs. Li/Li + ) to the polymer electrode for approximately 30 minutes. This converted it to the essentially colorless 1A form. The experiment was carried out in an argon filled glove bag. The ZnCl 2 electrolyte solution was found to have a pH of approximately 4.5. Zn was used as a counter electrode during reduction of the polyaniline. The potential then rose to 0.80 V vs. Zn 2+ /Zn during 10 seconds due to removal of polarization and related effects and then remained constant at this value for 5 minutes before it was washed with distilled water. After 48 hours pumping in a dynamic vacuum, a three electrode electrochemical cell was constructed in the dry box as described in Example 3. The open circuit potential of polyaniline was found to be 2.90 V vs. Li/Li + (approximately -0.39 V vs. SCE).
(B) Electrochemical Properties of the Electrode
First an initial potential of 2.5 V vs. Li/Li + was applied to the polyaniline electrode. Then a potential scan with 50 mv/s scan rate between 2.5 V and 3.5 V was applied to the polymer electrode for 4 cycles. The upper limit was then increased to 4.0 V. 5.26×10 -3 coulombs were passed during the oxidation cycle. 5.09×10 -3 coulombs were passed during the reduction cycle. The coulombic efficiency was therefore 96.8%.
EXAMPLE 7
Approximate Emeraldine Base Form of Polyaniline Synthesized Electrochemically and Chemically
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
The polyaniline film from Example 6 was oxidized at 3.5 V for 5 minutes vs. Li/Li + in a dry box in PC electrolyte to convert it to an approximate emeraldine salt form. The film was then rinsed with dilute NH 4 OH (0.1M) to remove PC electrolyte. It was then washed with 50 ml of dilute NH 4 OH solution for 6 hours. The color of the polyaniline film changed from green to blue as it was converted from an approximate emeraldine salt form to an approximate emeraldine base form. It should be noted that even water will deprotonate 2S' and 2S" forms of polyaniline; however, the NH 4 OH solution was used as a precautionary measure to ensure complete deprotonation. After 24 hours pumping in dynamic vacuum, a three electrode electrochemical cell was constructed in a dry box as described in Example 2. The open circit potential of the polyaniline was 2.81 V vs. Li/Li + . As can be seen from FIG. 5, the potential of a polyaniline film having a composition approximately that of emeraldine, decreases significantly with decreasing protonation.
(B) Electrochemical Properties of the Electrode
First, an initial potential of 2.5 V vs. Li/Li + was applied to the polyaniline electrode for 10 minutes to reduce it to the maximum possible extent. It had a blue color whereas the emeraldine salt form at the same potential is essentially colorless. This is indicative of the presence of non-reduced quinoid groups. A potential scan with 50 m V/s scan rate between 2.5 V and 3.5 V was applied to the polymer electrode for 6 cycles. The upper limit was then increased to 4.0 V. During the anodic (oxidative) scan, the color changed from blue (at 2.5 V) to green-blue (at 3.2 V). 3.89×10 -3 coulombs were passed during the oxidation cycle. 3.68×10 3 coulombs were passed during the reduction cycle. The coulombic efficiency was therefore 94.6%.
EXAMPLE 8
Approximate Emeraldine Salt Form Synthesized Electrochemically and Chemically
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
The polyaniline film from Example 7 (i.e. approximate emeraldine base) was oxidized by applying a potential of 3.5 V vs. Li/Li + to the polymer electrode for 5 minutes. It was then converted to the approximate emeraldine salt form using the same HClO 4 treatment as described in Example 5. The open circuit potential of the polyaniline was 3.53 V vs. Li/Li + .
(B) Electrochemical Properties of the Electrode
The polyaniline was then cycled between 2.5 V and 4.0 V (vs. Li/Li + ). At 2.5 V it was essentially colorless while at 4.0 V it was blue. 5.66×10 -3 coulombs were passed during the oxidation cycle. 5.29×10 -3 coulombs were passed during the reduction cycle. The coulombic efficiency was therefore 93.5%.
EXAMPLE 9
Approximate Emeraldine Base Form Synthesized Electrochemically and Chemically
(A) Synthesis of Desired Composition of "Polyaniline" Electrode
The polyaniline film from Example 8 was oxidized at 4.0 V vs. Li/Li + for 3 minutes in a dry box in the PC electrolyte. It was then converted to the approximate emeraldine base form using the same NH 4 OH treatment as described in Example 7. The open circuit potential of the polyaniline electrode in the cell was 2.82 V vs. Li/Li + .
(B) Electrochemical Properties of the Electrode
The polyaniline was then cycled between 2.5 V and 4.0 V (vs. Li/Li + ). 3.16×10 -3 coulombs were passed during the oxidation cycle. 2.92×10 -3 coulombs were passed during the reduction cycle. The coulombic efficiency was therefore 92.4%.
It should be noted that in Experiment 7, the polyaniline was first oxidized at 3.5 V before treatment with NH 4 OH. This is consistent with more 2A units being formed in the present experiment than in Experiment 7, resulting in a smaller capacity in this experiment. This is consistent with the effect that the higher the oxidation potential employed, the smaller the capacity.
EXAMPLE 10
Relative Capacity of Different Polyaniline Forms
The amount of charge out during the cathodic scan of polyaniline in different forms as described in Examples 4 to 9 is tabulated below. All samples were oxidized from 2.5 V to 4.0 V (vs. Li) to give Q in , i.e. the charge involved in the oxidation (charge) cycle. Then they were reduced from 4.0 V to 2.5 V vs. Li to give Q out , i.e. the charge involved in the reduction (discharge) cycle. All experiments were carried out under essentially identical conditions. In each of Examples 4-9, the recycling was conducted about 5 times. There was no significant change in the number of coulombs involved from those listed.
__________________________________________________________________________Q.sub.out Q.sub.in Approximate(Coulombs) (Coulombs) Composition ofExample(Reduction) (Oxidation) Q.sub.out /Q.sub.out #5 Polyaniline used__________________________________________________________________________4 5.21 × 10.sup.-3 5.44 × 10.sup.-3 96.0% [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].su b.2a5 5.43 × 10.sup.-3 5.81 × 10.sup.-3 100.0% ##STR23##6 5.09 × 10.sup.-3 5.26 × 10.sup.-3 93.7% [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].su b.2a7 3.68 × 10.sup.-3 3.89 × 10.sup.-3 67.8% ##STR24##8 5.29 × 10.sup.-3 5.66 × 10.sup.-3 97.4% ##STR25##9 2.92 × 10.sup.-3 3.16 × 10.sup.-3 53.8% ##STR26##__________________________________________________________________________Approximate Composition of Approximate Composition ofExampleReduced Form (at 2.50 V) Oxidized Form (at 4.0__________________________________________________________________________ V)4 [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].sub.2a ##STR27##5 [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].sub.2a ##STR28##6 [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].sub.2a ##STR29## ##STR30## ##STR31##8 [(C.sub.6 H.sub.4)N(H)(C.sub.6 H.sub.4)N(H)].sub.2a ##STR32##9 ##STR33## ##STR34##__________________________________________________________________________ | Electrochemical electrodes are provided having improved capacity and efficiency. In accordance with preferred embodiments polyaniline species wherein oxidation and hydrogenation levels are carefully controlled are formulated into such electrodes and into batteries and fuel cells. | 2 |
BACKGROUND
[0001] 1. Field of the Invention
[0002] The present invention relates generally to a kitchen tool for food core extraction, and particularly for hollowing out the inside of vegetables and/or fruits and other foods, leaving a cavity or a hole as desired.
[0003] The general area of kitchen tool corers is not new. Hollowing out a zucchini can be challenging, and very unsuccessful. One apple corer having four molded plastic components are fitted together. They are a hollow cutting tube, a core remover slidable along the cutting tube, a handle attached at the end of the cutting tube, and a compression plug inserted at the same end for locking the handle in place. The tip of the cutting tube has serrated teeth for smooth boring into the apple. In operation, the handle is oscillated while applying pressure to it. This causes the cutting tube to bore through the apple.
[0004] While popular, the hollow cutting tube variety wastes material, since corers do not actually need a full tube. Moreover, the “compression plug” for locking the handle in place and the additional parts make this type of corer wasteful and complicated. Further oscillation of the handle makes this an awkward and unnecessarily hard way to extract the meat.
[0005] Some corers can better be categorized as melon-ballers, melon-cutters, and zucchini corers where they are used primarily to create a decorative effect rather than to solve a basic food preparation problem.
[0006] Other corers have a coring assembly comprising a continuous ring of thin stainless steel circle or ring. The ring is joined to, or is an extension of, a thin zig-zag band portion which is joined to the handle. While an improvement, this type still lacks ease of use, tearing the core out of the fruit or vegetable instead of an easy insert and slice removal. Still most corers use a non-elegant once through method of leaving the object with a through hole, thus making it difficult to contain ingredients and forcing the food prepared to look less appealing.
[0007] Another corer comprises a cylindrically shaped or tubular body with an axially-slidable side member that alternately ejects and retracts a core-slicing or cutting structure removable of a portion of the core of a fruit, and provided with another axially-slidable ejector member. This type of corer is good for straight through boring and is a slight improvement on the tubular boring corer. However, most designs still suffers from the heavy wasteful inelegant tubular body and complications in the practical application of extraction of the core with the axially-slidable side members. The corers which are not totally tubular, are straight through corers, leaving a hole and not a cavity. The designs which leave a cavity leave an incomplete core which must be ripped out forcibly. Other types of corers do not allow that corer to be inserted smoothly and then attaching to the flesh to remove the body of a zucchini or other base for fill with other ingredients. Another type is a one piece tool for boring through an apple but not removing the core for filling, only a straight through core removal leaving a hole.
[0008] At times, food preparation requires the creation of an internal cavity for inserting ingredients for creative and ethnic dishes. Current corers punch a hole through the food item on both ends, not allowing inset ingredients, therefore losing all the precious healthy succulence in food dishes. A food item that can be filled with additional ingredients to make a healthy and delicious dish. A family favorite is stuffed zucchini, where the extraction of the body of the zucchini and insertion of several various ingredient options are required, followed by a slow cook for several hours. What are needed are coring feature which allow removal of seeds from vegetables such as cucumbers, which in some cases are required or needed for health requirements. Many corers on the market, allow “punching” a core out, but what is sometimes needed is a cavity for placement of other ingredients, without additional work or effert.
[0009] There is still need for a kitchen tool that can penetrate through the flesh and remove the body from a vegetable efficiently with a comfortably. Some settle for a tool difficult to assemble, use, disassemble and to clean, while other use a combination of multiple tools. For instance, in the past, a corer and a potato peeler would give you a good result. The flesh can be eaten, thrown away or used in a recipe. The precision of the tool would make the task much more efficient and a lot simpler. What is needed is an extracting corer, a one piece, no assembling or disassembling, possibly adjustable and without any attachments. What is needed is an easy to use, fast and simple to clean, without assembling/disassembling and still just hollowing out a a given fruit or vegetable. What is needed is a clean corer, cutting and attaching to the flesh in order to remove the body in the center for use in preparing food for filling
SUMMARY
[0010] The present invention discloses a system for single piece device for coring fruits and vegetables and food comprising a handle, thin flat stem coupling an annular cutting ring to the handle, a serrated cutting edge on the distal end of the annular cutting ring, and a flattened curved hook element coupled to the opposite end of the annular cutting ring, hook tip extending substantially toward the cent of the ring axis. The annular cutting ring jagged cutting edge is inserted in the food object to be cored, to the depth desired and the axially rotated allowing the curved hook to circumscribe the inside food object end freeing the food core for hollowing.
[0011] An aspect of the single piece device provides for extracting the inside meat without a full penetration for insertion of alternate food ingredients.
BRIEF DESCRIPTION OF DRAWINGS
[0012] Specific embodiments of the invention will be described in detail with reference to the following figures.
[0013] FIG. 1 a is a side view of the extracting corer in accordance with an embodiment of the invention.
[0014] FIG. 1 b is a top view of the extracting corer in accordance with an embodiment of the invention.
[0015] FIG. 2 a is an enlarged side view of the extracting corer detailing the serrated edge and the core extract hook in accordance with an embodiment of the invention
[0016] FIG. 2 b is an enlarged front view from the distil end of the extracting corer in accordance with an embodiment of the invention
[0017] FIG. 3 is a perspective view an extracting corer in accordance with an embodiment of the invention
DETAILED DESCRIPTION
[0018] In the following detailed description of embodiments of the invention, numerous specific details are set forth in order to provide a more thorough understanding of the invention. However, it will be apparent to one of ordinary skill in the art that the invention may be practiced without these specific details. In other instances, well-known features have not been described in detail to avoid unnecessarily complicating the description.
[0019] Objects and Advantages
[0020] There are several objects or advantages of the present invention. First, it can come in one piece tool for efficiency and ease to perform a task.
[0021] This corer is simpler for hollowing out the flesh from inside of the zucchini than any other tool invented. An aspect of the invention design has a curved triangular core extraction hook that enables the inside to be pulled out of the food object after the core flesh has been completely severed, core removal without ripping flesh. This makes it easier to remove the flesh without damaging other portions and consistency with just one tool. For example, one would be able to core many zucchini in a short period of time. Allowing the zucchini to be hollowed without breaking the skin or leaving too much of the flesh inside which makes it hard to fill for your recipes. Further objects and advantages of our invention will become apparent from a consideration of the drawings and ensuing description of the invention.
[0022] It is another object of the present invention to provide embodiments designed for simplicity of use, even elegance. The tool should be self evident as to its function. The tool should be easily cleanable.
[0023] It is yet another object of the present invention to reduce time in the coring process. A simple quick operation should render the food cored efficiently. Yet provide a cavity for a more complex or exotic dish.
Embodiments of the Invention
[0024] FIG. 1 a and FIB. 1 b are side view and top views respectively of the extracting corer in accordance with an embodiment of the invention.
[0025] The handle 109 is coupled to a thin stem 107 . The stem 107 may be flat, with or without curvature, with or without cutting edges, or simply a sturdy rod construction. The stem may be coupled to the handle in a fixed configuration or a flexible pivotal coupling allowing the user to unsnap and rotate the handle 109 to provide the user with a corkscrew handle purchase. The stem 107 distal end is coupled to an annular ring element 103 . The annular ring 103 serves several purposes. The ring 103 distal edge 101 is a cutting edge and may be sharpened in many ways. The annular ring 103 opposite or handle facing edge is coupled to a curved cutting surface core cutting and extract hook 105 . The hook 105 , ring 103 and stem 107 can be make from typical metal materials used in cutlery. The handle 109 can be composed of metal, plastic, composite, or most any rigid material which can sustain a torque required for cutting fruits, vegetables or other food items.
[0026] FIG. 2 a and FIG. 2 b are an expanded side view and an expanded front view of the distil end of the extracting corer respectively detailing the serrated edge and the core extract hook in accordance with an embodiment of the invention
[0027] The annular ring 203 is rigidly coupled to the stem 205 distal end. The rings 203 cutting edge 201 is shown serrated as it servers to cut through the interior of a food item. This can be done with a hand twisting back and forth with some forward force of the device. Once the ring 203 is to the desired depth, a complete hook rotation will sever the core, since the sharp triangular curved hook penetrates to the core axis center, and allow a smooth tear free extraction. The handle 207 is shown coupled rigidly to the stem 205 but this will vary on other embodiments, where the handle is coupled to unsnap from the stem and pivotably coupled such that the hand can be rotated and used perpendicular to the stem, as in the case of a bottle cork screw.
[0028] FIG. 3 is a perspective view an extracting corer in accordance with an embodiment of the invention
[0029] Not shown in this embodiment, the annular ring 305 can be adjustable having a curling ring with wrap stabilizers for varying rind 305 diameters. Thus a small vegetable or large fruit will have different diameter cores to extract, accommodating size with the same tool. Also, the stem 307 can be slidably adjustable withdrawing inside the handle for longer or short food insertion depth. Also not shown are the industrial food processing attachment for coring mass quantities of fruits and or vegetables.
[0030] Operation
[0031] The invention tool would be inserted, the serrated end of the corer first, into the food item while rotating the handle back and forth. Upon reaching the desired depth of the food item, the corer is rotated axially one complete circle, which severs the core from the food. The core extract hook of the corer first cuts and then attaches to the inside core, which is then withdrawn and core removed. Food ingredients can then be added to the cavity created.
[0032] Therefore, while the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this invention, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Other aspects of the invention will be apparent from the following description and the appended claims. | The present invention discloses a one piece food corer with a hook design providing an efficient and elegant tool for coring food. The basic design is without attachments or other accoutrements. The user of the corer is able to use one tool for a specific purpose, hollowing out the flesh from a vegetable or fruit. | 0 |
FIELD OF THE INVENTION
This invention relates to improvements in a semiconductor laser having a structure which avoids reduction of the performance and life of the semiconductor laser resulting from degradation by stresses acting on a diode chip due to the shape thereof upon mounting the semiconductor laser on a heat sink.
DESCRIPTION OF THE PRIOR ART
FIGS. 1a and 1b are vertical sectional views each of which shows the structure of a prior-art, mesa-stripe geometry semiconductor laser. On an N-type GaAs substrate 1, epitaxial layers are successively grown of an N-type Ga 1-x Al x As (0<x<1) layer 2, P-type GaAS layer 3, P-type Ga 1-x Al x As layer (0<x<1) 4 and P-type GaAs layer 5. Further, the surface of the epitaxially grown layers on one or both sides of a central region 11 is selectively etched by photolithography so as to form a groove or grooves. Thus, a mesa-shaped semiconductor for supporting a diode chip 12 (and 12') is formed, which stands adjacent to a mesa-shaped semiconductor containing a current-conducting region 11 and separated by the etched groove. Subsequently, the entire surface of the epitaxially grown layers formed with the mesa-shaped portions is coated with SiO 2 6 as a dielectric layer. Thereafter, in order to conduct an operating current without spreading, the SiO 2 layer 6 on the current-conducting mesa 11 has only the central part removed with the shoulder part remaining as illustrated in FIG. 1a or 1b. Thereafter, an electrode 7 and an electrode 8 are respectively formed by vacuum evaporation, the resultant substrate is split into a plurality of elements by cleavage or scribing, and the individual split element (diode chip) is bonded to a heat sink of copper 10 by solder 9. In the prior-art mesa-stripe geometry semiconductor laser described above, the SiO 2 layer 6 is left at the shoulder of the mesa 11, and hence, the supporting mesas 12, 12' and the current-conducting mesa 11 have equal heights. In this respect, the following disadvantages occur upon bonding the diode chip to the heat sink 10 by the solder 9.
(A) Since pressure is applied in the bonding to the heat sink, a stress is exerted on the active region of the P-type GaAs layer 3 under the current-conducting mesa 11. (b) When the SiO 2 layer 6 remains at the upper shoulder of the current-conducting mesa 11, a stress is exerted by the edge of the SiO 2 layer. (c) Due to heating for the soldering, stresses which are caused by respectively different thermal expansions of the heat sink 10, solder 9, electrode 7 and SiO 2 film 6 are exerted on the active region of the P-type GaAs 3 as in (a). When the stresses are exerted on the active region of the P-type GaAs layer 3 in this manner, laser oscillation does not occur. Even if the oscillation is possible and no problem is posed as to the performance, the life will become short.
In a planar-type semiconductor laser, the supporting mesa is not provided and a heat sink is mounted on an electrode on a diode chip through solder unlike the case of the mesa-type semiconductor laser. As in the foregoing, therefore, stresses are exerted on an active region, so that the planar-type semiconductor laser is incapable of laser oscillation and becomes short-lived.
SUMMARY OF THE INVENTION
This invention has been made in order to eliminate the disadvantages in the prior-art semiconductor lasers.
This invention is so constructed that a semiconductor layer of a current-conducting portion in a diode chip formed by an etched groove is lower than a supporting mounting semiconductor layer and that no dielectric layer remains on the upper surface of the current-conducting semiconductor layer.
When the semiconductor laser is formed with such construction, there is prevented degradation of laser oscillation performance and reduction of life which are attributed to a stress exerted on the active region of the current-conducting semiconductor layer upon bonding the diode chip to a mount. Moreover, influences on the active region by a stress resulting from etching the dielectric layer remaining on the current-conducting semiconductor layer and a stress resulting from to different coefficients of thermal expansion of the heat sink, solder, an electrode and the dielectric layer at the time of heating for soldering can be obviated, so that an enhancement in the performance of laser oscillation and a long life can be further realized.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a and 1b are vertical sectional views each showing the structure of a prior-art semiconductor laser,
FIGS. 2a and 2b are vertical sectional views each showing the structure of an embodiment of the semiconductor laser of this invention,
FIG. 3 is a vertical sectional view of another embodiment of the semiconductor laser of this invention, and
FIGS. 4, 5 and 6 are vertical sectional views each showing the structure of a further embodiment of the semiconductor laser of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiment 1:
FIGS. 2a and 2b are vertical sectional views of embodiments of this invention both of which are applied to the mesa-stripe geometry semiconductor laser. On an N-type GaAs substrate 1; N-type Ga 1-x Al x As layer (0<x<0.3) 2, P-type GaAs layer 3, P-type Ga 1-x Al x As layer (0<x<0.3) 4 and P-type GaAs layer 5 are successively formed by liquid epitaxial growth. Grooves are formed on both sides of the central part of the grown layers by photolithography, to form supporting mesas 12 and 12' through the grooves (in FIG. 2b, only one supporting mesa is formed with one groove). On the entire surface of the semiconductor wafer formed with the mesas (including a current-conducting mesa 11), an SiO 2 film 6 is formed to a thickness of about 5000 A by chemical vapor deposition (CVD). Subsequently, using photolithography, the SiO 2 film 6 is completely removed only at the top part of the current-conducting mesa 11. Thereafter, an electrode 7 and an electrode 8 are respectively formed by vacuum evaporation, the semiconductor wafer is split into chips of 400 μm×400 μm, and each chip is bonded to a heat sink 10 with solder 9. In this way, the current-conducting mesa 11 is spaced from the heat sink 10 and becomes lower than the supporting mesas 12 and 12' by about 5000 A corresponding to the thickness of the SiO 2 film 6. In consequence, in bonding the diode chip to the heat sink, stresses are prevented from acting on the active region of the P-type GaAs 3.
Embodiment 2:
FIG. 3 is a view of another embodiment of this invention. On an N-type GaAS substrate 1; N-type Ga 1-x Al x As layer (0<x<0.3) 2, P-type GaAs layer 3, P-type Ga 1-x Al x As layer (0<x<0.3) 4 and P-type GaAs layer 5 are successively grown by liquid epitaxial growth. Using photolithography, supporting mesas 12 and 12' and a current-conducting mesa 11 are formed. Subsequently, only the current-conducting mesa 11 is etched with a known etchant containing phosphoric acid by the use of photolithography, to partially or wholly reduce the height of this mesa as shown in FIG. 3. Thereafter, an SiO 2 film 6 being about 5000 A thick is formed on the entire mesa-forming surface by the CVD process, and the SiO 2 film 6 is completely removed only at the top surface of the current-conducting mesa 11 by photolithography. Further, an electrode 7 and an electrode 8 are respectively deposited, the substrate is split into diode chips of 400 μm×400 μm, and each diode chip is bonded to a heat sink 10 with solder 9. In this way, the height of the current-conducting mesa 11 becomes less than the height of the supporting mesas 12, 12' by the sum between about 5000 A corresponding to the thickness of the SiO 2 film 6 and the etched component of the mesa 11.
According to any of the embodiments illustrated in FIGS. 2a, 2b and 3, owing to the fact that the height of the current-conducting mesa 11 is made less than that of the supporting mesas 12, 12' and the fact that the SiO 2 film on the top of the current-conducting mesa 11 is completely removed, all the stresses occuring when the chip is set on the heat sink act on the supporting mesas 12, 12', and no stress acts on the current-conducting mesa 11. Besides, since the SiO 2 film 6 on the current-conducting mesa 11 is completely removed, the stress has been reduced which occurs on account of the differences of the thermal expansions of the metal, SiO 2 and semiconductors at the time of heating for bonding the diode chip to the heat sink with the solder. Thus, the stresses acting on the active layer of the P-type GaAS 3 have been significantly relieved. As the result, the occurrence of dark-line defects and dark-spot defects which arise in the active layer due to the stresses has been lowered, the yield rate of elements capable of oscillation has been enhanced by about 40%, and it has become possible to reliably fabricate the elements having a life longer than 5000 hours. In the embodiment shown in FIG. 3, it is not prefered from the viewpoint of thermal conductivity to excessively increased the etching depth of the crystal forming the current-conducting mesa. It has been experimentally verified that, when the etching depth is increased to beyond a certain extent, the solder coagulates, a clearance is formed between the heat sink and the current-conducting mesa, and the thermal conductivity is degraded. The absence of the contact between the solder on the heat sink and the current-conducting mesa is demeritorious from the point of thermal conductivity, but it is meritorious from the point of stresses acting in the element because no pressure is applied to the laser active region upon bonding the semiconductor laser chip to the heat sink. In some cases, therefore, such expedient is of useful value. Although the supporting mesa is disposed on only one side of the active region defining mesa in the embodiment of FIG. 2b and the pair of supporting mesas are disposed on both the sides of the active region defining mesa in the embodiments of FIGS. 2a and 3, the number of supporting mesas may be further increased, and the arrangement of the supporting mesas can be provided as desired. Further, although the foregoing embodiments exemplify the semiconductor lasers of the GaAS-GaAlAs system, a very small amount of Al can be contained in the GaAs active layer as is known. This invention is also applicable to the mesa-type semiconductor laser employing any other semiconductor material.
Embodiment 3:
FIG. 4 shows an embodiment in the case of a diffusion type planar semiconductor laser in which a current path is formed by employing diffusion.
After cleaning the surface of an N-type GaAs substrate 1 by etching, Sn-doped N-type Ga 1-x A x As layer (x˜0.3) 2', P-type GaAs layer 3, Ge-doped P-type Ga 1-x Al x As layer (x˜0.3) 4 and Sn-doped N-type GaAS layer 5 are epitaxially grown on the substrate in the order mentioned. Subsequently, an oxide film (of SiO 2 or Al 2 O 3 ) is formed on the resultant wafer by the CVD process. Using photolithography, the oxide film is partially removed to form a diffusion window. The diffusion of Zn is carried out at 700° C. for 15 minutes, to form a diffused region 13. Subsequently, grooves or defects 14, 14', 15 and 15' are formed by photolithography and etching. Subsequently, an oxide film (of SiO 2 or Al 2 O 3 ) 6 is formed by the CVD process on the surfaces of supporting mesas 12, 12' (100 μm wide and 5 μm high) and a region constructing a planar semiconductor laser, 16 (300 μm wide and 5 μm high), the supporting mesas and the region having been formed through etching grooves and defects. Using photolithography, the oxide film is removed only at the top of the region forming the planar semiconductor laser 16. The top surface with the oxide film removed therefrom is somewhat (1-5 μm) etched, and Cr-Au 7 as a P-type electrode is formed on the surface by vacuum evaporation. The electrode material deposited on any other place is removed by etching. The GaAs substrate 1 has the lower surface polished and etched into a total thickness of 100-150 μm, and Au-Ge-Ni 8 is formed as an N-type electrode by the vacuum evaporation.
The semiconductor laser wafer thus formed is cleaned along the defects 15, 15' and in a direction orthogonal thereto to be split into chips of 600 μm×400 μm. The chip is bonded to a heat sink 10 with solder 9. At this time, the planar type semiconductor laser region 16 is lower than the supporting mesas 12, 12' by the amount removed by etching (1-5 μm) and the thickness of the oxide film formed on the supporting mesas 12, 12'. Therefore, the pressure at the bonding of the chip to the heat sink is fully applied to only the supporting mesas 12, 12'. As the result, no stress acts on the planar type semiconductor laser region 16, and it has become possible to obtain the elements of long life reliably.
Embodiment 4:
FIG. 5 shows an embodiment in the case of an ion implantation type semiconductor laser in which a portion other than a current path is put into a high-resistance region by the ion implantation.
The epitaxial growth on a GaAs substrate 1 is carried out as in Embodiment 3 with the exception that the last grown layer is changed to Ge-doped P-type GaAs layer 5'. Au (2-3 μm) is formed on this epitaxial grown layer as a protective film at the implantation of protons, and a high-resistance region 17 is formed by the known proton implantation. As described in Embodiment 3, the epitaxially grown layers are formed with grooves and defects 14, 14' and 15, 15' so as to form supporting mesas 12, 12' and a planar type semiconductor laser region 16. As explained in Embodiment 3, the top of the planar type semiconductor laser region 16 is somewhat (1-5 μm) removed by etching, and a P-type electrode 8 is formed by the vacuum evaporation and an oxide film by the CVD process. The crystal is split into chips of 600 μm×400 μm, and the chip is bonded to a heat sink with solder 9. At this time, as in Embodiment 3, the height of the planar semiconductor laser region 16 is less than that of the supporting mesas 12, 12'. Consequently, no stress has come to act on the planar type semiconductor laser region 16, and it has become possible to obtain elements of long life reliably.
Embodiment 5:
FIG. 6 shows an embodiment in the case of the planar type semiconductor laser of an InP-GaInAsP-InP system. On an N-type InP substrate 1; Ga x In 1-x As y P 1-y (x=0.12, y=0.23) layer 3, and P-type InP layer 4' are successively grown epitaxially. The crystal grown wafer is treated by the same method as stated in Embodiment 3, and the chip is soldered to a heat sink 10. As the result, as in Embodiment 3, no stress acts on a planar type semiconductor laser region 16, and the effect of rendering the life of the element longer has been achieved. | A semiconductor layer for supporting a diode chip of a semiconductor laser is formed to be higher than a semiconductor layer containing a current-conducting region, whereby stresses acting on the diode chip by mounting the diode chip are relieved to prevent degradation of performance and reduced life of the semiconductor laser. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of prior application Ser. No. 12/564,869, filed Sep. 22, 2009.
BACKGROUND OF THE INVENTION
[0002] A storm panel, also known as a hurricane panel, is used to protect a building opening, such as a door or window, during severe weather. The storm panel may also be used for security. There are many different types of mounting brackets used for storm panels installation. One method of mounting the storm panel is to install “F” track horizontally and/or vertically on the sides of the window or door openings. Then, bolts are placed in the track by sliding one bolt at a time by hand, the storm panel is mounted on the bolts, and the storm panel is secured with wing nuts.
BRIEF SUMMARY OF THE INVENTION
[0003] The present disclosure describes a strap to secure bolts at a proper spacing for installing a storm panel with mounting holes to an “F” track using bolts and fasteners, the bolts consisting of a bolt shaft connected to a bolt head, the track having a thickness and width for receiving the bolt heads, the storm panels being used to protect a building opening, and the strap comprising: a flexible material with two parallel sides, a top end connecting the parallel sides, a bottom end connecting the parallel sides, and a thickness between 1/64″ and ½″; and a plurality of circular openings for holding the bolts in place to mount the storm panel with mounting holes, the bolt heads held approximately 1/16 of an inch from the material, the openings centered between the two parallel sides of the material, the bolt heads being unable to pass through the material, the openings being equidistant from each other, and the openings having a smaller diameter than the bolt shaft diameter. The storm panels are typically used to protect building openings, such as windows and doors, during periods of bad weather. The storm panels may also be used for security purposes.
[0004] The bolts are threaded into the strap, where they are held in place. The bolt heads are then individually slid into the track and the strap is used to pull the bolts into the proper position to receive the storm panels. The storm panel is mounted on the bolts and then secured with fasteners such as wing nuts.
[0005] The strap has a thickness between 1/64″ and ½″ an inch. The thickness affects the ease of holding the bolts in place. The strap comprises a flexible material including leather, nylon, polypropylene, polyester, cloth, nylon webbing, polypropylene webbing, nylon webbing, or the like. Strap lengths can vary since the strap is cut during installation to match the length of track. The strap holes may be reinforced with grommets or strengthened with a coating to minimize wear from installing and removing bolts.
[0006] The strap has smaller hole diameters than the bolts it receives, so that the bolts are held tightly to prevent them from falling out. The strap openings are also properly spaced to match the storm panel openings. The bolts are threaded into the openings instead of being pushed through. Threading minimizes damage to the strap opening and enables the strap to better hold the bolt in place. The bolts are not fully threaded, so that a gap is left between the bolt head and the strap.
[0007] In one embodiment, the strap has a trapezoidal-shaped or rectangular shape, consists of a polypropylene webbing material, has a width of 1 inch, has a thickness between 0.50 and 0.55 inches, has a tensile strength of at least 800 pounds, has circular openings with a diameter of 3/16 of an inch for securely holding larger diameter ¼-20 sized bolts, the circular openings spaced approximately 6 inches apart, the bolts consisting of a bolt shaft connected to a bolt head, and the bolt heads being securely held approximately 1/16 of an inch from the strap.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 shows a cross-section side view with bolts threaded into a strap.
[0009] FIG. 2 shows a cross-section side view of a vertical storm panel installation.
[0010] FIG. 3 shows an exploded view of a horizontal storm panel installation.
[0011] FIG. 4 shows a front view of an embodiment of the strap.
DETAILED DESCRIPTION OF THE INVENTION
[0012] A storm panel is used to protect a building opening, such as a door or window, during severe weather. The storm panel may also be used for security. There are many different types of mounting brackets used for storm panel installation. One method of mounting the storm panel is to install “F” track horizontally and/or vertically on the sides of the opening. Then, bolts are placed in the track by sliding one bolt at a time by hand, the storm panel is mounted on the bolts, and the storm panel is secured with wing nuts.
[0013] One problem with the above method is that the bolts are loose in the track. Hence, the bolts may not lie perpendicular to the building and may not easily fit into storm panel mounting holes. The problem is especially acute in vertical installations where gravity forces the bolts to slide downward in the track. Therefore, mounting the storm panel requires at least one additional person to simply hold the bolts in place. Larger storm panels can come in lengths of 88 and 102 inches. When mounting these larger panels vertically, the bolts can be forced out of alignment during installation.
[0014] The present disclosure solves the above problem with a strap for use in mounting storm panels. The strap enables bolts to be installed in a track and held in place during storm panel mounting. Therefore, no one is required to hold the bolts in place during mounting. The strap also saves installation time and is more efficient when time is of the essence with a storm imminent. It allows one person to install storm panels when no other individual is available to help, no matter how long the storm panel is. This is very important on a commercial building.
[0015] One unexpected result of using the strap is that it prevents metal on metal wear, scratching, and nicking.
[0016] Another unexpected result of using the strap is that the storm panels are much quieter in bad weather. This is because the amount of “metal on metal” contact is reduced.
[0017] Another unexpected result is that the strap may be easily stored with the bolts installed. This saves time every time that the storm panels are reinstalled, after the first installation. Note that the strap is flexible and bending it does not affect its future utility. Also, the strap is able to last for many years because of its material of construction.
[0018] Another unexpected result is that it is now easier to place storm panels on each end of the building opening, allowing light or an object to pass through the unobstructed portion of the building opening.
[0019] Directions for using the present invention in a vertical installation are as follows. First, mount “F” track vertically onto the building on both sides of the building opening. Second, cut the strap to match the length of the track. Third, thread bolts through holes, leaving a 1/16 inch gap between the head of the bolts and the strap. Fourth, start at the top of the track, install the bolt heads in the track, and slide them down the track until all of the slack is taken out of the strap. Fifth, secure the uppermost bolt with a fastener at the proper height for storm panel installation. Sixth, repeat the second through the fifth steps for the other side of the building opening. Make sure that the bolts on both sides of the building opening are aligned at the same height. Seventh, place a storm panel on the three (3) lowest bolts and secure a fastener onto the center bolt of both sides of the storm panel. Eighth, secure fasteners onto the remaining bolts of the lowermost storm panel. Ninth, install additional storm panels. Tenth, prior to installing the final storm panel, remove fastener from the uppermost bolt.
[0020] Directions for using the present invention in a horizontal installation are as follows. First, mount “F” track on the top and bottom of the building opening. Second, cut the strap to match the length of the “F” track. Third, thread bolts through holes, leaving a 1/16 inch gap between the head of the bolts and the strap. Fourth, install the bolt heads in the track and slide them across the track until all of the slack is taken out of the strap. Sixth, repeat the second through the fourth steps for the other side of the building opening. Make sure that the bolts on the top and bottom of the building opening are aligned. Seventh, place a storm panel on three (3) bolts and secure a fastener onto the center bolt of both sides of the storm panel. Eighth, secure fasteners onto the remaining bolts of the first storm panel. Ninth, install additional storm panels. Note that if the strap is too short, more than one strap may be used in series by overlapping the end bolt and the added strap.
[0021] Note that it is possible for a storm panel to have more or less than three (3) openings. In that case, the above directions would be modified accordingly.
[0022] While descriptions of vertical and horizontal installations are given above, the descriptions are not meant to be limiting. Storm panel installations may occur in many angles and positions, being limited only by the location of building openings which must be protected.
[0023] FIG. 1 shows a cross-section side view with bolts threaded into a strap. The strap 101 has a plurality of openings 102 . The bolts 103 are threaded into the strap openings 102 . A gap 105 exists between each bolt head 104 and the strap 101 .
[0024] FIG. 2 shows a cross-section side view of a vertical storm panel installation. The bolts 103 sit in a track 201 . The bolts 103 are held in position with the strap 101 which is adjacent to the track 201 . A storm panel 202 is mounted on the bolts 103 and is adjacent to the strap 101 . The storm panel 202 is secured with fasteners 203 which thread onto the bolts 103 . In this example, the fasteners 203 are wing nuts but many types of fasteners are possible.
[0025] FIG. 3 shows an exploded isometric view of a horizontal storm panel installation. The bolts 103 sit in a track 201 . The bolts 103 are held in position with the strap 101 which is adjacent to the track 201 . A storm panel 202 is mounted on the bolts 103 and is adjacent to the strap 101 . The storm panel 202 is secured with fasteners 203 which thread onto the bolts 103 . In this example, the fasteners 203 are wing nuts but many types of fasteners are possible.
[0026] FIG. 4 shows a front view of an embodiment of the strap. The strap 101 has two long parallel sides 401 with a plurality of openings 102 which are circular and evenly spaced. There is a top end 402 and bottom end 403 . The openings 102 are centered between the two long parallel sides 401 .
[0027] While the present invention has been described herein with reference to an embodiment and various alternatives thereto, it should be apparent that the invention is not limited to such embodiments. Rather, many variations would be apparent to persons of skill in the art without departing from the scope and spirit of the invention, as defined herein and in the claims. | A strap to secure bolts at a proper spacing for installing a storm panel to a track using bolts and fasteners. The strap holds the bolts in place, allowing ease of storm panel installation. The storm panels are typically used to protect building openings, such as windows and doors, during periods of bad weather. The storm panels may also be used for security purposes. | 4 |
FIELD OF THE INVENTION
The invention deals with a method and an arrangement for temperature monitoring of AC/DC motors, which comprise at least one field winding in series with an armature.
BACKGROUND OF THE INVENTION
In universal motors, particularly in electric tools, there is the danger of overheating through excessive loading which can lead to irreversible motor damage.
This danger of overheating is usually countered by switching the motor current off, if a temperature limit is exceeded, or by reducing said current to values presenting no danger. For this the temperature of the motor winding must either be directly measured by means of a temperature sensor, for instance, a positive temperature coefficient (PTC) resistance wound into the winding or it must be indirectly determined from magnitudes which can be handled by measurement technology, for instance, by means of a cooling shunt.
The direct measuring method has the advantage of high precision. It is, however fraught with a high expenditure of additional component costs, installation work and separate wiring. Indirect methods avoid this effort as a rule. They have, however, the disadvantage of being somewhat imprecise and, above all, they cannot reproduce the true motor temperature with sufficient accuracy, above all, because of inherent time delays.
With direct measuring methods, such as those with a measuring sensor or sensors, there are known, for instance, heat sensor elements such as positive temperature coefficient- and negative temperature coefficient resistors or thermal contacts attached to the motor windings (mostly at the or the plurality of the starter windings), whose respective output signals are evaluated.
Measuring methods without measuring sensors are also used as direct measuring methods, which include a known, if however, not very widespread method, to measure the ohmic resistance of at least one motor winding, which constitutes a nearly directly proportional measurement for its temperature. Resistor measurement methods of this type are known in many variants and are described in the professional literature. It is, however, difficult to apply this method to AC motors, because in this case, ohmic resistance must be differentiated from the AC current impedance.
In the indirect temperature measuring method, equipment-modifying, as well as computerized methods, are known.
With the equipment-modifying methods, it is attempted to determine the motor temperature by suitable cross-switched electronic and/or electric components, from which a signal corresponding to the motor temperature can be tapped. Usually, the current flowing through the motor and/or the applied voltage is processed for this purpose. The simplest and mostly widespread type is the use of a thermal circuit breaker, which is wired in series with the motor and which is heated by the motor. When a limit temperature is exceeded, a contact opens and interrupts the current circuit.
In this connection, a method is, for instance, also known to the effect of having the motor current flow through a heating resistance, which is in thermal contact with a temperature sensitive component and which is dimensioned, in such a way, that the absolute value as well as the chronological course of its temperature corresponds to the best possible degree to the motor temperature. By arranging the heating resistance in the motor cooling airflow, another refinement of the method can be achieved.
In the computerized methods, motor temperature is, as a rule, reconstructed with the help of a thermal model. Herein, easily measured magnitudes, such as voltage, current, rpm and/or phase operating angles are processed in such a way by means of a digital computer (frequently a micro-controller), that output data is indicative of the motor temperature. In this connection, methods are known which utilize empirically determined, motor specific, stored characteristic field tables (compare DE 31 11 818 A1), as well as those which compute closed mathematical models (compare DE 31 07 123 A1).
SUMMARY OF THE INVENTION
The invention is based upon the task of indicating a direct measuring method based upon measuring a resistance or an apparatus suitable for performing said measuring method, by means of which a precisely reproducible data corresponding to the operational temperature of universal motors (AC/DC motors) can be obtained, especially for motors which are used in electrically driven tools.
In a method for temperature monitoring of universal motors, the invention is characterized in that a direct current component having a lower value, compared to the effective AC current component, is superimposed upon the motor AC current, wherein the voltage drop is determined at a field winding of the motor, is then relieved of its AC current share. After having been processed in this way, said voltage drop in its capacity of a DC voltage component, proportional to the temperature dependent ohmic resistance of the field winding, is compared to a temperature-invariable DC voltage component. This component is obtained in an analogous manner by means of a current measuring shunt, through which the motor AC current, including the superimposed DC current, component flow.
Compared to the known resistance measurement methods, the temperature monitoring method, according to the invention, has the advantages that, on the one hand, the standard temperature can be measured very accurately and especially without specific measurement sensors. On the other hand, the resistance measurement method in the invention can be ideally combined with existing and known phase operating angle controls.
The mode of operation of the method is based upon a resistance measurement of one of the usually two field windings. In order to overcome the difficulty of having to use the mere alternating current flowing through the motor for this purpose, a low DC current share is superimposed over said motor current. This DC current share causes a DC voltage drop U fdc at the field winding which, if the DC current I dc is known, is directly proportional to the ohmic resistance R f of the field winding and thus to the temperature:
U.sub.fdc =I.sub.dc ·R.sub.f
This DC voltage drop can be measured and, further, processed in a relatively simple manner.
The circuitry means necessary for the realization of the method in the invention are largely contained in customary motor electronics. Additional design effort consists only in an additional field winding connection to the control and regulation-electronics. In addition, assembly effort is not required.
An inventive arrangement for temperature monitoring of universal motors, with at least one field winding in series with an armature, is characterized by a first electronic unit which superimposes a DC current component of lower magnitude compared to the effective AC current component of the motor current, upon the motor current flowing through the field winding and the armature; a second electronic unit, which determines the voltage of the field winding and which eliminates the AC voltage component and delivers an equal magnitude corresponding to the temperature dependent ohmic resistance of the field winding to a first input of a comparator; and a current measurement shunt, which does not vary with temperature, through which flows the motor current including the superimposed DC current component, with a voltage being able to be tapped from said current measuring shunt by a third electronic component, which voltage after elimination of the AC voltage share can be directed to a second input of the comparator as a comparative equal magnitude, with the output of the comparator providing a signal changing with the temperature of the field winding.
The superimposed DC current component is preferably kept constant by means of an integrated current regulator which is coupled to the phase operating angle control and to which the acquired comparative equal magnitude as an actual value is applied.
The second and third electronic units are preferably formed as a voltage amplifier, which is acted upon on its input side by the voltage which can be tapped from the field winding on the one hand and the current measurement shunt on the other hand and which is coupled to a filtering unit for the purpose of eliminating the AC current component.
Accordingly, it is an object of the present invention to provide a method and apparatus for temperature monitoring of universal or AC/DC motors which is based upon the task of creating a direct measuring method based upon measuring a resistance and an apparatus suitable for performing said measuring method, by means of which a precisely reproducible data corresponding to the operational temperature of universal motors (AC/DC motors) can be obtained, especially for motors which are used in electrically driven tools.
Other objects and advantages of the present invention will be apparent to those skilled in the art upon a review of the Description of the Preferred Embodiment taken in conjunction with the Drawings which follow.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a circuit diagram of a circuit arrangement for temperature monitoring of universal motors according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 illustrates a basic circuit diagram which shows an AC current universal motor with an armature A and the field windings F as well as a phase operating angle control 1, as it is customarily used, in order to change or regulate the rpm of a motor. Further, a current measuring shunt 2 is located in the motor current circuit, which can be integrated into the component of the phase operating angle control 1. As a rule, all of these elements or components already exist in an electric tool. Power supply terminals are designated by Un.
The arrangement of FIG. 1 is supplemented in the invention by a current regulator 3 which superimposes a DC current component of smaller, but constant magnitude, upon the motor AC current, which will be explained in detail below. The regulator 3 is acted upon at the input by an actual current value derived from the current measurement shunt 2, which has been freed from the AC current share after amplification and filtering in a filter-amplifier 4.
The voltage drop at one of the two field windings F is measured, in a manner similar to that at the current measuring shunt 2, by means of a field voltage amplifier filter 5. The AC voltage component is eliminated by the filtering and there remains DC voltage share generated by the superimposed DC current, which DC voltage share is directly proportional to the DC current and to the ohmic resistance of the field winding F.
If one now compares the DC voltage drops at the non-variable temperature of the temperature measuring shunt 2 and the temperature dependent field winding F by means of a comparator 6, then one obtains a switching signal T, if a suitable selection of the amplifier factors has been made, which displays that a specific preselectable temperature of the field winding F has been reached. This switching signal can be processed further in the most different ways, for instance, into an optical or acoustical warning display for switching the apparatus off and/or for limiting the motor current to a non-critical value.
The individual components of the circuit arrangement are described in detail below.
The phase operating angle control 1 consists, as a rule, of a triac (bi-directional thyristor triode) and the associated actuation circuit which, depending upon a control value, predetermines the firing angle of the triac and, with this, the effective motor voltage. The control value can, on its part, be an output value of an rpm- and/or current regulator. For the actuation circuit, there exists a plurality of embodiment forms well known to the specialist versed in the art in the form of discrete circuit buildups or as integrated circuits.
The current measuring shunt 2 consists, as a rule, of a relatively low ohmic resistance, in which a measuring voltage directly proportional to the motor current is degraded. Usually, metal alloys, properties of which substantially do not change with a change in temperature, for instance, constantan and similar known materials, are used as resistor material.
The current regulator 3 is not absolutely necessary for the functioning of the invented temperature monitoring. This is because the DC voltage drops in the current measuring shunt 2 and at the field winding F are compared, meaning subtracted, in the comparator 6. Therefore, the circuit operates within reasonable limits basically independently of the magnitude of the DC current component. Difficulties, however, can arise at the selection or rejection boundaries, or modulation range, of the phase operating angle control 1 and in specific conceivable loading cases, in particular, at very low motor voltages or in case of full motor voltage. In this case, it is difficult to obtain a sufficiently high DC current component. A simple, however not the only, possibility of circumventing this difficulty consists in keeping the DC current constant at a sufficiently high, however compared to the AC current low, value. This is assured by the current regulator 3, which compares a predeterminable, constant actual value I ref to the DC voltage--actual value (DC-Actual Value) supplied by the shunt voltage amplifier and filter 4. Depending on the difference resulting therefrom, a control signal is formed, which causes an increase or a decrease of the DC current component in the phase operating angle control 1.
The circuit group of the filter amplifier 4 (shunt voltage amplifier and filter) consists operationally of two parts, namely, on the one hand of a low pass filter whose cut-off frequency is small compared to the power supply voltage frequency, so that the AC component of the motor current, or the associated measuring voltage, can be adequately dampened. On the other hand, this circuit group comprises an amplifier which amplifies the comparatively low DC signal for further processing in stages located downstream. As far as circuit technology is concerned, both of these objectives can be attained by an amplifier with a resistance/capacitance circuitry.
The circuit group of the field voltage amplifier and filter 5 is basically identical to the shunt voltage amplifier 4 described above as far as function and construction is concerned. Since the falling voltage component (AC as well as DC) are considerably greater than those at the current measuring shunt 2, the circuit technology layout of the amplifier circuitry elements must, however, be selected in a different manner. If the values are measured at the top field coil F, as is shown in FIG. 1, then, as a rule, a differential amplifier is necessary. It could, however, also be feasible to measure at the bottom field coil F, since the same current flows through both coils and since they are normally constructed identically. In such cases, one can do without a differential amplifier.
The comparator 6, with a timing unit, compares the DC voltage drops at the current measuring shunt 2 and the field winding F. Since an unavoidable residual ripple content exists in both signals in spite of filtering, a mere comparator would continuously switch back and forth in the vicinity of the switch-over point, meaning, where the limit temperature has been reached. In order to eliminate this, a low pass filter with a very low cut-off frequency is located downstream, as is shown in FIG. 1.
In an advantageous embodiment form for both circuitry parts, a subtracting integrator is used. It subtracts the two input signals and integrates the difference. The output signal assumes stationarily only two different states in spite of the input signals containing ripples. These two different states correspond to the top or low rejection or selection boundary and, thus, the output signal can be further processed just like a binary signal. A further advantage of this operational group consists in not reacting immediately after attaining the temperature limit, but rather, to provide a desired time delay adapted to the drive unit to be protected, wherein a short-time overload is tolerated. The function of the time delay with short time overload can, however, also be achieved in a different manner, for instance, by utilizing a monostable flipflop.
It is evident that the described circuit arrangement influences in such a way the phase operating angle control, that the positive and negative voltage half-waves assume unequal magnitudes. As a result, a DC voltage component of the motor voltage entails a corresponding DC current component. An advantageous possibility to achieve this consists in making the firing angles for the triac in the phase operating control 1 (see the above explanation) for the positive and negative voltage half-waves (which are normally equal) unequal. In this connection, it is possible to influence a signal voltage which exists and is accessible in most phase operating angle controls, which signal voltage affects the firing angle. Other, if however less attractive, possibilities of producing the DC current component, consist in, for instance, blending out periodically entire half-waves of one polarity or to produce in the motor current paths different voltage drops for different current directions by means of suitable circuitry elements, such as zener diodes, diode-resistor combinations or the like.
While the present invention has been described and illustrated in a preferred embodiment, such is merely illustrative of the present invention and is not to be construed to be a limitation thereof. Accordingly the present invention encompasses any and all modifications, variations and/or alternate embodiments with the scope of the present invention being limited only by the claims which follow. | The method and the arrangement for temperature monitoring of universal motors based upon a resistance measurement of a field winding, wherein a DC current component of low magnitude is superimposed upon the motor current for elimination of the complex values of the AC current impedance, and wherein the voltage drop in the field winding is amplified and freed from the AC voltage component and is compared as a DC voltage component proportional to the ohmic resistance of the field winding to a temperature independent DC voltage component, which is obtained in an analogous manner from a current measuring shunt, through which the motor AC current, including the superimposed DC current component, flows. | 7 |
CROSS-REFERENCES TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
BACKGROUND OF THE INVENTION
The invention relates to a candle holder for mounting on a support, such as a bakery product.
TECHNICAL FIELD
Candle holders for holding and for mounting candles on a support, for example on a bakery product, are used on many festive occasions. A typical intended use is the application of a number of candles associated with the age to a birthday cake.
Typical problems generally arise through the number of candles which have to be placed with increasing age of a person celebrating his or her anniversary and which have to be anchored in the generally only slightly stable mass of the bakery product in a small space, and for the lighting and burning of candles. In addition to the difficulties of handling, the contamination by soot and wax which arises from the burning of the candles gives rise to at least aesthetic limitations. A very fast and easy lighting of a relatively large number of candles presents a further difficulty.
U.S. Pat. No. 3,819,455 discloses a hood-like cake protector which is also equipped for holding candles. The fastening and retention are effected here without direct contact with the cake by inverting over the cake protector in which the candles rest in fixed mounts unchangeable in their positioning.
U.S. Pat. No. 4,721,455 describes a construction which can be pushed onto or into a cake and has candle mounts around a cylindrical center.
U.S. Pat. Nos. D 285,159, 4,938,688 and 4,884,966 disclose protective plastic cake covers which have a number of holes into which candles can be inserted. In one embodiment, a special arrangement of the holes enables numerical symbols represented as figures and comprising candles to be inserted.
U.S. Pat. No. 298,859 describes a shield-like cake attachment which can be pushed into a cake and has, on its upper surface, holders for a few candles.
However, none of these publications describes a possibility for fast and easy lighting of candles, in particular a relatively large number thereof, as are used especially on birthdays, company anniversaries and other celebrations. In all cases, the candles must be lit individually, which proves to be particularly disadvantageous since, in addition to the complicated handling, nonuniform burning of the candles results, which is aesthetically not very advantageous and, in the most unfavorable case, can result in the candles lit first already going out before the last candle burns. In particular, candle size and number of candles are negatively correlated with one another owing to the limited space available on a bakery product, so that an individually short burning time of the candles is likely in the case of large numbers of candles and the problems described may occur to a greater extent.
U.S. Pat. No. 6,186,766 B1 describes a candle lighting system for fast lighting of a plurality of candles. There, the candles are lit by means of a burnable connection from candle to candle by means of a fuse cord. This solution has the disadvantage that special candles or candle attachments have to be used and the lighting process is likely to release a relatively large amount of combustion substances, which in turn can contaminate the cake or the surrounding air. Because of the requirements associated with the handling of many ignition leads, their use for a relatively large number of candles is complicated and susceptible to problems.
U.S. Pat. No. 5,439,376 discloses a special type of candle which has a lighting cord connected to the wick and is likewise lit by means of a fuse. In addition to the disadvantages already described for the preceding solution and also relevant here, the difficulty of correct transmission of the igniting flame from the lead to the candle wick additionally occurs.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a candle holder, in particular for a relatively large number of candles, which permits the lighting of all candles quickly and easily without having to use special igniting leads.
This object is achieved, according to the invention, by a candle holder for mounting on a support, such as a bakery product, including at least two bearer elements, on each of which at least one candle mount is mounted, wherein the bearer elements are displaceably connected to one another, in a first position of the bearer elements, it being possible for wicks of at least two candles introducible or introduced in each case into the candle mounts to be brought into an ignition distance relative to one another and it being possible for the bearer elements then to be moved, in particular pushed, turned or folded, into a second position in which the wicks are a larger distance apart. Advantages and alternative embodiments and further developments of the apparatus are evident from the following description of the invention.
In the subject of the invention, the candles are held in mounts which can be moved relative to one another in such a way that, in a first position, easy and fast lighting of the candles is possible and said position is determined so that wicks of the candles are present an ignition distance apart. Owing to the geometric conditions, it will in general not be possible to find a position of all wicks in which the lighting of a single candle leads to transmission of the flame to all remaining candles.
An embodiment comprises bringing together the candle mounts and hence the wicks in a plurality of rows of candles so that the candles to be lit are reduced to the candles present in each case at the front position in the rows. The candle holder is held in such a way that the candles of a row are present perpendicularly one on top of the other and, as a result of lighting the wick of the lowermost candle, transfer to the candle above by the “upward burning” of the flame is possible.
If the distance of the rows from one another is chosen so that the ignition distance is reliably exceeded, it is possible to ensure that only the intended part of the candles is ignited quickly in succession and uncontrolled burning is avoided. This makes it possible to take into account particular risk aspects associated with specific groups of persons, such as, for example, children.
After all candles have been lit, their spacing is increased by moving the candle mounts until, after reaching or assuming a second position, which, for example, may meet decorative requirements, it is possible to mount the holder on a support.
The individual candle mounts can be mounted on bearer elements which can be displaced, rotated, tilted or moved in another manner relative to further bearer elements present. The second position designed for mounting of the candle holder may have a form which primarily conforms to decorative aspects but must also take account of the mechanical requirements of the movement. A ring, star, fan, shield, grid or spiral represents a suitable form. A movement of the components, such as, for example, the bearer elements, from the first to the second position and vice versa can be effected by means of generally known mechanical connections, such as, for example, joints, flexible connections or sliding connections.
The movement can take place in a plane as well as include changes in further dimensions, for example folding together of a plurality of arm-like bearer elements toward a common center. The first position thus assumed may have, for example, the form of a spherical cap or a pyramid, in the center of which or at the vertex of which all wicks or at least a relatively large proportion of the wicks have been brought within an igniting distance of one another. After lighting, the bearer elements can be moved back to their position. Arrangement of the candle mounts or bearer elements in different planes or at different angles is also possible, for example their terraced or step-like arrangement can help to give a particular impression of the candle holder.
The production of a plurality of components of the candle holder, including the candles, from a single, common material permits integrated, simple and economical production, for example of disposable candle mounts for events which have a singular character, such as, for example, a golden wedding anniversary or an eightieth birthday.
BRIEF DESCRIPTION OF THE DRAWINGS
The candle holder according to the invention is described in more detail below, purely by way of example, with reference to embodiments shown schematically in the drawing.
FIG. 1 a shows an overall view of the exemplary embodiment of a candle holder according to the invention, in plan view;
FIG. 1 b shows the view of a bearer element with burning candles;
FIG. 2 a shows the exemplary embodiment of a candle holder according to the invention, in the second position, in plan view;
FIG. 2 b shows the same candle holder in the first position, in plan view;
FIG. 3 shows a schematic representation of the lighting of candles for an exemplary embodiment of a candle holder according to the invention;
FIG. 4 shows a figurative representation of the lighting of candles for an exemplary embodiment of a candle holder according to the invention;
FIG. 5 shows the change in the candle holder from the first to the second position;
FIG. 6 a shows a wheel-like embodiment of a candle holder according to the invention, in first position, in plan view;
FIG. 6 b shows the same candle holder in the second position, in plan view;
FIG. 7 shows a figurative representation of the lighting of candles for the same candle holder;
FIG. 8 shows a second heart-shaped embodiment of a candle holder according to the invention in the second position, in plan view, and
FIG. 9 shows an arm-like component belonging to this candle holder and comprising candle mounts displaceable relative to one another.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 a shows an overall view of the exemplary embodiment of a candle holder according to the invention, in plan view, which candle holder consists of a plurality of bearer elements 2 which are connected to one another in a grid by means of pivot points in a scissors-like manner. Candles 4 are mounted at the points of intersection of the bearer elements 2 . The embodiment shown by way of example has the same distances between the candles 4 in the second position which is suitable for mounting on a support, which represents only one of a plurality of possible embodiments. Mounting on the support and fixing there may be facilitated, for example by spike-like or nail-like extensions on that side of the candle holder which is opposite the candles 4 .
FIG. 1 b shows one of the bearer elements 2 individually and on a larger scale. Candle mounts 3 are fastened in a linear arrangement on the bearer element 2 and in turn hold candles 4 . Since the candles 4 are fastened to the bearer elements 2 by means of the candle mounts 3 , candle mounts 3 are no longer shown in the following figures although they are always taken into account as a suitable fastening means without wishing herewith to justify the exclusiveness of this apparatus for candle fastening.
The second position of this candle holder is shown in FIG. 2 a, in which the candles 4 fastened to the bearer elements 2 are at the spacing A for use.
As shown in FIG. 2 b, the distance between the candles 4 is reduced in the direction toward the igniting distance B by pushing together the candle holder, and is increased in the direction perpendicular thereto.
In FIG. 3, the candles 4 now positioned in a plurality of rows at the igniting distance on the bearer elements 2 are recognizable. For lighting, the candle holder 1 is turned so that the candles 4 in a row are present one on top of the other. A burning candle moved along the lowermost candles of the row lights this lowermost candle, from which the flame is then transmitted to the other candles of the row.
FIG. 4 shows this procedure in the figurative representation. The candle 4 is moved from right to left so that this flame touches the wicks 5 of the lowermost candles of a row. The first three rows have already been lit in their bottom region, and the ignition can spread upward to the further candles of the row. If the lowermost candles of all rows have been passed, all remaining candles light independently through the gradual transmission of the flames upward from below.
Finally, when all candles have been lit, the candle holder 1 can be moved back to the second position, as shown in FIG. 5 .
An alternative wheel-like or star-like embodiment of the candle holder 1 according to the invention is shown schematically in FIG. 6 a, in the first position. The candles 4 are now fastened to the bearer elements, which in turn form holding arms 6 or are displaceably connected to the separate holding arms 6 and which are fastened in a star-like manner to a common fixed point C. By rotating the candle holder 1 positioned perpendicularly to a separate candle 4 , the outermost candles 4 of a row which are present at the ignition distance are lit and the ignition is transmitted upward toward the common fixed point C.
After complete ignition of all candles 4 , the candle holder 1 can be brought into the second position by stretching the holding arms 6 , as shown in FIG. 6 b.
The lighting process is shown figuratively in FIG. 7 . It should be noted here that, after lighting of the lowermost candle 4 in each case, it is necessary to wait until all candles of a row have been lit since further rotation of the candle holder eliminates the perpendicular positioning of the candles 4 one on top of the other for the respective row.
A further heart-shaped or fan-shaped embodiment of the candle holder 1 according to the invention is shown in FIG. 8 .
The holding arms 6 of the candle holder are fastened to one another at a common fixed point C. The individual holding arms 6 are of different lengths, the matching of which with one another in the second position gives the desired overall impression of a heart-shaped or fan-shaped overall figure D. The first position can be achieved by folding together the holding arms 6 toward a central line E of the overall figure D while simultaneously pushing together the holding arms 6 .
A holding arm 6 which can be used for this embodiment is shown in FIG. 9 . One candle 4 in each case is present on a bearer element 2 , which is connected to other bearer elements 2 of the same type, in each case by means of an intermediate part 7 on both sides. Only the bearer elements 2 at the end of the holding arm 6 have a fastening at intermediate part 7 only on one side. These intermediate parts 7 can be formed in such a way that they can be inserted into the bearer elements 2 so that the total holding arm 6 can be shortened telescopically.
Of course, the figures shown represent one embodiment out of many embodiments, and a person skilled in the art can derive alternative forms for realization, for example with the use of other materials, candle forms or geometries. | Candle holder for mounting on a support, such as a bakery product, comprising at least two candle mounts which are displaceable relative to one another so that the wicks of at least two candles present in each case on the candle mounts can be brought into an ignition distance relative to one another in a first position and can then be moved into a second position in which the wicks are a larger distance apart. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to an esterase, its DNA, its overexpression and a method for preparing optically active aryl propionic acids using the same in high yield. More particularly, the present invention relates to an esterase having a stereoselective hydrolyase activity, its manufacturing method for mass production by employing recombiant E. coli expression system and a method for preparing optically active aryl propionic acids expressed by the following formula (1) using the same,
[0002] wherein R 1 represents an aryl group; and R 2 represents a hydrogen atom.
BACKGROUND OF THE INVENTION
[0003] Indeed, FDA's (Food and Drug Administration's) Policy Statement for Development of New Drugs recommends “that the pharmacokinetic profile of each isomer should be characterized in animals and later compared to the clinical pharmacokinetic profile obtained in Phase I” drug testing. Thus, the demand for racemic switch technologies to produce each pure isomer has been rapidly increased in recent years.
[0004] Aryl propionic acids are non-steroidal anti-inflammatory drugs and known as profen drugs such as ibuprofen, ketoprofen, naproxen, flurbiprofen, fenoprofen, suprofen and the like. It is generally alleged that the (S)-profens has the higher pharmacological effect of the racemic mixture of profens bearing at least one benzene ring a-position to aliphatic carboxylic function. A method for preparing optically pure (S)-profen drugs involves the conversion of a racemic mixture of profen ester to optically active profen carboxylic acid by reacting with a stereoselective chiral enzyme.
[0005] However, it has been recently reported that (R)-enantiomers of porfens exhibit novel therapeutic effect. Particularly, U.S. Pat. No. 6,255,347 discloses that (R)-enantiomer of ibuprofen may be used as a prophylactic and herapeutic agent in the treatment of disease such as cancers, Alzheimer's and Alzheimer's related diseases. In the method for preparing (R)-enantiomer of aryl propionic acid, a racemic mixture of aryl propionic acid is treated with an esterase to produce an ester of (S)-enantiomer of aryl propionic acid and un-reacted (R)-enantiomer of aryl propionic acid is recovered.
[0006] Further, inventors of the present invention have previously identified that Pseudomonas sp. has a stereoselective hydrolase activity and its use in the preparation of (S)-profen (KR Patent Application No. 2000-02565). U.S. Pat. No. 6,201,151 discloses a process for preparing an optically active (S)-aryl propionic acid by hydrolyzing racemic thioester of aryl propionic acid in the presence of a (S)-stereoselective lipase. KR Patent Application No. 2001-0044879 discloses a process for preparing optically pure acetylmercaptoisobutylate using Pseudomonas aeruginosa as an esterase. KR Patent Application No. 1996-14399 discloses a process for preparing optically pure aryl carboxylic acid stereoselectively from a racemic mixture of α-aryl carboxylic acid using S-(-)-α-ethyl benzylamine. KR Patent Application No. 1999-0042314 discloses a process for preparing optically active carboxylic acids and esters as drugs for the treatment of hypertension using Klebsiella pneumoniae as a hydrolase. U.S. Pat. No. 5,516,690 discloses that (S)-ketoprofen can be produced in greater than 95% purity using isolated Trichosporon laibacchii.
[0007] However, it is still unsatisfactory to produce optically pure (S)— or (R)— enantiomer of aryl propionic acid using the above-mentioned enzymes and no one has reported in the literature regarding mass production of the enzyme being used therefore.
SUMMARY OF THE INVENTION
[0008] Accordingly, an object of the present invention is to provide an esterase having excellent stereoselectivity and its DNA sequence.
[0009] Another object of the present invention is to provide a method for producing the esterase in a mass production scale by overexpression of the esterase in recombiant E. coli.
[0010] Further object of the present invention is to provide a process for preparing optically pure aryl propionic acid in high yield using the esterase,
[0011] wherein R 1 represents an aryl group; and R 2 represents a hydrogen atom.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The above and other objects and features of the present invention will become apparent from the following description of the invention, when taken in conjunction with the accompanying drawings, in which:
[0013] [0013]FIG. 1 represents a manufacturing process of an esterase expression vector, pEESTa;
[0014] [0014]FIG. 2 represents a manufacturing process of an esterase expression vector, pEUbiESTa;
[0015] [0015]FIG. 3 represents a manufacturing process of an esterase expression vector, pErxESTa;
[0016] [0016]FIG. 4 represents an acryl amide gel electrophoresis of an esterase expression;
[0017] [0017]FIG. 5 represents an acryl amide gel electrophoresis of an esterase purified via anion exchange chromatography; and
[0018] [0018]FIG. 6 represents an acryl amide gel electrophoresis of an esterase purified via gel chromatography.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The present invention provides an esterase having excellent stereoselectivity, its DNA and its mass production by transformation thereof. In accordance with one aspect of the invention, there is provided a method for preparing optically pure aryl propionic acid of formula (1) using the same esterase,
[0020] wherein R 1 represents an aryl group; and R 2 represents a hydrogen atom.
[0021] The present invention is described in detail as set forth hereunder. The esterase of the present invention is identified by the SEQ. ID. NO: 1 for its gene and the SEQ. ID. NO: 2 for its amino acid sequence and has a molecular weight of 41 kDa.
[0022] Further, the esterase derived from Pseudomonas sp. BHY-1 hydrolyzes racemic ester of a carboxylic acid unsymmetrically to produce the corresponding optically pure carboxylic acid. On the other hand, Pseudomonas sp. BHY-1 has a stereoselective hydrolase activity to convert racemic ester of aryl propionic acid to one-enantiomer aryl propionic acid. The racemic ester of aryl propionic acid used as a substrate may be prepared from racemic profen by a conventional method. Examples of the profen include ketoprofen, ibuprofen, naproxen, flurbiprofen, fenoprofen, suprofen and the like.
[0023] The inventors of the invention have selected Pseudomonas sp. BHY-1 exhibiting excellent stereoselectivity from soil and analyzed gene sequence of the esterase to obtain optically pure aryl propionic acid. Further, the present invention provides a construction of a recombiant E. coli expression vector to produce the esterase in an industrial scale. A novel esterase expression vector named as a pEESTa is constructed by introducing an NdeI restriction site to the N-terminal of the esterase and an XhoI restriction site to the C-terminal, performing PCR (Polymerase chain reaction) to amplify DNA fragments, and incorporating a T7 promoter and T7 terminator. Other pEUbiESTa and pETrxESTa vectors are also constructed by introducing ubiquitin and thioredoxin to improve production efficiency. These vectors are also incorporated with T7 promoter and T7 terminator and produce an active esterase more effectively. Theses expression vectors are then transformed into E. coli to produce E. coli transformants BL21(DE3)/pEESTta, BL21/ pEUbiESTa, and BL21/ pETrxESTa.
[0024] The obtained E. coli transformants BL21(DE3)/pEESTta is cultured and the cultured E. coli is then recovered. Examples of the profen used as the substrate to identify an activity of the obtained recombiant esterase include ethyl esters of ibuprofen, ketoprofen, naproxen, and flurbiprofen. As a result, an enantiomeric excess (ee p ) of (S)-enantiomer profen produced by using the recombiant esterase of the present invention is not lower than 98%. It is preferable to maintain the pH in the range of from 6.0 to 12.0, more preferably from 8.0 to 10.0 and a temperature of from 15 to 80 ° C., more preferably 30 to 80° C. during resolution of aryl carboxylic acids. The obtained recombiant esterase may be purified by ion exchange chromatography, metal affinity chromatography or gel chromatography.
[0025] This invention is explained in greater detail based on the following Examples but they should not be construed as limiting the scope of this invention.
Preparation Example
[0026] Preparation of racemic profen ethyl ester
[0027] Racemic profen (30 g) and ethanol (100 mL) were mixed and reacted in the presence of hydrosulfuric acid (2.5 mL) at 90° C. for 5 hours. The unreacted ethanol was removed by evaporation under the pressure. The reaction mixture was extracted with 1 M of sodium bicarbonate solution three times to obtain racemic profen ethyl ester.
Conversion ( % ) = Conc . of ( S ) - arylpropionic acid + Conc . of ( R ) - arylpropionic acid Conc . of arylpropionic ester
× 100 Equation 1 Enantiomeric excess ( % ) = Conc . of ( S ) - arylpropionic acid - Conc . of ( R ) - arylpropionic acid Conc . of ( S ) - arlypropionic acid + Conc . of ( R ) - arylpropionic acid × 100 Equation 2
Example 1
[0028] Sequence Analysis of a Novel Esterase Gene
[0029] Chromosomal DNA isolated from Pseudomonas sp. BHY-1 was partially digested with Sau3A, ligated with BamHI-digested pUC119 vector and then was transformed into E. coli DH5μ. One of the clones, carrying a plasmid named as pT7HY (about 3 kb), exhibited enzymatic activity producing (S)— ketoprofen from (R, S)-ketoprofen ester and was chosen for the further study. And also, the results showed that the novel esterase gene has a molecular weight of about 41 kDa. Transformants were selected based on a tributyrin hydrolysis as well as a stereoselectivity towards ketoprofen ester. The results showed that the novel esterase gene has a molecular weight of about 41 kDa and consists of 1,143 bp nucleotides (381 amino acids). The gene was registered in Genbank of NCBI and was assigned the Reg. No. AF380303 but has not been published yet. The novel esterase is identified by the SEQ. ID. NO: 1 for its gene and the SEQ. ID. NO: 2 for its amino acid sequence.
Example 2
[0030] Construction of an Expression Vector for a Novel Esterase Gene
[0031] Chromosomal DNA isolated from Pseudomonas sp. BHY-1 was partially digested with Sau3A, ligated with BamHI-digested pUC119 vector and then was transformed into E. coli DH5μ. One of the clones, carrying a plasmid named as pT7HY (about 3 kb), exhibited enzymatic activity producing (S)-ketoprofen from (R, S)-ketoprofen ester. The novel estererase cDNA coding sequence was amplified by PCR using pT7HY as a template. The primers used in the above PCR are as follows.
N-terminal primer 5′-GGG AAT TTC CAT ATG CAG ATT CAG GGA CAT TAC GAG CTT CAA TTC-3′ [SEQ.ID.NO:3] C-terminal primer 5′-CCG CTC GAG TTA CAG ACA AGT GGC TAG TAC CCG CGC CAG-3′ [SEQ.ID.NO: 4]
[0032] The N-terminal primer was introduced with an NdeI restriction site and also ATG was introduced as an initiation codon in place of GTG, whereas the C-terminal primer was introduced with an XhoI restriction site. The product, about 1,100 bp in size, obtained from the above PCR was double-digested with NdeI and XhoI and then separated on an agarose gel. The novel esterase gene fragment isolated from the above agarose gel was ligated into a 5,400 bp DNA fragment of pET22b(Novagen Co., Ltd., U.S.), an E. coli expression vector, double-digested with NdeI and XhoI by using a ligase. Then, an expression vector was constructed so that the novel esterase gene can be expressed, wherein its gene translation is carried out by T7 promoter and T7 terminator, and was named as pEESTa (FIG. 1). The vector pEESTa was then transformed into E. coli BL21(DE3) according to Simanis. The transformed E. coli BL21(DE3)/pEESTa was deposited to the Genebank of KRIBB on Nov. 20, 2001 and assigned the Accession No. KCTC 10122BP.
Example 3
[0033] Expression of a Novel Esterase Gene
[0034] The above E. coli transformant BL21(DE3)/pEESTa(KCTC 10122BP) was cultured in a solid LB medium(yeast extract 0.5%, tryptone 1%, and NaCl 1%). The above cultured E. coli was inoculated into a liquid LB medium containing ampicillin (50 μg/mL), and then re-cultured at 37° C. until the OD 600 reached 0.6. Then, the culture was added with isopropylthio-β-D-galactoside (IPTG) to the final concentration of 1 mM and cultured further for 4 hr for the expression of an esterase gene. Cold shock response was employed for the production of an active esterase because an esterase becomes in the form of an insoluble inclusion body, which has little enzyme activity, when E. coli transformant BL21(DE3)/pEESTa(KCTC 10122BP) is produced by culturing at 37 ° C. (FIG. 4). Cold shock response is a method to produce an active enzyme wherein a given culture is incubated at 37° C. until the expression is induced by IPTG followed by lowering the culturing temperature to 5-25° C (Pamela G. Jones & Masayori Inouye, The cold-shock response, Mol. Microbiol., 11, 5,1994).
Example 4
[0035] Construction of an Expression Vector for a Novel Ubiguitin-Fused Esterase Gene
[0036] A 228 bp fragment encoding ubiquitin (76 amino acids) was amplified by PCR using Saccharomyces cerevisiae genomic DNA as template. The primers used in the PCR are as follows.
N-terminal primer 5′-GGG AAT TTC CAT ATG CAC CAC CAC CAC CAC CAC CAA ATT TTC GTC AAA ACT CTA ACA-3′ [SEQ.ID.NO:5] C-terminal primer 5′-ACC ACC CCT CAA CCT CAA GAC-3′ [SEQ.ID.NO: 6]
[0037] The N-terminal primer was introduced an NdeI restriction site while the C-terminal primer, where a novel esterase is to be ligated, was treated blunt-ended. The product (fragment 1: 228 bp) obtained from the above PCR was digested with NdeI and then separated on an agarose gel.
[0038] The coding region of novel esterase was isolated by PCR. The primers used in the above PCR are as follows.
N-terminal primer 5′-CAG ATT CAG GGA CAT TAC GAG CTT CAA TTC-3′ [SEQ.ID.NO:7] C-terminal primer 5′-CCC CTC GAG TTA CAG ACA AGT GGC TAG TAC CCG-3′ [SEQ.ID.NO:4]
[0039] The N-terminal primer was treated blunt-ended so that it can be ligated to ubiquitin sequence and then introduced with an XhoI restriction site. The product (fragment 2: 1,100 bp) obtained from the above PCR was digested with XhoI and then separated on an agarose gel.
[0040] The novel esterase gene fragment as well as the ubiquitin gene fragment (PCR-amplified product) isolated from the above agarose gels were ligated into a 5,400 bp DNA fragment of pET22b(Novagen Co., Ltd., U.S.), which was digested with NdeI and XhoI by using a ligase. Then, an expression vector was constructed so that an esterase can be expressed, wherein its gene translation is carried out by T7 promoter and T7 terminator, and was named as pEUbiESTa (FIG. 2). The expression vector was not deposited because it can be readily constructed by a person with the skill in the pertinent art.
Example 5
[0041] Construction of an Expression Vector for a Novel Thioredoxine-Fused Esterase Gene
[0042] In order to increase the rate of production and expression of the novel esterase having an activity, an expression vector introduced with thioredoxine was constructed. The novel estererase cDNA coding sequence was amplified by PCR using pT7HY as a template. The primers used in the above PCR are as follows.
N-terminal primer 5′-CCG GAA TTC CAG GGA CAT TAC GAG CTT CAA TTC-3′ [SEQ.ID.NO:8] C-terminal primer 5′-CCG CTC GAG TTA CAG ACA AGT GGC TAG TAC CCG-3′ [SEQ.ID.NO:4]
[0043] N-terminal of primers were treated with EcoRI so that they can be ligated to thioredoxine sequences and then introduced with an XhoI restriction site. The PCR product (1,100 bp) was gel purified and digested with EcoRI and Xhol.
[0044] The novel esterase gene fragment isolated from the above agarose gel was ligated into a 5,900 bp DNA fragment of pET32b(Novagen Co., Ltd., U.S.), an E. coil expression vector that contains thioredoxine which was double-digested with EcoRI and XhoI, by using a ligase. Then, an expression vector was constructed so that the esterase can be expressed, wherein its gene translation is carried out by T7 promoter and T7 terminator, and was named as pETrxESTa (FIG. 3). The expression vector was not deposited because it can be readily constructed by a person with the skill in the pertinent art. The two fusion partners have six histidine tags and are thus easily purified and are also characterized in that they have special cleavage sites for ubiquitin hydrolase and enterokinase (FIGS. 2 and 3).
Example 6
[0045] Expression of an Esterase
[0046] The above E. coli transformant BL21(DE3)/pEESTa(KCTC 10122BP) was inoculated into an LB medium and cultured at 37 ° C. until the OD 600 reached 0.6. Then, the culture was added with IPTG to the final concentration of 1 mM and cultured further for 4 hr to induce the expression of the fused esterase gene. The expressed fused esterase was identified on an SDS-PAGE gel (12% acrylamide) (see Example 3) and compared with the esterase in the Example 3(FIG. 4). Cold shock response was employed for the production of an active esterase because an esterase becomes in the form of an insoluble inclusion body, which has little enzymatic activity, when E. coli transformant BL21(DE3)/pEESTa(KCTC 10122BP) is produced by culturing at 37° C. (FIG. 4). It is noteworthy that the culture is incubated at 37 ° C. until the expression is induced by IPTG followed by lowering the culturing temperature to 20° C., whereby the esterase is produced in an active form. The result showed that the above two fused proteins of ubiquitin-esterase and thioredoxine-esterase, which were both produced by cold shock response, were shown to retain their optical selectivity and hydration capability.
Example 7
[0047] Identification of a Novel Esterase Expression
[0048] The culture was centrifuged for 20 min at 7,000 rpm and the cells were recovered. To study the expression level of the esterase that is expressed, the whole cell was divided into a soluble fraction and an insoluble fraction via sonication and its expression was examined. Three samples such as a whole fraction, a soluble fraction and an insoluble fraction, was dissolved in 100 μL of protein solubilizing buffer solution(12 mM Tris-HCl pH 6.8, 5% glycerol, 2.88 mM mercaptoethanol, 0.4% SDS, 0.02% bromophenol blue) and then heated for 5 min at 100° C. Ten μL each of thus formed solutions was loaded onto a polyacrylamide gel, wherein a 0.75 mm thick 12% gradient separating gel (pH 8.8, 20 cm(W)×10 cm(H)) was covered with a 5% stacking gel (pH 6.8, 10 cm(W)×12 cm(H)). Then, electrophoresis was performed for 80 min (120 V, 60 mA) and the gel was stained with Coomassie Blue. The gel scanning (BioRad, Imaging Densitometer GS-700, U.S.) result of the esterase revealed that the expression level after IPTG induction was 46.7%, and 94.2% of the total expression was present in the form of an insoluble inclusion body.
Example 8
[0049] Purification of a Novel Esterase via Anion Exchange Chromatography
[0050] Ion exchange chromatography was performed to purify the novel esterase produced from the recombinant E. coli. The chromatography was performed by using Q-Sepharose(Pharmacia Co., Ltd., Sweden) as a resin at pH 8.5 at the rate of 4.0 mL/min. Samples were prepared by crushing cell walls of E. coil by using a sonicator followed by filtering thus obtained soluble fraction through micro filter(0.2 μm). Q-Sepharose was equilibrated with 50 mM Tris-HCl(pH 8.5) buffer solution. The esterase was fractioned by using NaCl linear gradient of an eluent buffer solution (1N NaCl/50 mM Tris-HCl, pH 8.5) wherein the sample was first put into the chromatography column followed by a thorough rinse with an equilibrium buffer solution. Thus purified esterase was identified on an SDS-PAGE gel electrophoresis as in the Example 6 (FIG. 5).
Example 9
[0051] Purification of a Novel Esterase via Gel Chromatography
[0052] Gel chromatography was performed by using the fraction obtained from the above anion exchange chromatography. The chromatography was performed by using Sephacry S-200-HR(Pharmacia Co., Ltd., Sweden) as a resin at pH 8.5 at the rate of 0.3 mL/min. Samples were prepared by filtering the fraction obtained from the ion exchange chromatography through micro filter(0.2 μm). Sephacry S-200-HR was equilibriated with 50 mM Tris-Cl/10 mM NaCl buffer solution. The esterase was fractioned after putting the sample into the chromatography column and flowing it at the rate of 0.3 mL/min. Thus purified esterase was identified on an SDS-PAGE gel as in the Example 6(FIG. 6).
Example 10
[0053] Effect of Optical Resolution Conditions on Optical Resolution of a Novel Esterase
[0054] 1. Effect of pH
[0055] The hydration by a novel esterase is mostly performed in a buffered solution and thus the structure of the enzyme can be influenced much by the pH and chemical properties of a buffer solution being used. When using Pseudomonas sp. BHY-1 as a whole cell enzyme, the optimal enzyme activity was observed at pH 8.5. In the case of the novel esterase, the enzyme activity was shown to have a relatively wide pH range of 7-11 and the optical selectivity was shown to be optimal at pH 10.0 as shown in the following Table 1.
TABLE 1 Optimal pH of Esterase PH 7.0 8.0 8.5 9.0 10.0 11.0 Conversion (%) 1.8 2.4 2.0 2.2 7.9 5.4 Enantiomeric excess (%) 100 100 100 100 100 41
[0056] 2. Effect of Temperature
[0057] Optimal temperature for optical resolution is affected by the fictive temperature, defined as racemic temperature, and the optical selectivity in response to a temperature increase tends to vary depending on the kind of an enzyme. The novel esterase of the present invention is shown to have an excellent optical selectivity and the following shows the reaction rate of the enzyme. The reaction rate was observed at 10° C.-90° C., a temperature range for culturing Pseudomonas sp. BHY-1, and the optimal reaction rate was observed at 60° C.
TABLE 2 Optimal temperature of Esterase Temperature (° C.) 30 40 50 60 70 80 90 Conversion (%) 7.9 8.9 11.5 13.1 12.8 10.9 9.9 Enantiomeric 100 100 100 100 100 41 41 excess (%)
[0058] 3. Type of Reaction Substrates
[0059] Reaction substrates are in the form of ester and are mostly water insoluble. Therefore, it becomes necessary to mediate the reaction substrate to bind the enzyme for a desired enzyme reaction. In general, organic solvents such as dimethylsulfoxide, dimethylformamide, tetrahydrofuran, cyclohexane, benzene, etc., or non-ionic surfactant are used to serve the above mediation purpose. It is important to determine an organic solvent or a surfactant suitable for a given substrate. In profen pharmaceuticals, for example, Triton X-100 and dimethylsulfoxide were shown most effective.
Example 11
[0060] Optical Resolution of aryl propionic acid by Using a Novel Recombinant Esterase
[0061] Hydration was performed using 20 mM esters of ibuprofen, ketoprofen, and flurbiprofen to produce optically active ibuprofen, ketoprofen, and flurbiprofen. The reaction was performed at 37° C. (pH 8.5) with a reaction volume of 500 μL. Twenty four hours after the enzyme reaction, there was about 40% of conversion and enantiomeric excess (ee p ) was higher than 98.5% of optical selectivity as shown in the following Table 3.
TABLE 3 Substrate Conversion (%) Enantiomeric excess (%) Ibuprofen 40.9 >99 Ketoprofen 39.3 >99 Flurbiprofen 41.4 99
[0062] The novel esterase of the present invention derived from Pseudomonas sp. BHY-1 can be used in producing optically pure (S)— or (R)— type of aryl propionic acid having a pharmaceutical activity with high efficiency from racemic aryl propionic acid. | The present invention relates to an esterase, its DNA, its overexpression and a method for preparing an optically active aryl propionic acid of formula (1) using the same in high yield,
wherein R 1 represents an aryl group; and R 2 represents a hydrogen atom.
<110>KRIBB □SEQ:ID□ <120>Novel esterase, its DNA, overexpression, and production of optically active aryl propionic acids using same <160>8 <170>Kopatentln 1.71 <210>1 <211>1143 <212>DNA <213>Pseudomonas sp. BHY-1(KCTC 0688BP) <400>1 atgcagattc agggacatta cgagcttcaa ttcgaagcgg tgcgcgaagc tttcgccgca 60 ctgttcgacg atccccagga acgcggcgcc gcgttgtgca tccgggtcgg cggggaaacc 120 gtcctcgacc tctggtccgg caccgccgac aaggacggcg ccgaggcctg gcacagcgac 180 <213>Pseudomonas sp. BHY-1(KCTC 0688BP) <400>2 Met Gln Ile Gln Gly His Tyr Glu Leu Gln Phe Glu 1 5 10 Ala Val Arg Glu Ala Phe Ala Ala Leu Phe Asp Asp 15 20 Pro Gln Glu Arg Gly Ala Ala Leu 25 30 | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a method or process of making bread products using various types of processed and unprocessed, hulled and hulless, waxy barley flours to replace shortenings and/or oils.
Food products made from waxy barley is known in the ark. But, food products such as bread has always been made using animal shortenings and/or vegetable oils which enhanced the taste of the bread and acted as a lubricant and as a binder. Nowhere has waxy barley been used as a substitute in place of the animal shortenings and/or vegetable oils which resulted in the food product having a high fat content, becoming stale, having a reduced shelf life, and having to be used in conjunction with artificial preservatives.
One known prior art is a METHOD OF PREVENTING RETROGRADATION OF FOODSTUFFS, U.S. Pat. No. 4,690,829, INVENTOR: TAKAYUKI USUI, which used waxy barley starch as part of the starchy material and which added a polysaccharide to the starchy material but which did not substitute and did not suggest substituting the waxy barley starch for shortenings and/or oils.
Another known prior art is a PROCESS FOR PRODUCING A FAT-SUBSTITUTE BAKERY DOUGH AND THE FAT SUBSTITUTE BAKERY PRODUCTS, U.S. Pat. No. 5,344,663, INVENTOR: ANNE M. JEWELL, which comprises a wheat flour, potato flour, non-fat dry milk solids, emulsifying binders such as molasses and corn syrups, and a leaving agent to produce essentially fat-free bakery products unlike the present invention which uses waxy barley flour in place of shortenings and/or oils to produce fat-free bakery products.
None of the prior art describes using waxy barley as a substitute for animal shortenings and/or vegetable oils. Even in the patent which used waxy barley starch, animal shortenings and/or vegetable oils were still used to make the foodstuffs. Nowhere in the prior art has it been suggested that waxy barley can effectively be used as a substitute of the conventionally used animal shortenings and/or vegetable oils to preferably make or bake bread products.
SUMMARY OF THE INVENTION
This invention relates to a process or method of making or baking leavened bread products without shortenings and/or oils which have been one of the staple or prime ingredients used especially for making or baking bread products. Hulled and hulless waxy barley has been used as a replacement for the shortenings and/or oils in bread products.
One objective of the method of making bread products without shortenings and/or oils is to make healthier bread products having zero fat content.
Another objective of the method of making bread products without shortening and/or oils is to produce bread having a longer shelf life.
Also, another objective of the method of making bread products without shortenings and/or oils is to produce bread having a high volume of moisture for preventing the drying out of the bread.
Yet, another objective of the method of making bread products without shortenings and/or oils is to produce bread without preservatives.
Further objectives and advantages of the present invention will become apparent as the description proceeds and when taken in conjunction with the accompanying drawings wherein:
DETAILED DESCRIPTION OF THE INVENTION
Through intensive research and testing, a method of making bread products without animal shortenings and/or oils was developed using processed and unprocessed, hulled and hulless or nonhulled waxy barley in place of the shortenings and/or oils which resulted in bread products having a high moisture content. The waxy barley fibers hold and absorb moisture throughout the bread baking process and into the finished product. It wasn't until recently that waxy barley, a crop plant, has been successfully grown in the United States. Prior to this, waxy barley was known only in countries in the Orient such as China Korea, and Japan. Waxy barley flour is produced from a variety of waxy barleys and is characterized by having soluble fiber which has a high viscous state especially when used in the baking of breads. The high viscous state of the soluble fiber of the waxy barley flour is believed to be the reason why the waxy barley flour can be successfully substituted for animal shortenings and/or vegetable oils which prior to this invention, were the staple ingredients for bread products. The soluble fibers in the waxy barley flours are capable of absorbing and holding high volumes of moisture which are needed to keep the bread products fresh and to prevent the bread products from becoming stale and drying out.
Waxy barley flour is essentially made from hulled and hulless or nonhulled, processed and unprocessed waxy barley including berries which are either heat treated or left untreated. The waxy barley flour made from heat treated berries retained more moisture than the waxy barley flour made from untreated berries. Further, the waxy barley flour made from the hulless variety of waxy barley retained 10 to 15 percent more moisture than the hulled variety of waxy barley.
In making bread products, the waxy barley flour used in place of the animal shortenings and/or vegetable oils should be in the range of 15 to 40 percent by weight of the total material used in the recipe or the bread dough to make the bread products. Concentrations higher than 40 percent by weight of the waxy barley flour in the total recipe of the bread dough results in the bread dough retaining too much moisture and becoming essentially uncontrollable. Concentrations lower than 15 percent by weight of the waxy barley flour in the total recipe results in the bread dough being too dry. Further, two different types of barley bread bases were used to make the bread products, and both barley bread bases contained waxy barley flour in the range of 35 to 60 percent by weight of the total bread bases. A barley white bread base was made by using both hulled and hulless, processed or heat treated and unprocessed waxy barley and also includes wheat flour, wheat gluten, dextrose, salt, diacetyl tartaic acid esters of mono-diglycerides (DATEM), mono-diglycerides, soy flour, lecithin, calcium salts, ascorbic acid, azodi-carbonamide, carbamide, vegetable powder, fungal amylase, and sodium stearoyl lactylate, and a barley wheat bran bread base was made by using the same varieties of waxy barley and adding wheat bran for added texture, taste, and color and also includes wheat bran, wheat flour, wheat gluten, dextrose, salt, diacetyl tartaic acid esters of mono-diglycerides (DATEM), mono-diglycerides, soy flour, lecithin, calcium salts, ascorbic acid, azodi-carbonamide, carbamide, vegetable powder, fungal amylase, and sodium stearoyl lactylate. A good bread dough can be achieved from combining or mixing 50 pounds of the barley bread base either white or wheat bran with 100 pounds of wheat bread flour, 110 to 120 pounds of water, and yeast minus animal shortenings and/or vegetable oils.
EFFECTS OF THE INVENTION
This invention can be applied to various types of conventional leavened bread baked items such as white bread loaves, bran bread loaves, hamburger buns, dinner buns, bread sticks, cinnamon rolls, and cinnamon crisps. Hence, animal shortenings and/or vegetable oils can be readily and totally replaced by waxy barley flours to produce bread products which are soft, elastic, digestible and have good quality texture without the fats effected by the shortenings and/or oils.
(EXAMPLE 1)
White bread loaves were produced using a conventional baking method and using the following recipe. All ingredients are expressed in pounds:
______________________________________Barley white bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Yeast (Red Star Cake) 3/4 lbs.______________________________________
To keep this product essentially fat free, flour was used to coat the mixing bowl instead of oil. Loaves were baked in glazed pans. The dough was mixed 12 to 18 minutes with temperatures maintained between 78 to 80 degrees Fahrenheit. After mixing, the dough was scaled to 19 ounces loaf weight and rounded up. The dough was allowed to rest for 10 to 15 minutes before it was molded into a loaf shape. The loaves were baked at 380 to 400 degrees Fahrenheit for 30 to 32 minutes which resulted in essentially fat-free finished products.
(EXAMPLE 2)
White 2 ounce hamburger buns were produced using a conventional baking process and using the following recipe:
______________________________________Barley white bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Yeast (Red Star Cake) 3/4 lbs.______________________________________
After mixing in a bowl lined with flour instead of oils and/or shortenings for 12 to 18 minutes with the dough temperatures maintained between 78 and 80 degrees Fahrenheit, the dough was scaled into 2 ounce portions. The portions were then rounded up and rested for 10 to 15 minutes. The portions were then rounded up again and placed on pans with liners. The buns were then flattened and placed on racks to proof. The buns were baked to 375 to 400 degrees Fahrenheit for approximately 15 to 18 minutes which resulted in essentially fat-free buns.
(EXAMPLE 3)
White 1.3 ounce dinner rolls were produced using a conventional baking method and using the following recipe:
______________________________________Barley white bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Yeast (Red Star Cake) 3/4 lbs.______________________________________
After mixing these ingredients in a bowl lined with flour instead of oil for 12 to 18 minutes with the dough temperatures maintained between 78 and 80 degrees Fahrenheit, the dough was scaled into 1.3 ounce portions. The portions were rounded up and rested for 10 to 15 minutes, and then rounded up again and placed on lined baking pans. The rolls were placed on racks to proof for several minutes. These rolls were baked at 375 to 400 degrees Fahrenheit for approximately 13 to 15 minutes.
(EXAMPLE 4)
White 1.6 ounce bread sticks were produced using a conventional baking process and using the following recipe:
______________________________________Barley white bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Yeast (Red Star Cake) 3/4 lbs.______________________________________
After mixing these ingredients in a bowl lined with flour instead of oil for 12 to 18 minutes with the dough temperatures maintained between 78 and 80 degrees Fahrenheit, the dough was scaled into 1.6 ounce portions. The portions were rounded up and rested for 10 to 15 minutes, and then rounded up again and placed on lined baking pans. The bread sticks were placed on racks to proof for several minutes, and then baked at 375 to 400 degrees Fahrenheit for approximately 13 to 15 minutes.
(Example 5)
White 2.5 ounce cinnamon rolls were produced using a conventional baking process and using the following recipe:
______________________________________Barley white bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Granulated sugar 1 lbs.Yeast (Red Star Cake) 3/4 lbs.Cinnamon 1/2 oz.______________________________________
After mixing the base, flour, water, and yeast ingredients in a bowl lined with flour instead of oil for 12 to 18 minutes with the dough temperatures maintained between 78 and 80 degrees Fahrenheit, the dough was rolled flat and sprinkled with sugar and cinnamon. The dough was then rolled up and scaled into 2.5 ounce portions. The portions were placed on lined baking pans and rested 10 to 15 minutes before baking at 375 to 400 degrees Fahrenheit for approximately 13 to 15 minutes.
(EXAMPLE 6)
Wheat bran loaves were produced using a conventional baking process and using the following recipe:
______________________________________Barley with bran bread base 5 lbs.Wheat bread flour 10 lbs.Water 10-12 lbs.Yeast (Red Star Cake) 1/2 lbs.______________________________________
After mixing the base, flour, water, and yeast ingredients for 12 to 18 minutes, the mixing bowl was lined with flour instead of oil to aid in the removal of the dough from the bowl. Dough Temperatures were maintained between 79 degrees and 80 degrees Fahrenheit. After mixing, the dough was scaled to approximately 19 ounces and rounded up. The dough was rested for 10 to 15 minutes, and then molded into loaves and baked in glazed pans at 380 to 400 degrees Fahrenheit for approximately 30 to 32 minutes.
(EXAMPLE 7)
Wheat bran 2 ounce hamburger buns were produced using a conventional baking method and using the following recipe:
______________________________________Barley with bran base 5 lbs.Wheat bread flour 10 lbs.Water 12 lbs.Yeast (Red Star Cake) 1/2 lbs.______________________________________
The ingredients were mixed 12 to 18 minutes with the dough temperatures maintained between 78 and 80 degrees Fahrenheit. The dough was removed from the mixing bowl using flour instead of oil to separate the dough from the bowl. The dough was scaled into bun portions, rounded up, rested for 10 to 15 minutes, and then rounded up again and placed on lined pans. The dough was flattened and allowed to proof for several minutes before baking for approximately 15 to 18 minutes at 375 to 400 degrees Fahrenheit.
Various changes and departures may be made to the invention without departing from the spirit and scope thereof. Accordingly, it is not intended that the invention be limited to that specifically described in the specification or as illustrated in the drawings but only as set forth in the claims. | The method of making bread products without animal shortenings and/or vegetable oils comprises substituting waxy barley flour made from processed or unprocessed, hulled or nonhulled waxy barley for shortenings and/or oils. Bread products comprising waxy barley flour less the shortenings and/or oils which were one of the staple ingredients for making bread products, are essentially fat free, have a longer shelf life and are healthier for people than conventional bread products. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to dispensing apparatus and more particularly, to a toothpaste or cream dispensing apparatus which may be designed for wall mounting or for positioning on a counter top or lavatory for dispensing of the desired toothpaste or cream. The dispensing device of this invention is characterized by a base member, a brush holder, and a removable cover, whch in combination carry a movable carriage and roller and a chain and cooperating lever for effecting controlled travel of the carriage and roller with respect to the base and cover to facilitate the emission of a controlled quantity of toothpaste or cream from a supply tube placed inside the cover and in cooperation with the travelling carriage and roller system. The dispensing device is characterized by high efficiency in that a controlled quantity of toothpaste or other cream, such as hand lotion, can be dispensed with each manipulation of the lever, and leakage of paste or cream from the tube between dispensing operations is kept to a minimum. The dispensing device can be easily fitted to an interior wall at a convenient location, and in another embodiment may be placed on a counter top for portable access. The dispensing mechanism is simple yet efficient, and can be manipulated by persons of all ages.
2. Description of the Prior Art
Dispensing apparatus for toothpaste and other viscous materials such as hand cream and the like have long been known in the prior art. For example, U.S. Pat. No. 1,156,106 to R. S. Smart discloses a toothpaste dispensing device which includes a tubular container carrying a tube of toothpaste and a ratchet mechanism for effecting forced collapse of the tube to cause emission of toothpaste at the bottom of the device responsive to manipulation of a spring-loaded lever mechanism. A later device is disclosed in U.S. Pat. No. 1,930,821 to P. A. Newcomer, et al, in his Tube Cream Dispenser, which also includes a generally cylindrically shaped body with a threaded post in the center and a carriage and roller combination travelling on the threaded post to effect forced collapse of the tube and ejection of a controlled quantity of toothpaste responsive to manipulation of a lever located at the top of the apparatus. Another similar dispenser is disclosed in U.S. Pat. No. 3,257,037 to C. B. Watson, Jr. The Collapsible Tube Squeezer illustrated in that patent includes yet another cylindrically shaped device capable of housing a collapsible tube of toothpaste or other cream, and is fitted with a pair of rollers at the base, which rollers are positioned in cooperation with a pair of flat metal members traversing the length of the tube and caused to approach each other to squeeze the tube upon manipulation of a lever located at the top of the device to eject a controlled quantity of paste or cream from the tube.
Some of the primary problems realized in prior art cream or toothpaste dispensing apparatus is the lack of positive sealing to prevent leakage and hardening of the material dispensed, and lack of mechanical simplicity of such devices, and the general lack of asthetic appeal regarding design and ease of operation. Cost of manufacture is another problem inherent in many of these devices, and this factor becomes more important as the dispenser design becomes more complex.
Accordingly, it is an object of this invention to provide a new dispensing device which is characterized by positive sealing to prevent leakage of the dispensed material, and aesthetic appeal both as to design and ease of operation, as well as functional utility in providing a support for toothbrushes and a glass or cup, which device may be wall mounted, or in another embodiment, placed on a counter top, lavatory or sink area.
Yet another object of the invention is to provide a new and improved toothpaste dispensing device which is lever-operated and which can be quickly and easily utilized to dispense a controlled quantity of toothpaste on a toothbrush in a single manipulation of the lever.
Another object of this invention is to provide a toothpaste or other cream dispensing device which is characterized by a travelling carriage and roller combination in cooperation with a lever-manipulated chain, which lever effects a controlled movement of the carriage and roller against an internally positioned collapsible tube to dispense a selected quantity of toothpaste from the device during each manipulation of the lever.
A still further object of the invention is to provide a new and improved toothpaste dispensing device, the cover of which can be quickly and easily removed from the base member and brush holder to remove a depleted tube and insert a fresh tube by anyone of sufficient age to need the use of a toothbrush.
A still further object of the invention is to provide a new and improved paste or cream dispensing device for ejecting a controlled quantity of toothpaste or cream by manipulation of a lever, which further includes a mounting base sufficiently large to carry several toothbrushes and a glass or cup mounted in cooperation with the dispensing mechanism for improved efficiency and utility of the dispensing device.
SUMMARY OF THE INVENTION
These and other objects of the invention are provided in a dispensing device which includes a base member, a brush holder in cooperation with the base member and interiorly provided with a paste cavity and a lever slidably positioned beneath the paste cavity and attached to one end of a length of pull chain. The opposite end of the pull chain is attached to the base member by means of a spring, and a carriage and roller combination travels on the chain in cooperation with the base member. The device further includes a removable cover for securing a collapsible paste or cream supply tube adjacent the roller and carriage means to facilitate controlled collapse of the tube by successive downward movement of the carriage and roller on the chain responsive to manipulation of the lever to dispense a controlled quantity of toothpaste or cream from the paste cavity.
BRIEF DESCRIPTION OF THE DRAWNGS
The invention will be better understood by reference to the accompanying drawing, wherein:
FIG. 1 is a perspective view of a preferred embodiment of the dispensing device of this invention adapted for wall mounting;
FIG. 2 is a sectional view of the dispensing device illustrated in FIG. 1 and taken along lines 2--2 in FIG. 1, more particularly showing a preferred interior mechanism of the device;
FIG. 3 is another sectional view of the dispensing device illustrated in FIG. 1 and taken along lines 3--3 in FIG. 1, more particularly illustrating the lever and pull chain combination;
FIG. 4 is another sectional view of the dispensing device illustrated in FIG. 1 also taken along lines 3--3 of FIG. 1, with the lever moved forward of its position shown in FIG. 3;
FIG. 5 is a sectional view of the dispensing device illustrated in FIG. 1 and taken along lines 5--5 in FIG. 1, and further illustrating the carriage and roller combination of the dispensing mechanism;
FIG. 6 is another sectional view of the dispensing device illustrated in FIG. 1 and taken along lines 6--6 in FIG. 1, more particularly showing the carriage and roller mechanism;
FIG. 7 of the invention is a top view of the base member of the dispensing device illustrated in FIG. 1;
FIG. 8 is a perspective view, partially in section, of a frontal segment of the dispensing lever of this invention; and
FIG. 9 is a perspective view of a preferred nozzle of the dispensing device of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIGS. 1, 2, 6 and 7 of the drawing, the dispensing device of this invention is generally illustrated by reference numeral 1, and includes a cover 2, which removably slides over a mounting base 5 and cover base 17 to mate with cover slot 11, as illustrated in FIG. 1. A brace 18 is fitted between mounting base 5 and brush holder 8 as illustrated in FIG. 2. Cover 2 is fitted with projecting cover guides 3 which register with cover guide slots 6 in mounting base 5, as illustrated in FIGS. 6 and 7 of the drawing. In the case of models designed to rest on a sink, lavatory or counter top, the bottom surface of mounting base 5, illustrated in FIG. 1, would be generally coextensive with the bottom surfaces of cover base 17 and brush holder 8, and the dispensing device 1 is further mounted on a base (not illustrated) to permit placing toothbrushes in brush apertures 9 provided in brush holder 8. Accordingly, as further illustrated in FIG. 1, in a preferred embodiment of the invention the brush holder 8 further includes brush apertures 9 for receiving toothbrushes, and also features a glass or cup seat 10 to facilitate resting of a glass or cup securely but removably on brush holder 8. Furthermore, a nozzle 26 is mounted on the front end of brush holder 8, and a lever 20, fitted with a lever handle 21, is positioned immediately beneath nozzle 26 and is slidably disposed inside lever aperture 12 of brush holder 8 and in cover base 17, as is more particularly shown in FIG. 2. Brush holder 8 further includes a paste cavity 13 which is disposed in generally parallel relationship to lever aperture 12, and extends through the interior of cover base 17 with one end opening upwardly to receive a connecting tube 65. The opposite end of paste cavity 13 terminates in the interior of nozzle 26, with nozzle insert aperture 29 of nozzle insert 27 coextensive with the base of paste cavity 13, as illustrated. In a preferred embodiment of the invention, paste cavity 13 is also fitted with a surge chamber 14, which serves to reduce the paste or cream pressure in paste cavity 13 after the dispensing of a quantity of paste or cream, and helps reduce the leakage of paste or cream from nozzle 26 between manipulations of lever 20.
Referring now to FIGS. 2-4 of the drawing, as heretofore described, lever 20 is slidably positioned in lever aperture 12 provided in brush holder 8 and cover base 17. As illustrated in FIGS. 3 and 4, lever 20 is also provided with a paste access aperture 22 near the forward end, and an engaging plate slot 45, which narrows near the rear end thereof to form lever shoulders 39. An engaging plate 40 is fitted inside engaging plate slot 45 when lever 20 is in normally retracted position as illustrated in FIG. 3 of the drawing. Engaging plate 40 includes an engaging plate leg 42, which carries an engaging plate head 41 at the forward end thereof. Engaging plate leg 42 rests against a base rest 47 which is fitted with a base rest channel 48 to accommodate pull chain 31, one end of which is attached to engaging plate leg 42. Base rest 47 is mounted in cover base 17 in fixed relationship. Base pin 44 extends downwardly from a point of attachment to engaging plate leg 42 into a lever stop slot 15 provided in brush holder 8, which limits the travel of lever 20, as illustrated in FIG. 2. Lever 20 also carries a lever insert 23, fitted with a lever insert aperture 24, with lever insert 23 positioned in lever insert seat 25, as further illustrated in FIG. 8 of the drawing. The lever insert aperture 24 is designed to mate with nozzle insert aperture 29 of nozzle insert 27, with nozzle insert 27 fitted in nozzle insert seat 30, of nozzle 26, as illustrated in FIGS. 2 and 9. As further illustrated in FIGS. 3 and 4 of the drawing, in a preferred embodiment of the drawing pull chain 31 is characterized by a plurality of balls 32 connected by a plurality of links 33, with one end of the chain attached to engaging plate leg 42 of lever slide 40, and the opposite end attached to a spring 34, as illustrated in FIG. 2. Spring 34 is in turn suspended in the upper segment of a generally "dove tail" shaped carriage slot 7, provided in mounting base 5, by means of a spring pin 35, and pull chain 31 extends through carriage guide aperture 51 of carriage 49 downwardly through carriage slot 7 to spring roller 36, where it rides on roller drum 37 of spring roller 36 in a 90 degree turn to the point of attachment to engaging plate leg 42 of engaging plate 40. Spring roller 36 rotates on roller pin 38 responsive to the manipulation of lever 20 and the travel of pull chain 31 as hereinafter described.
Referring now to FIGS. 2, 5 and 6 of the drawing, carriage 49 is fitted with a carriage guide 50, which, in a preferred embodiment, is generally "dovetail" in shape in order to mate and register with carriage slot 7 in mounting base 5. Carriage 49 is slidably positioned inside cover 2 and carries a carriage roller 52, rotatable on a carriage roller pin 53, as illustrated. Carriage travel hinge 54 is attached to carriage 49 by means of a hinge mount 59 and hinge mount screws (not illustrated), with a retaining arm 55 extending toward pull chain 31, and a retaining arm slot 56, provided in retaining arm 55, pressed against one of the links 33 which is appropriate to the position of carriage 49 inside housing 2, as illustrated in FIG. 6. Arm release 57, which is provided on retaining arm 55, serves to pivot retaining arm 55 upward in carriage travel hinge 54 to release it from engagement with a selected one of balls 32 and links 33 in order to facilitate movement of carriage 49 upwardly on pull chain 31 with respect to housing 2 and mounting base 5 when it is desired to load a new collapsible tube 61 inside dispensing device 1. When retaining arm 55 is in functional position with retaining arm slot 56 adjacent a specified one of links 33 and retaining arm 55 is positioned beneath one of balls 32, arm bias 58, which is attached to carriage 49, serves to bias retaining arm 55 downwardly and against the top of carriage guide 50 and the respective one of balls 32 and links 33 in question. This mechanical arrangement permits a graduated downward movement of carriage 49 and carriage roller 52 with downward displacement of pull chain 31, as hereinafter described. As further illustrated in FIG. 2 of the drawing, a paste or cream-containing collapsible tube 61 is positioned inside cover 2 by inverting the tube, removing the cap, engaging the tube neck 60 with connecting tube 65 as hereinafter described, and attaching the tube base 64 to a tube clip 67, mounted by means of tube clip arms 68 to the top of mounting base 5.
In operation, referring again to the drawing, the dispensing device 1 of this invention is mounted, loaded and operated as follows. Cover 2 of dispensing device 1 is initially grasped and moved upwardly with cover guides 3 disengaging cover guide slots 6 to remove cover 2 from mounting base 5. A set of screws (not illustrated) are placed in registration with screw mount apertures 16 provided in mounting base 5, and mounting base 5 is tightened against a selected wall area by driving the screws into the wall. Arm release 57 is then manipulated to release the pressure of arm bias 58 from retaining arm 55 and remove retaining arm 55 and retaining arm slot 56 from engagement with the specific one of balls 32 and links 33 of pull chain 31 with which the arm and slot were engaged, to permit carriage 49 to slide freely upward on pull chain 31. The tube base 64 of a spent collapsible tube 61 is then removed from engagement with tube clip 67, and the connecting tube cap 62, flanged onto connecting tube 65 and fitted with interior connecting tube threads 63 is turned in the clockwise direction to disengage connecting tube threads 63 from the threads on tube neck 60 of collapsible tube 61, as illustrated in FIG. 2. The empty collapsible tube 61 is then discarded, and a fresh tube is secured to connecting tube 65 by counterclockwise rotation of connecting tube cap 62 to loosely secure connecting tube 65 to collapsible tube 61. The new collapsible tube 61 is then oriented with respect to tube clip 67 such that tube base 64 can be attached to tube clip 67 as illustrated in FIG. 2, and connecting tube cap 62 is tightened on tube neck 60. Expansion collar 66 is provided in connecting tube 65 to more easily align connecting tube cap 62 on the threaded tube neck 60 of collapsible tube 61 while inserting a new collapsible tube 61 in dispensing device 1. Cover 2 is then repositioned on mounting base 5 by engaging cover guides 3 with cover guide slots 6 and mating the bottom of cover 2 with cover slot 11, as illustrated in FIG. 1.
When, for example, the material in collapsible tube 61 is toothpaste and it is desired to dispense the toothpaste from the collapsible tube 61 and dispensing device 1, a toothbrush 69, having bristles 70, is removed from the appropriate brush aperture 9 of brush holder 8 and is positioned beneath nozzle 26 and lever 20, as illustrated in FIG. 1. Lever 20 is then pulled forward as indicated in FIG. 4 of the drawing to the point where lever shoulders 39, which narrow engaging plate slot 45, engage engaging plate head 41 of engaging plate 40. At this point, paste access aperture 22 in lever 20 is displaced in lever aperture 12 to a point beneath nozzle insert aperture 29, which provides an opening in lever 20 to permit paste located in paste cavity 13 to flow through paste cavity 13, surge chamber 14, and nozzle insert aperture 29 onto the toothbrush. Additional displacement of lever 20 in the direction of the arrow shown in FIG. 4 causes engaging plate 40 to move forward and displace pull chain 31 against the bias of spring 34 in carriage slot 7. Since retaining arm 55 and retaining arm slot 56 are secured beneath a selected one of balls 32 and links 33 of pull chain 31, carriage 49 and carriage roller 52 are displaced downwardly with pull chain 31 a selected distance to effect a partial collapse of collapsible tube 61 and force toothpaste from collapsible tube 61 through connecting tube 65 and into paste cavity 13 and surge chamber 14. It has surprisingly been found that the presence of an enlarged area or surge chamber 14 in paste cavity 13 reduces the post lever manipulation pressure at nozzle insert aperture 29 to prevent undesirable leakage. Return of lever 20 to its original position as illustrated in FIGS. 2 and 3 of the drawings releases tension on pull chain 31 and permits pull chain 31 to move upwardly in carriage slot 7 and through carriage guide aperture 51 in carriage 49 responsive to the pull of spring 34. Each successive one of balls 32 and links 33 which are in the vicinity of retaining arm 55 move upwardly past retaining arm 55 and retaining arm slot 56 until spring 34 returns to its original configuration, and a different and lower one of balls 32 and links 33 is positioned adjacent retaining arm 55 and retaining arm slot 56. Continued manipulation of lever 20 in the manner described above results in a controlled quantity of toothpaste dispensed from nozzle insert aperture 29 of nozzle 26 with the mating of lever insert 23 and nozzle insert 27 effecting a seal of nozzle insert aperture 29 to prevent undesirable leakage of the toothpaste or cream from, or hardening in, nozzle insert aperture 29, between each manipulation.
It will be appreciated by those skilled in the art that when the initial collapsible tube 61 is placed in dispensing device 1 as above described, several manipulations of lever 20 will be necessary in order to fill paste cavity 13 and surge chamber 14 prior to the dispensing of paste or cream from nozzle insert aperture 29. However, after paste cavity 13 is full, a single manipulation of lever 20 in the manner described above will effect ejection of a controlled quantity of paste or cream from nozzle insert aperture 29 each time lever 20 is pulled outwardly.
Referring now to FIGS. 8 and 9 of the drawing, in a preferred embodiment of the invention, and as heretofore described, lever 20 is fitted with a lever insert seat 25 provided in the surface of lever 20, and a lever insert 23 having a lever insert aperture 24, the top surface of which is substantially flush with lever 20. Furthermore, nozzle 26 is additionally provided with a similar nozzle insert 27, the nozzle insert mouth 28 of which is designed to mate with the bore of paste cavity 13 which is situated in essentially horizontal configuration inside nozzle 26. Nozzle insert 27 is also fitted with a nozzle insert aperture 29 and is designed to fit inside a nozzle insert seat 30 provided in nozzle 26 such that the bottom surface of nozzle insert 27 is essentially coextensive with the bottom surface of nozzle 26. Accordingly, referring again to FIG. 2 of the drawing, it will be appreciated that when lever 20 is in the normally closed position the exposed surfaces of lever insert 23 and nozzle insert 27 are in mating cooperation, and no toothpaste or cream is permitted to drip from paste cavity 13. Displacement of lever 20 in the direction indicated by the arrow in FIG. 4 of the drawing causes paste access aperture 22 to register with nozzle insert aperture 29 to permit paste or cream to flow from nozzle insert aperture 29 as heretofore described.
Referring again to FIGS. 2 and 5 of the drawing, it will be appreciated that while in a preferred embodiment of the invention collapsible tube 61 is positioned securely inside dispensing device 1 by means of a tube clip 67 which is mounted on mounting base 5 by means of a pair of tube clip arms 68, alternative tube mounting means known to those skilled in the art may be used to secure collapsible tube 61 inside dispensing device 1. Furthermore, referring again to FIG. 2, it will be further appreciated that in the embodiment of this invention wherein the dispensing device includes a base pin 44 carried by engaging plate leg 42 of engaging plate 40 to move in lever stop slot 15, the length of lever stop slot 15 can be varied or adjusted to control the length of travel of lever 20, and the amount of paste or cream ejected from nozzle 26 for each manipulation of lever 20. | A wall or table-mounted cream or paste dispensing device which includes a mounting base and a cooperating brush holder and cover and further characterized by a travelling carriage which is fitted with a roller to effect collapse of a toothpaste or other cream-containing tube, which roller is constrained to move downwardly against the tube in discrete increments by activation of a lever and pull chain combination. The carriage travels on the chain responsive to manipulation of the lever, and paste or cream is dispensed in controlled quantities from a nozzle communicating with the compressed tube. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to pellets of a chlorinated vinyl chloride resin (hereinafter referred to as "CPVC") compositon, pre-expanded particles and a process for preparing thereof, and more particularly to pellets of CPVC composition, pre-expanded particles prepared from the pellets and a process for preparing thereof for obtaining a foamed article having characteristics such that the foamed article generates little heat, produces little smoke and little poison gas and is hardly strained and cracked at burning, and further, has a large dimensional retention when an obtained foamed article is used in an atmosphere of high temperatures, i.e. the foamed article is excellent in heat resistance.
Since a CPVC has a large chlorine content, generates little heat and produces little smoke at burning, it is expected that the CPVC is employed as a heat insulating material having a high fireproofing property. However, a foamed article of the CPVC has a problem in fireproofing property, that is, the foamed article is largely shrunk when it is exposed in an atmosphere of high temperatures, for instance, in fire and the like. In order to prevent the foamed article from shrinkage, it has been studied to contain a large amount of inorganic materials in the foamed article.
However, it has not yet been succeeded to get an excellent foamed CPVC article containing a large amount of inorganic materials by using the pre-expanded particles of the CPVC and the process for preparing thereof.
On the other hand, the melt-adhesion of the particles is lowered when the pre-expanded particles containing a large amount of the inorganic materials are subjected to an expansion molding in a mold because the inorganic materials existing on the surface of the particles act as an anti-blocking agent.
Besides, since the CPVC has a high softening temperature and requires high temperatures to give the excellent melt-adhesion of pre-expanded articles of the CPVC, a conventional molding machine used for the expansion molding of polystyrene or polyethylene can not be employed. Accordingly, there is a problem that a molding machine which is proof against high temperatures and high pressures which are usually generated from steam employed as a heat sourse should be specially equipped.
Still more, even though a large amount of the inorganic materials can be contained in the foamed article, there are some problems such that the residual stress and/or residual strain in the foamed article which are caused by the drawing of the resin during expansion are large. In such case, the shrinkage is generated due to the residual stress and/or the residual stain when the article is exposed in an atmosphere of high temperatures. That is, the shrinkage of the foamed article can not be minimized by containing the inorganic materials.
As the result of repeating earnest studies in order to solve the above-mentioned problems in the conventional process, there have been found the pellets of CPVC composition, the pre-expanded particles and the process for preparing thereof which are capable of solving the problems, and the present invention has been accomplished.
SUMMARY OF THE INVENTION
According to the present invention, there are provided pellets of a CPVC composition comprising inorganic materials, a solvent and a blowing agent and pre-expanded particles of the CPVC comprising inorganic materials and a solvent. And further, according to the present invention, there is provided a process for preparing pre-expanded particles of the CPVC containing inorganic materials, which comprises kneading a CPVC, inorganic materials and a solvent, pelletizing the kneaded mixture, impregnating a blowing agent into the resulting pellets and pre-expanding the pellets.
According to the present invention, the above-mentioned problems are solved by employing pre-expanded particles of the CPVC containing a solvent prepared by expanding pellets of a CPVC composition containing inorganic materials, a solvent and a blowing agent.
That is, by employing a solvent compatible with the CPVC and by containing the solvent into the pellets of CPVC composition, the viscosity of the CPVC composition is lowered when the pellets of the CPVC composition are expanded, and thereby the residual stress and/or residual strain in the pre-expanded particles are released and further, the deterioration of the effect of dimensional stability which is occurred by containing inorganic materials is prevented by lowering the shrinkage due to residual stress and/or strain.
Also, the present invention makes it possible to obtain a foamed article having a high fusion percentage by employing a conventional molding machine used for the expansion molding of a polystyrene or polyethylene resin at low molding temperatures. And because of containing the solvent compatible with the CPVC, the softening temperature of the resin is lowered and the fusion percentage of the pellets which constitute the finished product is improved.
Further, the present invention makes it possible to prepare pre-expanded particles of the CPVC containing a large amount of the inorganic materials by preparing and kneading the CPVC and inorganic materials and a satilizer as occasion demands under the condition of the existence of the solvent to form a gel, pelletizing the formed gel, impregnating a physical blowing agent into the obtained pellets after not removing the solvent or removing the excess solvent by volatilization in the occasion that the amount of solvent which should be contained in the pre-expanded particles is small and then pre-expanding the pellets by heating then with a heating source such as steam.
That is, the present invention makes it possible to add a large amount of inorganic materials in the CPVC by forming a uniform gel phase of the CPVC and the solvent and wrapping the inorganic materials in the gel phase.
Though the functions of the solvent are not always obvious, it is thought that the solvent has a function to increase the degree of wrapping inorganic materials in the resin parts by forming a uniform gel phase and increasing the volume of the resin parts in comparison to the case that the solvent is not included and by lowering the viscosity of the resin parts. Also, it is thought that the air and moisture bonded on the surface of the inorganic materials are removed by wetting the surface of the inorganic materials with a solvent, and thereby the surface of the inorganic materials and the resin parts are stiffly adhered.
From the above-mentioned effects, the inorganic materials are completely wrapped with a thin film of the resin, and thereby the trouble that the cells are broken in the discontinuous part of the resin phase in the process of the expansion can be avoided.
Still more, since the solvent is existed in the pellets, the processing temperature for molding comes to be largely lower than a usual processing temperature for molding a CPVC and decrease dangers such as the troubles of decomposition and deterioration which are often occurred when the CPVC is produced are generated.
These and other objects of the present invention will become apparent from the description hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
The term "CPVC" in the present invention means not only an chlorinated polyvinyl chloride resin but also a mixed resin containing chlorinated polyvinyl chloride at a content of not less than 50% by weight. Examples of the resin which is mixed with chlorinated polyvinyl chloride are, for instance, vinyl chloride resin, chlorinated polyethylene, and the like.
As the vinyl chloride resin which is chlorinated, a copolymer containing vinyl chloride at a content of not less than 50% by weight can be used as well as a usual vinyl chloride resin.
Examples of the component which is copolymerized with vinyl chloride are, for instnace, vinyl acetate, vinylidene chloride, ethylene, and the like.
Any chlorinating methods which are conventionally adopted, for instance, photo-chlorination method under ultraviolet irradiation, and the like can be employed in the present invention.
When the average degree of polymerization of the CPVC is too small, the properties of the obtained foamed article is lowered, and when the average degree of polymerization is too large, it is difficult to industrially produce such a CPVC. Therefore, it is suitable that the CPVC has an average degree of polymerization of 300 to 5000 and a chlorine content of 60 to 75% by weight, preferably an average degree of polymerization of 1000 to 3000 and a chlorine content of 60 to 70% by weight.
The particle size of the CPVC is not limited in the present invention if it is in a range which is usually used.
The inorganic materials used in the present invention are, for instance, inorganic particles having an average particle size of about 0.01 to 300 μm, inorganic fibrous materials having an average fiber length of about 1 μm to 50 mm, and the like.
The kinds of the inorganic materials are not particularly limited in the present invention. However, from the viewpoint of cost and commercial availability, it preferable that the inorganic materials are, for instance, inorganic particles such as talc, calcium carbonate, aluminium hydroxide and magnesium hydroxide; inorganic fibrous materials such as asbestos, rock wool and glass fiber, and the like. Also, hollow materials such as shirasu balloon may be used. These inorganic materials may be used alone or in admixture thereof.
The amount of the inorganic materials is adjusted in accordance with the uses of the obtained foamed article which is a final product and is usually in a range of 5 to 1000 parts by weight, preferably 5 to 500 parts by weight based on 100 parts by weight of the CPVC.
As a solvent used in the present invention, any kinds of the solvent may be basically employed if the solvent has a compatibility with the CPVC. There are several methods to estimate the compatibility. Among the methods, the method that a mixture of 100 parts by weight of the CPVC having an average degree of polymerization of 2500 and a chlorine content of 67% by weight, 100 parts by weight of a solvent and 6 parts by weight of bis(di-n-butyltin monolaurate maleate) as a stabilizer is kneaded with a Brabender plastograph and then the temperature is measured when the mixture shows a maximum torque is employed. It is preferable that the solvent has a temperature of not more the 170° C. when the maximum torque is shown by measuring the above-mentioned method.
Examples of the solvent are, for instance, an aromatic hydrocarbon such as benzene, toluene, xylene or diethylbenzene (hereinafter referred to as "DEB"); a halogenated hydrocarbon such as 1,2,4-trichlorobenzene; a derivative of polyhydric alcohol such as butyl cellosolve (hereinafter referred to as "BC"); a ketone such as di-isobutyl ketone (hereinafter referred to as "DIBK") or cyclohexanone (hereinafter referred to as "CNON"); an ester such as isooctyl acetate (hereinafter referred to as "IOA"); a carbonic acid derivative such as diethyl carbonate; a phosphorus compound such as trischloroethyl phosphate; a nitrogen compound such as N,N-dimethylformamide; and the like. These solvents may be employed alone or in admixture thereof.
It is preferable that the solvent is contained in the pellets of the CPVC composition as much as possible so as to impregnate a large amount of the inorganic materials into the pre-expanded particles and the foamed article and so as to make the residual stress and residual strain remained in the pre-expanded particles small. However, when the amount of the solvent is too much, blocking is sometimes generated between the pelltes. Therefore, generally it is suitable that the amount of the solvent is 10 to 2000 parts by weight, preferably 50 to 500 parts by weight based on 100 parts by weight of the CPVC although the amount depends on the compatibility of the solvent and the CPVC.
Also, it is preferable that a large amount of solvent is contained in a pre-expanded particle to improve the fusibility of the pre-expanded particles and to lower the softening temperature of the resin at the time of foaming in a mold. However, when the amount of the solvent contained in the pre-expanded partilces is too much, a foamed article after expanding in a mold sometimes shows a shrinkage by vaporizing and escaping the solvent from the foamed article.
Therefore, it is suitable that the amount of the solvent is 1 to 200 parts by weight, preferably 5 to 100 parts by weight based on 100 parts by weight of the CPVC.
As the physical blowing agent used in the present invention, generally, any kinds of the blowing agent can be used if the blowing agent can be impregnated into the pellets of the CPVC compostion of the present invention. However, it is preferable that the physical blowing agent has a small afinity with a solvent in order to prevent that the efficiency obtained by impregnating the blowing agent into the pellets is lowered and that the blowing gases during the expansin are escaped. From the above-mentioned viewpoint, a physical blowing agent which is suitable for a solvent is preferably employed in the present invention. Examples of a physical blowing agent are, for instance, a fluorinated hydrocarbon such as trichlorofluoromethane, dichlorodifluoromethane or dichlorotetrafluoroethane; a hydrocarbon such as propane, butane or pentane, or the like, and they are suitably used in accordance with the kinds of the solvent.
The amount of the physical blowing agent impregnated into the pellet of the CPVC composition can be suitably prepared in accordance with a desired expansion ratio. Further, the conditions for impregnation such as a temperature at impregnating step and an impregnation period of time are adjusted in accordance with the amount of the physical blowing agent impregnated into the pellets of the CPVC composition.
As a stabilizer used in the present invention, any kinds of the stabilizer can be used if the stabilizer has a capacity to prevent the decomposition and deterioration of the CPVC.
In the present invention, a material which is usually used as an additive agent of a plastic material, for instance, a pigment such as titanium oxide or ultramarine blue; an antistatic agent such as a tertiary amine or an alkyl sulfonate, or the like can be used as occasional demands.
A representative example of the process for preparing the pellets of the CPVC composition and the pre-expanded particles is explained below.
First, the prescribed amount of materials in the form of powder are thoroughly mixed by employing a Henschel mixer, a super mixer, or the like. The mixed powder of the materials is put into an intensive kneader with liquid materials and then the mixture is kneaded to mix uniformly in an appropriate period of time.
The kneaded admixture is supplied to an extruder such as a screw extruder or a plunger extruder and then is extruded to give a strand. The strand is cut with a proper cutter such as a pelletizer to give pellets. Since a solvent is contained in the pellets, if necessary, the solvent may be reduced by volatilizing in accordance with the amount of the solvent to be remained in the pre-expanded partilces. Then the pellets are put into a sealed vessel with a physical blowing agent and the sealed vessel is kept at a prescribed temperature which is usually 10° to 70° C. and for a proper period of time which is usually 3 to 15 hours to impregnate the physical blowing agnet into the pellets.
The detailed conditions for the impregnation are properly determined in accordance with the grade of the CPVC, kinds and amount of the solvent, kinds of the physical blowing agent, a desired expansion ratio, and the like.
After completing the impregnation, the pellets are taken out from the sealed vessel and are pre-expanded by heating with, e.g., steam, hot water, hot air, or the like. The conditions for pre-expansion are properly determined in accordance with the grade of the CPVC, kinds and amount of the solvent, kinds and impregnated amount of the physical blowing agent, a desired expansion ratio, and the like.
After the amount of the solvent in the pre-expanded particles is adjusted to the desired amount by the method such as air-drying, if necessary, a physical blowing agent is impregnated again into the pre-expanded particles, and then the pre-expanded particles are foamed by a conventional process such as a process of foaming in a mold to give a foamed article. That is, the pre-expanded particles are filled in a mold and then heated with a heating source such as steam to fuse, adhere and expand each other in order to get a finished foamed article.
The above-mentioned process is only one example of the process of the present invention. Therefore, any processes may be employed in the present invention if the processes satisfy the fundamental principles of the present invention, that is, a uniform gel phase is formed by the CPVC and the solvent and the inorganic materials are wrapped with the gel phase.
The present invention is more specifically described and explained by means of the following Examples. It is to be understood that the present invention is not limited to the Examples, and various changed and modifications may be made in the present invention without departing from the sprit and scope thereof.
EXAMPLES 1 TO 11
There was prepared 2,500 g of a foamable composition by using the materials shown in Table 1 in the mixing ratio shown in Table 2. A CPVC and inorganic materials were mixed for 30 minutes in a Henschel mixer having a content volume of 10 l.
The mixed powder of the materials was poured into a intensive kneader having a content volume of 3 l with a solvent and a stabilizer, and the mixture was kneaded at 100° to 130° C. for 30 minutes. After the mixture was supplied to a plunger extruder and maintained at 185° C. for 35 minutes, the mixture was cooled to the temperature of 70° to 80° C. and was extruded through dies having a bore diameter of 3 mm to give a strand. The strand was cut into a length of 2 to 4 mm with a cutter (a pelletizer) to produce pellets.
An autoclave having a content volume of 8 l was charged with about 1000 g of the obtained pellets and thereto a physical blowing agent was poured. The autoclave was maintained at room temperature for the period of time shown in Table 2 under the state that the pellets were dipped in the physical blowing agent (hereinafter referred to as "liquid phase impregnation"). The vapour pressure of the physical blowing agent was confirmed with a manometer equipped to the autoclave.
Then, the pellets were taken out from the autoclave and were put into a net basket having a lid made of stainless steel, and the pellets were pre-expanded by dipping the basket into hot water at the temperature and for the period of time shown in Table 2.
The obtained pre-expanded particles were put into a net basket made of polypropylene and were air-dried at room temperature to adjust the amount of the solvent contained in the pellets. An autoclave having a content volume of 80 l was charged with the obtained pre-expanded particles and the above-mentioned physical blowing agent and was sealed. The particles were impregnated with the blowing agent again at room temperature for the period of time shown in Table 3 and were put into a mold of aluminium alloy having an inner size of 250 mm×250 mm×25 mm and having holes for introducing steam. The expansion was carried out in the mold by using a usual molding machine at the foaming temperature shown in Table 3 to give a foamed article.
The amount of the solvent and the blowing agent contained in the pre-expanded particles and the expansion ratio of the particles, and apparent density, expansion ratio and the percentage of melt-adhesion of the foamed article were measured in accordance with the following methods. The results are shown in Table 3.
Amount of the solvent and the blowing agent contained in the pre-expanded particles
After 0.5 to 1 g of the pre-expanded particles were weighed and were dissolved into 20 ml of tetrahydrofuran, the solution was subjected to gas chromatography analysis and amounts of the solvent and the blowing agent was measured.
Apparent density
A proper quantity of the pre-expanded particles or the foamed article was prepared and the weight was measured. The pre-expanded particles or the foamed article was put into a messcylinder having a volume of 100 ml in which water was poured to the amount of about half graduation of the messcylinder and then it was immersed under the surface of the water with a tool made of wire net. The volume was calculated from the difference of the graduations on the messcylinder before the pre-expanded particles or the foamed article was immersed into the water and after that. The apparent density is calculated in accordance with the following equation. ##EQU1##
Expansion ratio
The amount of the inorganic materials based on 100 parts by weight of the CPVC which was shown in Table 2 was measured, and then density of the CPVC contained in the obtained pre-expanded particles or foamed article was calculated in accordance with the following equation. ##EQU2##
Then, the expansion ratio was calculated in the condition that the specific gravity of the CPVC was 1.6 by the following equation. ##EQU3##
Percentage of melt-adhesion
The foamed article was torn off by bending and its cross section was observed. The number of the broken particles (n) and the whole number of the particles (N) on the cross section were measured. The percentage of melt-adhesion was calculated in accordance with the following equation. ##EQU4##
TABLE 1______________________________________Material Trade name Contents______________________________________CPVC XH 7225 *1 Average polymerization degree = 2500 Chlorine content = 67% XH 7211 *1 Average polymerization degree = 1100 Chlorine content = 67% XH 3112 *1 Average polymerization degree = 1200 Chlorine content = 63%Inorganic Talc Average particle size =materials 5.5 μm Calcium carbonate Particle size = 70 mesh pass Asbestos Yielded from Musori in South Africa 7M by the Quebec Asbester Mining Association Test ProcedureSolvent Toluene Benzene 1,2,4-Trichlorobenzene Butyl cellosolve (BC) Diisobutyl ketone (DIBK) n-amyl acetate CLP *2 Trischloroethyl phosphate Cyclohexanone (CNON) Diethylbenzene (DEB) Isooctyl acetate (IOA)Pysical R-11 *3 Trichlorofluoromethaneblowing R-114 *3 Dichlorotetrafluoroethaneagent R-12 *3 DichlorodifluoromethaneStabilizer F-22 *4 Bis(di-n-butyl tin monolaurate maleate)______________________________________ (Note) *1: Available from Kanegafuchi Kagaku Kogyo Kabushiki Kaisha *2: Available from Daihachi Kagaku Kogyosho Kabushiki Kaisha *3: Available from Du PontMitsui Polychemicals Company, Ltd. *4: Available from Akishima Kagaku Kogyo Kabushiki Kaisha The term "%" means "% by weight".
TABLE 2__________________________________________________________________________ Impregnation of blowing agent Impreg-Foamable composition (parts by weight) Physical nating Pre-expansionEx. Inorganic blowing time Temperature/No. CPVC material Solvent Stabilizer agent (hours) Time (°C./sec.)__________________________________________________________________________1 XH7225 Talc (100) BC (250) F-22 (6) R-114 12 74/14 (100) Asbestos (50)2 XH7225 Talc (100) BC (125) " " 5 77/15 (100) Asbestos (50) CNON (125)3 XH7225 Talc (100) BC (125) " " 13 75/13 (100) Asbestos (50) CNON (125)4 XH7225 Talc (50) BC (167) " " 3 70/60 (100) Asbestos (60) CNON (83)5 XH7225 Talc (100) DEB (125) " " 5 75/20 (100) Asbestos (50) CNON (125)6 XH7225 Talc (100) DIBK (125) " " 4 75/30 (100) Asbestos (50) BC (125)7 XH7225 Talc (6) IOA (167) " " 9 77/30 (100) Asbestos (50) CNON (83)8 XH7225 Talc (100) DEB (125) " R-11 5 77/20 (100) Asbestos (50) CNON (125)9 XH7225 Talc (5) BC (100) " R-114 5 100/20 (100)10 XH7225 Talc (250) BC (200) " " 5 65/30 (100) Asbestos (50) CNON (100)11 XH7211 Talc (6) BC (100) " " 5 65/15 (100) Asbestos (30) CNON (100)__________________________________________________________________________
TABLE 3__________________________________________________________________________ Second impregnation of blowing agent Foamed articlePre-expanded particles Physical Percent- Amount of Impreg- blowing Appar- Ex- age of Expansion solvent nating agent Foaming ent pansion melt-Ex. ratio (parts by time (parts by temperature density ratio adhesionNo. (times) weight) (hours) weight) (°C.) (g/cm.sup.3) (times) (%)__________________________________________________________________________1 30 BC (25) 6 R-114 (36) 113 0.107 38 732 30 BC (34) 2 R-114 (49) 113 0.111 37 90 CNON (18)3 34 BC (21) 1 R-114 (28) 100 0.108 38 80 CNON (25)4 24 BC (12) 4 R-114 (21) 115 0.093 37 82 CNON (5)5 31 DEB (20) 2 R-114 (30) 110 0.105 39 75 CNON (19)6 39 DIBK (25) 3 R-114 (37) 110 0.095 43 79 BC (28)7 21 IOA (21) 2 R-114 (31) 113 0.100 26 90 CNON (11)8 31 DEB (21) 2 R-11 (28) 110 0.113 36 78 CNON (17)9 26 BC (15) 2 R-114 (30) 115 0.047 36 9010 30 BC (21) 2 R-114 (29) 115 0.168 38 71 CNON (9)11 22 BC (25) 3 R-114 (33) 110 0.081 27 77 CNON (13)__________________________________________________________________________
COMPARATIVE EXAMPLE 1
The pre-expanded particles obtained in Example 2 were allowed to stand in a hot air circulating type oven at 60° C. for 14 days to remove the solvent contained in the pre-expanded particles by volatilization.
As the result that the amount of the solvent remained in the pre-exapnded particles was measured by gas chromatography analysis in the same manner as in Examples 1 to 11, 0.5 parts by weight of BC and 0.4 parts by weight of CNON based on 100 parts by weight of the CPVC were impregnated. Then R-114 was impregated into the particles again and the particles were subjected to foaming in a mold at 140° C. The percentage of melt-adhesion of the obtained foamed article was 20%.
EXAMPLES 12 TO 17
The procedure of Examples 1 to 11 was repeated except that the amount of the residual solvent in the pellets which were not pre-expanded was changed as shown in Table 4 to give pre-expanded particles and a foamed article.
In addition to the processes in Examples 1 to 11, before a blowing agent was impregnated into the pellets in an autoclave having a content value of 8 l, the space in the autoclave was partitioned into the upper part and the lower part with a wire net made of stainless steel, the physical blowing agent was poured into the lower part and the pellets were put on the wire net to contact with a gaseous blowing agent not contacting with a liquid blowing agent directly (hereinafter referred to as "gaseous phase impregnation"). Then the pellets were expanded in the same manner as in Examples 1 to 11 to give a pre-expanded particles (Examples 15 to 17).
The amount of the solvent, expansion ratio and volume retention of the obtained pre-expanded paticles and the foamed article were measured. The volume retention was measured in accordance with the following method. The results are shown in Table 4.
Volume retention
A proper quantity of the pre-expanded particle or the foamed article was prepared and was put into a messcylinder having a content volume of 100 ml in which water was poured about half of the maximum graduation. The pre-expanded particles or the foamed article were immersed under the surface of the water with a tool made of wire net. The volume of the pre-expanded particles or the foamed article before heating was calculated from the difference of the graduations on the cylinder before the pre-expanded particles or the foamed article were dipped into water.
After the pre-expanded particles or the foamed article were air-dried, they were allowed to stand in a hot-air circulation type oven at 200° C. for 1 hour.
The volume of the pre-expanded particles or the foamed article after heating were calculated in the same manner as in the above.
The volume retension was calculated in accordance with the following equation. ##EQU5##
TABLE 4__________________________________________________________________________ Impregnation of blowing agentFoamable composition (parts by weight) Physical Impreg- Impreg-Ex. Inorganic blowing nating time natedNo. CPVC materials Solvent Stabilizer agent (hours) Phase__________________________________________________________________________12 XH7225 Talc (100) BC (83) F-22 (6) R-114 32 Liquid phase (100) Asbestos (50) CNON (167)13 XH7225 Talc (100) BC (125) " " 4 Liquid phase (100) Asbestos (50) CNON (125)14 XH7225 Talc (100) BC (125) " " 3 Liquid phase (100) Asbestos (50) CNON (125)15 XH7225 Talc (100) BC (167) " " 10 Gaseous phase (100) Asbestos (50) CNON (83)16 XH7225 Talc (100) BC (167) " " 6 Gaseous phase (100) Asbestos (50) CNON (83)17 XH7225 Talc (100) BC (167) " " 3 Gaseous phase (100) Asbestos (50) CNON (83)__________________________________________________________________________ Pre-expanded particles Foamed article Amount of residual solvent Expansion Volume Expansion Volume Ex. in pellets (parts by weight) ratio retention ratio retention No. BC CNON Total amount (times) (%) (times) (%)__________________________________________________________________________ 12 9 31 40 43 28 56 19 13 46 27 73 39 60 54 35 14 57 31 88 39 70 55 45 15 71 36 107 30 79 43 57 16 95 40 135 22 97 39 61 17 104 44 148 19 123 31 72__________________________________________________________________________
EXAMPLES 18 TO 29
There was prepared 2,500 g of a foamable composition by using the materials shown in Table 1 in the mixing ratio shown in Table 5. A CPVC and inorganic materials were mixed for 30 minutes in a Henschel mixer having a content volume of 10 l.
The mixed powder of the materials was put into an intensive kneader having a content volume of 3 l with a solvent and a stabilizer, and the kneading was carried out at 100° C. for 30 minutes. After the mixture was supplied to a plunger extruder and was maintained at 185° C. for 35 minutes, the mixture was cooled to at the temperature of 80° to 90° C. Then the mixture was extruded through dies having an bore diameter of 3 mm to give a strand. The obtained strand was cut with a cutter (a pelletizer) in a length of 2 to 4 mm to produce pellets.
The solvent contained in the pellets was volatilized by heating the pellets in a hot-air circulation type oven at 80° C. for about twenty-four hours.
An ampule made of stainless steel having a content volume of 320 ml was charged with a physical blowing agent shown in Table 1 with about 100 g of the pellets from which the solvent was volatilized by means of the above-mentioned method and the ampule was sealed and was maintained at the temperature and for the period of time shown in Table 5. The vapour pressure of the physical blowing agent was confirmed by a manometer equipped to the ampule.
After the ampule was allowed to stand for 15 to 16 hours at the temperature, it was cooled to room temperaure. Then, the pellets were taken out from the ampule and the amount of the blowing agent impreganted in the pellets was measured.
The pellets containing the blowing agent were put into a basket made of stainless steel net and were pre-expanded in an autoclave by heating with steam at the temperature and for the period of time shown in Table 5.
As to the obtained pre-expanded particles, apparent density, expansion ratio and the percentage of closed cell were measured. The percentage of closed cell was calculated by the following method. The results are shown in Table 5.
Percentage of closed cell
The percentage of closed cell was measured in accordance with ASTM D 2856 with an air comparison type aerometer manufactured by Beckman Toshiba Kabushiki Kaisha.
TABLE 5__________________________________________________________________________Ex. Foamable composition (parts by weight)No. CPVC Inorganic material Solvent Stabilizer__________________________________________________________________________18 XH 7225 (100) Talc (50), Calcium Toluene (330) F-22 (6) carbonate (50), Asbestos (30)19 XH 7225 (100) Talc (50), Asbestos (40) Toluene (300) F-22 (6)20 XH 7225 (100) Talc (6), Asbestos (30) Benzene (260) F-22 (6)21 XH 7211 (100) Talc (6), Asbestos (30) Toluene (280) F-22 (6)22 XH 3112 (100) Talc (50) Toluene (200) F-22 (6)23 XH 7225 (100) Talc (100), Asbestos (50) Toluene (250), CLP (50) F-22 (6)24 XH 7225 (100) Talc (100), Asbestos (50) Toluene (250), CLP (50) F-22 (6)25 XH 7225 (100) Talc (100), Asbestos (50) Toluene (250), CLP (50) F-22 (6)26 XH 7225 (100) Talc (6) 1,2,4-trichlorobenzene (100) F-22 (6)27 XH 7225 (100) Talc (6) BC (100) F-22 (6)28 XH 7225 (100) Talc (6) DIBK (100) F-22 (6)29 XH 7225 (100) Talc (6) n-Amyl acetate (100) F-22 (6)__________________________________________________________________________Impregnation of the blowing agent Temperature Pre-expanded particles Physical Temperature Amount and time of Apparent Expansion PercentageEx. blowing Time (parts by pre-expansion density ratio of closedNo. agent (°C./hours) weight) (°C./min.) (g/cm.sup.3) (times) cell (%)__________________________________________________________________________18 R-11 80/16 22 113/2 0.161 23 9919 R-11 85/15 20 115/2 0.164 19 7420 R-11 80/16 22 120/1.5 0.091 24 9921 R-11 80/16 21 110/2 0.116 19 10022 R-11 80/16 25 120/2 0.098 24 9823 R-11 80/15 14 115/2 0.205 20 9724 R-114 80/15 20 106/1 0.379 11 9525 R-12 80/15 8 110/2 0.329 12 7726 R-114 30/15 7 100/2 0.222 8 8027 R-114 30/15 22 100/2 0.061 28 9828 R-114 30/15 18 100/0.5 0.108 15 8629 R-114 30/15 19 100/2 0.104 16 97__________________________________________________________________________
COMPARATIVE EXAMPLE 2
There were kneaded 100 parts by weight of XH 7211, 6 parts by weight of talc, 30 parts by weight of asbestos and 6 parts by weight of F-22 without mixing with a solvent by using a 6 inch biaxial roll at 210° C. to give a sheet having a thickness of about 2 mm.
The sheet was cut into small pieces having a side length of 3 to 4 mm. The pieces and R-11 were put into an ampule made of stainless steel having a content volume of 320 ml and the ampule was sealed. The ampule was maintained at the temeprature of 80° C. for 16 hours. The amount of the R-11 impregnated into the pieces just after the pieces were taken out from the ampule was 20 parts by weight. However, in comparison with the case in Example 21, R-11 was drained out from the pieces very rapidly, and further, the pieces were hardly expanded although they were subjected to the pre-expansion by heating with steam at 110° C. for 2 minutes.
In addition to the ingredients used in the Examples, other ingredients can be used in the Examples as set forth in the specification to obtain substantially the same results. | Pellets of a chlorinated vinyl chloride resin composition comprising inorganic materials, a solvent and a blowing agent; a pre-expanded particle of a chlorinated vinyl chloride resin comprising inorganic materials and a solvent and a process for preparing the pre-expanded particle of the chlorinated vinyl chloride resin containing inorganic materials which comprises kneading a chlorinated vinyl chloride resin, inorganic materials and a solvent, pelletizing the kneaded mixture, impregnating a physical blowing agent into the resulting pellets and pre-expanding the pellets. The present invention makes it possible to be contained a large amount of inorganic materials in a chlorinated vinyl chloride resin by forming a uniform gel phase of the chlorinated vinyl chloride resin and the solvent and wrapping inorganic materials in the gel phase. A foamed article produced by employing pre-expanded particles of the chlorinated vinyl chloride resin containing inorganic materials has an excellent heat resistance, i.e. the foamed article generates little heat, produces little smoke and little poison gas and is hardly strained and cracked at burning, and further, has a large dimensional stability. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application 60/341,517 filed Dec. 13, 2001, which is hereby incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to a non-mechanical (by-wire) driver control of a vehicle which permits the driver to face the direction of travel and control the vehicle from a plurality of movable driving positions.
BACKGROUND OF THE INVENTION
[0003] By-wire steering, braking and acceleration controls and control systems on a vehicle are not designed to accomodate a change in position of a driver. Thus, although a prior art vehicle may include a driver's seat that is rotatable, allowing the driver to shift his position, the controls typically do not move to accommodate the change in position. This requires that the driver navigate the vehicle from controls positioned to accommodate the driver in the original seat position. These system limitations create less than optimal convenience for the driver. Controlling the steering, braking and acceleration functions of a vehicle from different positions spaced from the original seat position is inherently more difficult.
SUMMARY OF THE INVENTION
[0004] This invention is based on a method of mechanization utilizing drive-by-wire for drive, steer, brake, throttle, etc. where the driver's seat with the vehicle controls can move into optimal seating positions within a vehicle. The method of movement is based on the concept in one embodiment of a carousel or merry-go-round. The driver's seat and the passenger seat are adjacent to one another on a platform that moves or revolves in a circular pattern. The two seats rotate around a center point of the carousel which houses a wire bundle passing vehicle control data from the vehicle chassis to the driver's vehicle controls. The driver's vehicle control interface in this concept provides one method of vehicle control with the vehicle's foot operations being integrated into the driver's vehicle interface, or steering wheel. This arrangement enables the driver to accelerate, brake, stop, start, or turn from one location. The technical advantage of this arrangement is the flexibility to drive the vehicle from different positions within the vehicle. In this one embodiment, there are four seat positions in this invention forming a diamond pattern; left-hand drive, right-hand drive, center-front drive, and center-rear drive. As the carousel revolves, the seats are designed to face in the forward direction the vehicle is traveling. However, each seat may also swivel or rotate so that the driver may face rearwardly. Other advantages may include fold-down seat backs that turn into tables or other holding devices for the interior of the vehicle.
[0005] The invention serves the primary purpose of allowing a driver to operate a vehicle in the forward direction from a plurality of different rotational and revolvable positions of a driver's seat and driver's vehicle interface with respect to the frame, chassis or rolling platform or other portion of the vehicle.
[0006] Accordingly, the invention is a driver control for a vehicle which has a chassis or vehicle portion, a seating structure movable with respect to the chassis or vehicle portion, and a driver's interface movable with the seating structure to a plurality of positions from which a driver can control the vehicle.
[0007] Also, accordingly, a driver control is provided for a vehicle which has a chassis, a carousel structure rotatable with respect to the chassis, and a seating structure revolvable with the carousel structure to a plurality of positions from which a driver can control the vehicle. The seating structure may also be rotatable with respect to the carousel structure. The rotation of the seating structure may also be coordinated with the rotation of the carousel structure so that the seating structure revolves and faces in one predetermined direction as the carousel structure rotates.
[0008] The invention may also provide a driver control cockpit adapted for a drivable vehicle which has a rolling platform controllable from the cockpit. The control cockpit has a carousel structure adapted to be rotatable with respect to the rolling platform and has a passageway or space beneath the carousel structure and adapted to be substantially fixed with respect to the rolling platform, a seating structure revolvable with the carousel structure and around or with respect to the passageway or space to a plurality of positions from each of which a driver can drive or control the vehicle, and a driver vehicle interface positionable with respect to the seating structure for operation in each of the positions and adapted to be connectable to the rolling platform to control the platform through the passageway or space in the carousel structure. The seating structure may be rotatable with respect to the carousel structure. The driver control cockpit may have up to four positions forming a diamond pattern for the seating structure sufficient to define selectively a left-hand drive, right-hand drive, center-front drive, and center-rear drive. The rotation of the seating structure may be coordinated with the rotation of the carousel structure so that the seating structure faces in one predetermined direction as the carousel structure rotates, and the rolling platform may be controlled for the at least one of the vehicle driving functions in accordance with the position of the seating structure.
[0009] The driver control cockpit may be installable as a supplier-provided assembly on the rolling platform of the vehicle so that the rolling platform may be controllable to drive the vehicle in at least one of the vehicle driving functions such as steering, accelerating, decelerating, clutching, and braking the vehicle. The rolling platform may also be controllable for at least another of the vehicle driving functions by a foot operation in the assembly.
[0010] The driver control cockpit of the invention may also have a seating structure which includes a driver seat with a passageway and a passenger seat adjacent to the driver's seat and rotatable around a passageway or space in the rolling platform so that a driver vehicle interface may be connectable to the driving functions in the rolling platform by a wire bundle adapted for passing control data through the passageway and the space between the driver vehicle interface and the rolling platform.
[0011] The invention may also be a vehicle which has a controllable rolling platform, a carousel structure rotatable with respect to the rolling platform and having a passageway substantially fixed with respect to the rolling platform, a rotatable seating structure revolvable on the carousel structure to a plurality of positions from each of which a driver can-control the rolling platform of the vehicle, and a driver vehicle interface which is positionable with respect to the seating structure for operation in each of the positions and which is connectable to the rolling platform to control the rolling platform through a passageway in the seating structure.
[0012] The invention may also be a drivable vehicle comprising a frame, rolling platform or vehicle portion, a drive-by-wire control mounted with respect to the frame or vehicle portion and operable by wire, a driver's seat movable to a plurality of driving positions by moving with respect to the frame or vehicle portion in one manner and by moving with respect to the frame in another manner. The driver's seat has an operator interface operatively connectable to the drive-by-wire control for driving the vehicle. The operator interface is operable to drive the vehicle from each of the plurality of driver's seat positions occasioned by moving the driver's seat. The vehicle also includes a connector operatively associated with the operator interface and configured for complementary engagement with a drive-by-wire connector port mounted with respect to the frame and operatively connected to the drive-by-wire control.
[0013] A more specific embodiment of the invention is a vehicle that has a frame, at least three wheels operable with respect to the frame, a steering system, braking system and energy conversion system, each of which is mounted with respect to the frame, operably connected to at least one wheel and responsive to non-mechanical control systems. The vehicle has a seat rotatable to a plurality of different rotational and revolvable positions with respect to the frame. The invention includes a configuration wherein the seat is sufficiently limited in its rotational and revolvable movement to prevent over-twisting the wire bundle between the interface and the rolling platform. The vehicle also has an operator interface that is operably connected to at least one of the steering system, braking system and energy conversion system for driving the vehicle, and that is movable with respect to the frame in a manner that does not interfere with the rotation of the seat. The operator interface is operable or usable for operating the at least one of the steering, braking and energy conversion systems by hand and without foot action when the seat is in any of the plurality of different rotational and revolvable positions with respect to the frame. The invention includes a configuration wherein the operator interface is mounted in a fixed position with respect to the seat and movable therewith in a manner that does not interfere with the rotation of the seat.
[0014] The invention may also include an embodiment wherein a motor unit or units is operably connected to the seat and the carousel structure for rotating and revolving the seat to effect a change in position of the seat and to a sensor and wherein one sensor is operably connected to the seat and operable to sense the change in position of the seat with respect to the carousel structure and another sensor is operable to sense a change in position of the carousel structure with respect to the rolling platform.
[0015] The control cockpit may also include a driver interface movable with the seat having a passageway and operable for operating a rolling platform having a space and a drive-by-wire connector port when the control cockpit is mounted on the rolling platform. The driver interface is mounted in a fixed position with respect to the seat and rotatable and revolvable therewith. The control cockpit may also include at least one connector configured for connection with the drive-by-wire connector port at one end and connected at the other end to the driver interface while extending through the passageway and the space. In another embodiment of the invention, the control cockpit may also include a sensor or sensors operably connected with respect to the seat and rolling platform and operable to sense a rotational and revolvable change in position of the seat with respect to the rolling platform and another connector operably connected to the sensor or sensors at one end and configured for connection with a connector port at the other end while extending through the passageway and space and operable to operate the rolling platform. In this configuration, the sensor and connector may be used to adjust the control of the vehicle in response to the position of the seat.
[0016] The invention may also include a vehicle embodiment wherein the driver's seat is movable transversely and longitudinally with respect to the vehicle. This embodiment may also include passenger seat which is movable likewise. This embodiment may also include a driver's vehicle interface which is movable with the driver's seat.
[0017] The above objects, features, and advantages, and other objects, features and advantages of the present invention are readily apparent from the following detailed description of the best mode for carrying out the invention when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a perspective front to rear view of a vehicle cockpit, partly in phantom, in accordance with an embodiment of the invention, the vehicle having a pair of fixed rear seats and a pair of front seats rotatable and revolvable between driving positions, and a driver's interface operably connected to the driver's seat for controlling the vehicle's steering system, braking system and energy conversion system;
[0019] [0019]FIG. 2 is a schematic illustration of a driver's seat revolved to a left-front driving position for the vehicle of FIG. 1;
[0020] [0020]FIG. 3 is a schematic illustration of the driver's seat revolved and rotated to a center-front driving position for the vehicle of FIG. 1;
[0021] [0021]FIG. 4 is a schematic illustration of the driver's seat revolved and rotated to a right-front driving position for the vehicle of FIG. 1;
[0022] [0022]FIG. 5 is a schematic illustration of the driver's seat revolved and rotated to a rear-center driving position for the vehicle of FIG. 1 with the seatback of the other front seat folded down; and
[0023] [0023]FIG. 6 is a schematic side illustration of the vehicle cockpit on a vehicle chassis or rolling platform with body and interface removed to show the electrical by-wire connector between the driver's seat (rotated in phantom) and the chassis or rolling platform of the vehicle of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring to FIG. 1, a vehicle 8 in accordance with the invention includes a body 10 (in phantom), a standard thin chassis or rolling platform 12 and a driver's seat assembly or carousel 14 . The vehicle 8 is preferably an automobile but the invention also contemplates that the vehicle may be a tractor or other industrial or commercial vehicle such as a bus. The invention also has utility in a non-automotive vehicle.
[0025] The chassis or rolling platform 12 includes a frame 16 having four wheels 18 , 20 , 22 , 24 that are operable with respect to the frame 16 , see FIG. 2. The chassis or rolling platform 12 together with the body 10 defines a vehicle, preferably an automobile, but the invention also contemplates that the vehicle may be a tractor, bus, or other industrial or commercial vehicle. Those skilled in the art will recognize materials and fastening methods suitable for attaching the wheels 18 , 20 , 22 and 24 to the frame 16 .
[0026] The chassis 12 further includes a steering system 30 , a braking system 32 and an energy conversion system 34 , each of which is mounted with respect to the frame 16 and responsive to a by-wire or non-mechanical control signals. Embodiments of such systems are described in the assignee's copending application, GP-301583, U.S. Provisional Application 60/314,501, filed Aug. 23, 2001, which is incorporated by reference herein, and related cases.
[0027] The structural frame 16 becomes the rolling platform 12 by providing a rigid structure forming spaces 36 , 38 in which the steering system 30 , braking system 32 and energy conversion system 34 may be packaged and to which the wheels 18 , 20 , 22 , 24 are mounted, as shown in FIG. 2. The rolling platform 12 is configured to support an attached body such as an automotive body 10 as taught in assignee's aforesaid copending application. A person of ordinary skill in the art will recognize that the structural frame 16 can take many different forms. For example, the structural frame 16 can be a traditional automotive frame having two or more longitudinal structural members spaced a distance apart from each other, with two or more transverse structural members spaced apart from each other and attached to both longitudinal structural members at their ends. Alternatively, the structural frame may also be in the form of a “belly pan,” wherein integrated rails and cross members are formed in sheets of metal or other suitable material, with other formations to accommodate various system components.
[0028] The chassis or rolling platform 12 includes a drive-by-wire connector port 42 that is mounted with respect to the frame 16 in or on a packaging space 40 . The connector port is operably connected to the steering system, the braking system, and the energy conversion system. Persons skilled in the art will recognize various methods for mounting the drive-by-wire connector port 42 to the frame 16 . In the preferred embodiment, the drive-by-wire connector port 42 is located in packaging space 40 near the top face of the rolling platform 12 beneath the driver's seat assembly or carousel 14 . Various embodiments of the manner for operably connecting the drive-by-wire connector port 42 to the steering system, the braking system and the energy conversion system are described in assignee's copending application (GP-301583, U.S. Provisional Application 60/314,501, filed Aug. 23, 2001, and related cases).
[0029] The driver's seat assembly or carousel 14 includes a driver's seat 46 and a passenger seat 48 , rotatably mounted on a rotatable, circular platform 52 which rotates on the top of and with respect to the rolling platform 12 . The circular platform pivots about a pivot point 54 affixed with respect to frame 16 , so that the rotatable seats 46 , 48 revolve with respect to the pivot point 54 . Two rear passenger seats 49 , 50 are mounted in fixed relation to the rolling platform 12 behind the carousel seat assembly 14 . The circular platform 52 of the carousel assembly 14 may be rotated by a pinion/gear arrangement 56 . The rotation of driver's seat 46 with respect to circular platform 52 may be powered in a similar manner by a pinion/gear arrangement 58 in the pedestal 60 of the driver's seat 46 . Circular platform sensors 62 and driver's seat sensor 63 sense the rotary position of the platform and seat, respectively. This results in a vehicle 8 which has a controllable rolling platform 12 , a carousel structure or assembly 14 rotatable with respect to the rolling platform 12 and having a passageway or space 40 in close proximity to the revolving driver's seat 46 and substantially fixed with respect to the rolling platform. Both the driver's seat 46 and the passenger seat 48 are rotatable with respect to the carousel platform and revolvable with the carousel platform to a plurality of positions and from the driver's seat of which a driver can drive the vehicle. The vehicle also has a driver vehicle interface or control panel 64 positionable with respect to the seating structure 46 by articulated arms 66 , 68 for operation in each of the driver's positions and connectable to the rolling platform 12 to control the platform through a passageway 70 in the driver's seat pedestal 60 of the carousel assembly 14 .
[0030] The operator interface 64 is operable for driving the rolling platform 12 through the drive-by-wire connector port 42 . The operator interface 64 may be fixed with respect to the seat 46 or movable in relation thereto. In the preferred embodiment of FIG. 1, the operator interface 64 is represented as being articulated for being pivotable with respect to the driver's seat 46 . In FIG. 1, the operator interface 64 is depicted as being connected to the drive-by-wire connector port 42 via a connector 74 for transmitting electrical signals from the operator interface 64 to the drive-by-wire connector port 42 when the connector 74 is interfitted therewith. The embodiment depicted in FIG. 1 includes the passageway 70 through the seat pedestal 60 and mounting arms 66 and 68 for the operator interface 64 through the hollow of all of which the connector 74 extends. The invention contemplates other configurations in which the connector 74 connects the operator interface 64 to the drive-by-wire connector port 42 by means other than a passageway. Furthermore, the invention contemplates configurations in which the connector 74 is a wire bundle linking the sensor 62 to the pinion/gear drive arrangement 56 for the circular platform and to the sensors 63 to the pinion/gear drive arrangement 58 for the driver's seat.
[0031] Those skilled in the art will recognize various designs for an operator interface 64 capable of transforming rotary position input from a driver's seat into an electrical signal to be transmitted to the drive-by-wire connector port 42 of the chassis or rolling platform 12 if the operator interface 64 is operably connected to the drive-by-wire connector port 42 by the connector 74 . The operator interface 64 could include one or more manual joysticks, and may further include a touch screen or keyboard design.
[0032] The drive-by-wire connector port 42 of the preferred embodiment may perform multiple functions, or select combinations thereof. First, the drive-by-wire connector port 42 may function as an electrical power connector, i.e., it may be configured to transfer electrical energy generated by components on the vehicle 8 to the operator interface 64 or other non-frame destination. Second, the drive-by-wire connector port 42 may function as a control signal receiver, i.e., a device configured to transfer non-mechanical control signals from a non-vehicle source, such as the operator interface 64 , to controlled systems including the steering system 30 , the braking system 32 , and the energy conversion system 34 . Third, the drive-by-wire connector port 42 may function as a feedback signal conduit through which feedback signals are made available to a vehicle driver. Fourth, the drive-by-wire connector port 42 may function as an external programming interface through which software containing algorithms and data may be transmitted for use by controlled systems. Fifth, the drive-by-wire connector port 42 may function as an information conduit through which sensor information and other information is made available to a vehicle driver. The drive-by-wire connector port 42 may thus function as a communications and power “umbilical” port through which all communications between the chassis or rolling platform 12 and the attached operator interface 64 and other attachments to the frame are transmitted. The drive-by-wire connector port 42 is essentially an electrical connector. Electrical connectors include devices configured to operably connect one or more electrical wires with other electrical wires. However, it is within the purview of this invention to have a foot pedal 65 in front of the left front driver's position of the carousel to provide for vehicle control by foot action such as braking.
[0033] The steering system 30 is housed in the chassis or rolling platform 12 and is operably connected to the front wheels 18 , 20 . Preferably, the steering system 30 is responsive to non-mechanical control signals. In the preferred embodiment, the steering system 30 is by-wire. A by-wire system is characterized by control signal transmission in electrical form. In the context of the present invention, “by-wire” systems, or systems that are controllable “by-wire,” include systems configured to receive control signals in electronic form via a control signal receiver, and respond in conformity to the electronic control signals.
[0034] Examples of steer-by-wire systems are described in U.S. Pat. Nos. 6,176,341, issued Jan. 23, 2001 and assigned to Delphi Technologies, Inc.; 6,208,293, issued Mar. 27, 2001 and assigned to Robert Bosch GmbH; 6,219,604, issued Apr. 17, 2001 and assigned to Robert Bosch GmbH; 6,318,494, issued Nov. 20, 2001 and assigned to Delphi Technologies, Inc.; 6,370,460, issued Apr. 9, 2002 and assigned to Delphi Technologies, Inc.; and 6,394,218, issued May 28, 2002 and assigned to T R W Fahrwerksysteme GmbH & Co. KG; which are hereby incorporated by reference in their entireties.
[0035] Referring again to FIG. 1, a braking system 32 is mounted to the frame 16 and is operably connected to the wheels 18 , 20 , 22 , 24 . The braking system is configured to be responsive to non-mechanical control signals. In the preferred embodiment, the braking system is by-wire, and is connected to the drive-by-wire connector port 42 and is configured to receive electrical braking control signals via the drive-by-wire connector port 42 .
[0036] Examples of brake-by-wire systems are described in U.S. Pat. Nos. 5,366,281, issued Nov. 22, 1994 assigned to General Motors Corporation; 5,823,636, issued Oct. 20, 1998 assigned to General Motors Corporation; 6,305,758, issued Oct. 23, 2001 assigned to Delphi Technologies, Inc.; and 6,390,565, issued May 21, 2002 assigned to Delphi Technologies, Inc.; which are hereby incorporated by reference in their entireties.
[0037] The energy conversion system 34 includes an energy converter that converts the energy stored in an energy storage system to mechanical energy that propels the vehicle 8 by applying the mechanical energy to rotate the front wheels 18 , 20 or rear wheels 22 , 24 . Those skilled in the art will recognize many types of energy converters that may be employed within the scope of the present invention. The energy conversion system is configured to respond to non-mechanical control signals. The energy conversion system of the preferred embodiment is controllable by-wire, as depicted in FIG. 6.
[0038] Referring again to FIG. 1, the sensor 63 is connected to the seat 46 . The sensor 63 is designed to sense a rotational change in position of the seat 46 and transmit information concerning the change in the form of an electrical current through the connector 74 to a control unit 76 located in the chassis or rolling platform 12 . The control unit 76 is operably connected to the steering system 30 , the braking system 32 and the energy conversion system 34 . The entire assembly of drive-by-wire connector port 42 , control unit 76 , steering system 30 , the braking system 32 and energy conversion system 34 is also referred to in the invention as a drive-by-wire control. The control unit 76 is programmed to adjust the nonmechanical control signals sent to the pinion/gear arrangements 56 , 58 based upon a rotational or revolvable change in seat position communicated via the sensors 62 , 63 and the connector 74 . The control unit 76 may be programmed to coordinate the rotation of seat 46 with the rotation of the circular platform 52 in response to signal received from sensors 62 and 63 so that the driver's seat will always be facing in the direction of vehicle travel and so that the rotation of both the driver's seat and the circular platform will be sufficiently limited so that the connector 74 will not be overly twisted. Those skilled in the art will recognize a variety of ways to program the control unit to respond-to such input factors.
[0039] The invention may also be a control cockpit adapted as a supplier subassembly for installation in and use on a vehicle that is controllable through a drive-by-wire connector port. An embodiment of the control cockpit 80 is depicted in FIG. 1. In this embodiment the control cockpit 80 includes the carousel circular platform 62 that is adapted to mount rotatably on the vehicle. The platform 62 has structure forming a first passageway 70 . The first passageway 70 is depicted in the form of a circular hole. The invention contemplates that the first passageway 70 may take a variety of other shapes and forms. The control cockpit 80 also has a driver's seat 46 and a passenger seat 48 that are mounted on the circular platform 52 in a manner to be rotatable and revolvable to a variety of different positions with respect to the rolling platform when the control cockpit 80 is mounted on the vehicle. The rolling platform 12 has structure forming a second passageway or space 40 . The second passageway or space 40 is depicted in FIG. 6 as being in the form of a packaging space beneath the seat 46 . The invention contemplates that the second passageway or space 40 may take a variety of other shapes and forms. The seat 46 is mounted on the circular platform 52 in such a manner that the second passageway or space 40 is in communication with the first passageway 70 . The control cockpit 80 includes the driver interface 64 that is movable with the seat 46 . The driver interface 64 is usable for operating the vehicle when the control cockpit 80 is mounted on the vehicle. In the embodiment depicted in FIG. 1, the driver interface 64 is mounted in a fixed position with respect to the seat 46 and is rotatable with the seat 46 . The invention also contemplates configurations in which the driver interface 64 is not mounted in a fixed position with respect to the seat 46 but is movable therewith. The control cockpit 80 also includes a connector 74 that is configured with enough slack for connection on one end with the drive-by-wire connector port 42 on the vehicle. The connector 74 is connected at the other end to the driver interface 64 and sensors 60 , 63 and motor driven pinion gear arrangements 56 , 58 . The connector 74 extends through the first passageway 70 and the second passageway or space 40 such that it does not interfere with the rotation of the seat 46 or overly twist the wires forming the connector.
[0040] The control cockpit 80 may also include sensors 62 , 63 that are operably connected with respect to the seat 46 and capable of sensing a rotational or revolvable change in position of the seat 46 . Those skilled in the art will recognize sensors capable of sensing and communicating such a change. The embodiment depicted in FIG. 6 shows the sensor 63 mounted directly to the bottom of the bodily support portion of the seat 46 and sensor 62 mounted in the rolling platform 12 adjacent the circular platform 52 . Other locations and mechanisms for operably connecting the sensor 63 to the seat 46 and the sensor 62 to the rolling platform 12 are also contemplated by the invention.
[0041] In the broadest sense and with reference to FIG. 4, the circular platform 52 may be a vehicle body floor portion fixed with respect to the chassis. This embodiment may have a transverse slot in the floor portion beneath seat 46 . A motorized drive connected to the driver's seat enables the seat to move laterally a short distance such as four to six inches to adjust the driver's position to his/her preference. Such adjustment may accommodate a passenger in the passenger seat 48 . Another slot at a right angle to the transverse slot may provide for a short longitudinal adjustment of the driver's seat.
Operation
[0042] [0042]FIGS. 1 and 2 show the driver's seat 46 in the left front driving position.
[0043] [0043]FIG. 3 shows the driver's seat revolved clockwise to a front center driving position. This results when such position is selected on the interface 64 to rotate the circular platform 52 90° from the left front position.
[0044] [0044]FIG. 4 shows the driver's seat revolved clockwise to a front right driving position. This results when such position is selected on the interface 64 to rotate the circular platform 52 180° from the left front position.
[0045] [0045]FIG. 5 shows the driver's seat revolved counter-clockwise (to avoid over-twisting connector 74 ) to a rear center driving position. This results when such position is selected on the interface 64 to rotate the circular platform counter-clockwise 90° from the left front position. In this position, the seatback 82 of the passenger seat 48 is folded down to form a flat surface in front of the driver for supporting driving aids such as maps and cups.
[0046] In the broader aspect of this invention and in another embodiment, the circular platform 52 is a fixed portion of the vehicle's floorboard. This floorboard portion has a lateral slot or other equivalent means beneath the driver's seat to accommodate lateral movement of the seat with respect to the vehicle's fixed portion. Such an arrangement may also be provided beneath the passenger's seat.
[0047] While the best modes for carrying out the invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the scope of the invention within the scope of the appended claims. | A vehicle has multiple movable driving positions resulting from a seat which is movable with respect to the vehicle chassis and has a driver's vehicle interface which moves with the seat. A wire bundle interconnects the driver's vehicle interface with controls for driving the vehicle. In one embodiment, a carousel rotates and a seat on the carousel revolves and rotates so that the seat continues to face forward. | 1 |
BACKGROUND OF THE INVENTION
Printing processes require that printing inks be both fluid and capable of subsequent ready conversion to a dry, smudge-resistant film once in place on paper or another substrate. One common type of printing ink consists primarily of a pigment and a binder which are suspended or dissolved in a volatile diluent. The binder serves the purpose of adhering the pigment to the printed substrate. The diluent must subsequently be removed by allowing it to evaporate either at room temperature, or for higher printing speeds, by heating. Large amounts of heat are needed to vaporize the ink diluent, which requires that substantial quantities of fuel be consumed. Since large volumes of air must be drawn over the drying ink film to remove the diluent vapor, frequently much heat is wasted. Further, the evaporation of the ink diluent into the open atmosphere can be a source of pollution. In many instances, it is necessary or desirable to burn off or otherwise remove the solvent vapor from the drying air before discharging it to the atmosphere. Additional fuel is consumed and special equipment must be installed for this purpose.
A second common type of printing ink consists of mixtures containing oleoresinous varnishes and/or drying oils which set by air oxidation. These inks set slowly so it is necessary to take precautions to avoid set-off (transfer) of ink between printed sheets.
Inks may also be formulated which contain drying oils or the like together with some binder and volatile diluent. In the usual printing operation, heat is applied to such an ink immediately after it is printed onto the substrate. At this stage, the diluent is driven off, reducing or minimizing problems of ink set-off. However, the ink is not fully set and rub resistance is inadequate. A subsequent drying stage is necessary in which the drying oil or the like hardens, as by oxidation and/or polymerization.
While it is necessary that a printing ink set rapidly and conveniently after printing, it is equally necessary that it not set or dry on the press. Inks containing volatile components may thicken on the press as the solvent evaporates, making it difficult or impossible to control the printing process. Air oxidizing varnishes, drying oils, and the like, may thicken or gum on the press on exposure to the atmosphere. Such inks are especially inclined to "skin over" when the press is shut down during a run. An ink which is not subject to such changes while on the printing press is said to "stay open".
Ink technologists have sought to achieve inks which set rapidly with a low level of energy input to initate setting, which do not release polluting materials to the atmosphere, and which stay open on the press, while at the same time meeting the physical and mechanical requirements of the printing process. Much attention has been directed to highly chemically reactive formulations. After printing, such inks are set by polymerization and/or crosslinking which is initiated by heat or radiation. A typical chemically reactive system contains polyfunctional acrylate esters (often in combination with other unsaturated materials), one or more ultraviolet photoinitiators, pigment and a variety of secondary components to control ink physical properties. See U.S. Pat. No. 3,804,640 and U.S. Pat. No. 3,881,942, both to Buckwalter. In normal use, such inks are printed on presses equipped with ultraviolet lamps which expose the film on the paper or other substrate immediately after printing. The inks set rapidly and with essentially no emission of polluting materials. Inks based on such highly reactive materials, however, have limited storage stability. The acrylates and other reactive materials in common use have been found to be chemically incompatible with some pigments which are desirable in printing inks. They present toxicity hazards, or are dangerous eye irritants, and are frequently skin sensitizers. When the inks are designed to be set by an ultraviolet light initiated reaction, the ultraviolet radiation itself and the high voltages necessary to power the ultraviolet lamps are additional health and safety hazards.
U.S. Pat. No. 3,024,213 to Ludlow discloses a heat drying ink vehicle based on poly(vinyl chloride) plastisols, more particularly finely divided poly(vinyl chloride) polymer dispersed in liquid plasticizers, all of which have low viscosity and solubility parameters closely matched to poly(vinyl chloride), and containing a compatible thermoplastic resinous binder to increase ink cohesion and tack. Further improvements in inks based on poly(vinyl chloride) and vinyl chloride copolymer plastisols are disclosed in U.S. Pat. No. 3,760,724 to Budzinski. These inks are set by applying heat which causes the liquid plasticizers and poly(vinyl chloride) or vinyl chloride copolymer to co-dissolve. Thus, such poly(vinyl chloride) plastisol-based inks are readily heat-settable without significant release of volatile materials to the atmosphere. These inks, however, do not have good press running characteristics. Undesirable build-up of material on the blanket of lithographic offset presses occurs when poly(vinyl chloride) plastisol inks are used. Further, both Ludlow and Budzinski require the use of at least one plasticizer in such poly(vinyl chloride) ptastisol inks. Such plasticizers may, as Ludlow discloses, damage ordinary natural rubber rolls on printing presses. It is thus necessary that ink rolls of polyurethane rubber or other plasticizer resistant compositions be used.
SUMMARY OF THE INVENTION
The present invention provides nonvolatile, heat-set pastes. It has been discovered that pastes of particulate, glassy thermoplastic poly(vinyl acetate) type polymers dispersed in a soft resinous phase can be prepared which heat-set by the fusion of the poly(vinyl acetate) binder. When pigmented or otherwise colored, these formulations have utility as printing inks. When uncolored, they can be used as clear over-print coatings. In addition, these fusible pastes have utility as specialty coatings and adhesives and can be fabricated into self-supporting shapes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to this invention, nonvolatile, heat-set vehicles for printing inks can be made by dispersing particulate, poly(vinyl acetate) type polymer binders in a soft resinous phase. More particularly, the printing ink vehicles of this invention contain particulate, poly(vinyl acetate) type polymers dispersed in a tackifying, cohesion-increasing material which may be a resin or mixture of resins whose softening point is either at or below room temperature, or has been lowered by dilution with an oil.
The binder materials used in this invention comprise particulate, glassy thermoplastic poly(vinyl acetate) type polymers with a molecular weight above about 50,000.
While the particle size of the binder is not critical, for lithographic or letterpress inks particles about 0.05 to about 2.0 microns in cross-section are preferred, with particles of about 0.1 to 0.5 micron in cross-section being most preferable. Larger particles may give poor uniformity and press performance. In screen printing, much heavier ink films are printed, so much larger particle sizes may be tolerated. The limit in particle size for inks used in screen printing is fixed by the mesh size of the printing screen and the thickness of the ink film desired. For use with coarse mesh screens and heavy ink films, particle sizes as high as about 50 microns can be used.
The poly(vinyl acetate) type polymers used in the pastes of this invention are based on vinyl acetate, either alone or in combination with one or more comonomers, with at least 60% of the monomers being vinyl acetate. Comonomers with the vinyl acetate monomer may include one or more addition polymerizable compounds such as other vinyl esters, including vinyl formate, vinyl propionate, vinyl stearate and vinyl benzoate; the saturated esters of ethylenically unsaturated carboxylic acids, including acrylate-type monomers, which class is here taken to include acrylates, methacrylates, acrylonitrile and methacrylonitrile, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like; and vinyl and vinylidene halides, including vinyl chloride and vinylidene chloride.
Other comonomers may be included if they do not interfere with the operation of the invention. It may be desirable to include certain additional polymer components to facilitate the preparation of particles of appropriate size. Such monomers may include ethylenically unsaturated carboxylic acids which may be mono- or polycarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and anhydride, citraconic acid and anhydride and other such acids.
Thermoplastic poly(vinyl acetate) type polymer particles of a size useful in this invention can be conveniently obtained by evaporating the diluent from emulsion or dispersion polymerized systems, as described in Dispersion Polymerization In Organic Media, edited by K. E. J. Barrett (John Wiley & Sons, N.Y., 1975). For materials with glass transition temperatures below about 50° C., it may be desirable to add some portion of the soft resin phase of the paste to the polymer dispersion before evaporating the polymerization diluent. Alternatively, particles may be prepared by grinding or milling the polymers, by controlled precipitation from solution. In many cases, a particle size classification process may be necessary to obtain the optimum size of the material.
The continuous soft resinous phase of the paste is comprised of a tackifying, cohesion-increasing material which may be a resin or mixture of resins with a softening point at or below room temperature, or which has been diluted with an oil to suitably lower the softening point. The term "resin" is here restricted to amorphous organic solids, semi-solids and viscous liquids with room temperature viscosities above about 2000 centipoise. Such resins are commonly polymeric, but number average molecular weight must be under about 5000. Typical classes of resins which may be used are hydrocarbon resins, including naturally occurring coal tar and other fossil resins, synthetic aliphatic and aromatic hydrocarbon resins prepared from petroleum- or coal-derived feedstocks, and resins based on pure hydrocarbon monomers and combination of monomers, such as styrene and alkyl-substituted styrenes, indene and dicyclopentadiene; terpene resins; rosin and rosin esters such as hydrogenated methyl ester of rosin and phenolic modified pentaerythritol ester of rosin; ketone formaldehyde thermoplastic resins; condensed ketone thermoplastic resins; and resins based on acrylate esters and alkyl-substituted acrylate esters; and transesterification products of alcohols with dimethyl terephthalate process residues.
Diluent oils may be aliphatic, aromatic or naphthenic in character, and may contain polar functionality, but must be compatible with and dissolve in the resin system. Typically, they have solubility parameters between about 7.0 and 8.5. They must be substantially nonvolatile at the temperature at which the ink is set, typically 150° C. or higher. It is important to choose diluents which do not rapidly solvate the particulate thermoplastic phase at room temperature. This may be accomplished by avoiding those diluent oils which closely match the solubility parameter of the particulate thermoplastic. Typically, the solubility parameter midpoint for poly(vinyl acetate) with respect to weakly hydrogen-bonded solvents such as hydrocarbon oils or chlorinated hydrocarbons is at or about 9.4. Poly(vinyl acetate) is insoluble in strongly hydrogen-bonding solvents. Liquid plasticizers of the sort typically used to prepare poly(vinyl chloride) plastisols (commonly referred to as "primary plasticizers") such as those disclosed by Ludlow in U.S. Pat. No. 3,024,213, have solubility parameters between about 8.5 and 11 and are not used in the pastes of this invention.
There is no such restriction on the solubility parameter of the resin itself. The rate of solvation is slow enough that even inks containing resins which closely match the solubility parameter of the particulate thermoplastic may be prepared and run on a press. In extreme cases, solvation may proceed at a rate that would limit certain combinations of resin and thermoplastic polymers to applications where inks are prepared as needed, and are not stored longer than a day or so. Printing inks are commonly prepared as needed in larger printing plants. Under such circumstances, the chemical composition of the particulate thermoplastic polymers and the resin may be essentially identical, the materials differing only in physical form and molecular weight.
The poly(vinyl acetate) polymer and soft resin of this invention should be used in proportions such that the ratio of polymer to resin will preferably be between about 1:6 and about 1:1. Also, the ratio of soft resin to diluent oil may range from these cases in which the formulation is oil-free (i.e., where the soft resin is naturally thin enough to achieve the desired rheology in the final fusible paste formulation) to about a 1:15 ratio of resin to oil.
In addition to the above-described essential ingredients, when the pastes are used as printing inks surface active agents, pigment dispersing aids, waxes, slip aids, tack modifiers and the like may be included.
The primary mechanism by which the pastes of this invention set appears to be the fusion of the particulate thermoplastic poly(vinyl acetate) binder to form a continuous film on heating the plate, in which the soft resinous phase is largely dissolved and/or entrapped. In some circumstances, it may be desirable for the paste film to harden further. This can be achieved by choosing for the soft resinous phase, either in whole or part, materials capable of undergoing polymerization or cross-linking during the thermal fusion of the particulate thermoplastic material or subsequent to it. In such cases, it may be appropriate to include suitable catalysts, driers, accelerators, or other additives which are necessary or desirable to initiate or promote the desired polymerization or cross-linking reaction. Such subsequent hardening of the thermally set paste film may be achieved by including one or more unsaturated alkyd resins as part of the resinous phase, such as alkyds based on phthalic, isophthalic, adipic, azelaic, sebacic, terephthalic, hydrophthalic, maleic, fumaric, and benzoic acids and anhydrides modified with unsaturated fatty acids; rosin modified alkyds; phenolic modified alkyds; epoxy alkyds; polyamide alkyds; isocyanate alkyds; and styrene or substituted styrene alkyds, such as styrene and acrylonitrile modified alkyds. The unsaturated isophthalic alkyds are preferred.
Similarly, drying oils or semi-drying oils such as linseed oil, tung oil, oiticica oil, dehydrated castor oil, soya oil, safflower oil, fish oil, tall oil, or the like may be used as hardening agents in the resinous phase. These oils may be used in the natural state or may be bodied to increase viscosity by heating or other partial polymerization.
When such oxidation drying materials are included in the paste, suitable driers or catalysts which promote oxidative cross-linking and polymerization may be included, typically salts or complexes of metals capable of existing in more than one valence state, such as vanadium oxyacetylacetonate, vanadium oxysulfate, vanadium oxy-1,1,1-trifluoroacetylacetone, vanadium oxy-1-phenylacetylacetonate, ferric acetylacetonate-benzoin, manganese octoate, lead naphthenate, cobaltic acetylacetonate, titanyl acetylacetonate, cobaltous naphthenate, cobaltous 2-ethylhexanoate, cobaltous stearate, cobaltic stearate, cobaltous acetylacetonate, manganous stearate, manganic stearate, manganous acetylacetonate, manganic acetylacetonate, manganese naphthenate, zirconium acetylacetonate, vanadyl naphthenate, ferrous sulfate, ferrous pyrophosphate, ferrous sulfide, the ferrous complex of ethylenedinitrolotetraacetic acid, ferrous o-phenanthroline, ferrous ferrocyanide, ferrous acetylacetonate and the corresponding nickel, copper, mercury and chromium compounds.
The use of a colorant is not critical to the invention. The fusible paste dispersions can be used unpigmented as a clear overprint varnish. When a colorant is desired, it may be a pigment or dye. The colorant normally may be most conveniently dispersed in the continuous soft resinous phase of the ink. However, it may be desirable in some circumstances to include the colorant within the particulate thermoplastic material.
When used as printing inks, the pastes of this invention may be printed by any of the printing processes which require a paste type ink. Common printing processes in which paste inks are used include letterpress, lithography, and screen printing. Printing may be sheet-fed or web-fed, and may be on paper, board, fabric, metal, glass, plastic, wood, leather, rubber, or other substrates. Variations in ink rheology and tack properties are required for optimum performance for any chosen printing process and substrate. Inks based on the pastes of this invention can be suitably formulated to meet these specific requirements by appropriate choice and relative concentration of materials used in the resinous phase. This will be readily apparent to those skilled in printing ink formulation.
In addition to printing, pastes may be applied to substrates by roll-coating, doctoring, screening, dipping, or the like, especially for the preparation of speciality coatings or for use as heat-set thermoplastic adhesives. Self-supporting shapes may be prepared by cavity molding, dip molding, rotational molding, slush molding or the like. Variations in place rheology and tack properties are required for optimum performance for any chosen fabrication process. The pastes can be formulated to meet these requirements by appropriate choice and relative concentration of materials used in the resinous phase. This will be readily apparent to those skilled in the art of materials fabrication.
After printing, coating, or forming, the pastes of this invention may be set by heating to at least about 75° C. and preferably to at least about 150° C. to fuse the particulate, thermoplastic polymer. This may be done in a conventional forced-air drying oven, in common use in the printing industry. However, since no air flow is necessary to remove volatile material, it is frequently advantageous to heat the paste film by irradiation, typically in the infrared spectral region. At 150° C., the paste may be fused by heating for from about 0.01 second to about 2 minutes, longer times being required for those pastes which do not contain pigments than for those which do contain pigment. Also, the duration of the heating may vary depending upon the thickness of the paste coating, substrate, or purpose for which the paste is used (e.g., adhesive, molding material, etc.).
EXAMPLE 1
Finely divided poly(vinyl acetate) is prepared as follows. A solution is prepared which consists of 223 parts n-heptane, 148 parts n-hexane, 59.3 parts vinyl acetate, (VAc) 0.8 grams azobisisobutyronitrile (AIBN) and 18.4 parts of poly(lauryl methacrylate-co-glycidyl methacrylate) in which 80% of the glycidyl groups had been reacted with methacrylic acid (mole ratio of LMA to GMA=19). The solution is heated to 85° C. for 45 minutes and then a solution of 0.8 part AIBN in 337.8 parts VAc is added over 3 hours while the mixture is held at 80°-85° C. The dispersion that results has a solid content of 52.4%, and a particle size of 0.47 micron. The PVAc in the dispersion has a molecular weight of 225,000 and a glass transition temperature of 37° C.
One hundred grams of this dispersion is mixed with 52.4 grams of the hydrogenated methyl ester of rosin (Hercolyn D) and the volatile hydrocarbons are removed by distillation under reduced pressure. The resulting dispersion of PVAc in resin is mixed with a dispersion of carbon black in the hydrogenated methyl ester of rosin plus ink varnish.
The final composition is:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate 100Hydrogenated methyl ester of rosin 180with a viscosity of 5800 cps.Ink varnish-pentaerythritol ester 60of dimerized rosin in liquid iso-phthalic alkyl resin in a weightratio of 1:2 and less than 0.1%volatility at 150° C.Carbon black 60______________________________________
The ink is printed on paper on a lithographic offset press. The printed sheets are passed at about 45 meters/minute under a 100 watt/cm infrared lamp with a peak output of about 1 micron (model 5193-5 line heater manufactured by Research Incorporated, Minneapolis, Minnesota, operated at 230 volts) at a distance of 2.5 cm from the lamp reflector edge which results in the rapid setting of the ink film. After setting, the ink is dry and resistant to smudging or smearing.
EXAMPLE 2
An ink is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - largely aromatic; 160based on petroleum and coal-derivedmonomers with a ring and ball soften-ing point of 10° C., and a numberaverage molecular weight below 5000.Ink varnish - phenolic-modified 100pentaerythritol ester of rosindissolved in alkali-refined linseedoil with a solubility parameter of about7.8 in a weight ratio of 40:60 and lessthan 0.1% volatility at 150° C.Carbon black 36______________________________________
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging or smearing.
EXAMPLE 3
An ink is prepared as in Example 1. The final formulation is:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - based principally 160on alpha-methyl styrene and styrene;ring and ball softening point 25° C.,and with a number average molecularweight below 5000.Extending oil - petroleum derived; 80solubility parameter about 7.8;less than 0.1% volatility at 150° C.Carbon black 34______________________________________
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 4
An ink is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - largely aliphatic; 160based on petroleum-derived monomerswith a ring and ball softening pointof 10° C. and a number average molecularweight below 5000.Extending oil - petroleum derived; 50solubility parameter about 7.8;less than 0.1% volatility at 150° C.Carbon black 31______________________________________
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 5
An ink was prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Methyl ester of rosin with a viscosity 160of about 2700 centipoise. -Ink varnish - phenolic-modified 40pentaerythritol ester of rosin dissolvedin alkali-refined linseed oil with asolubility parameter of about 7.8 in aweight ratio of 40:60 and less than 0.1%volatility at 150° C.Carbon black 30______________________________________
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smearing and smudging.
EXAMPLE 6
An ink is prepared as in Example 1 having the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - largely aromatic; 160based on petroleum- and coal-derivedmonomers with a ring and ball softeningpoint of 10° C. and a number averagemolecular weight below 5000.Ink varnish -phenolic-modified 100pentaerythritol ester of rosin dissolvedin long oil linseed isophthalic alkydin a weight ratio of 20:80 and less than -0.1% volatility at 150°C.Carbon black 40______________________________________
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 7
An ink is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin -largely aromatic, 80based on petroleum- and coal-derivedmonomers with a ring and ball softeningpoint of 10° C. and a number averagemolecular weight below 5000.Hydrocarbon resin- largely aromatic; 40based on petroleum- and coal-derivedmonomers; a ring and ball softeningpoint of 25° C.Radiant fluorescent chartreuse pigment 95(Hercules Incorporated)______________________________________
The ink is printed and set as described in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 8
An ink is prepared as in Example 1 having the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin -largely aromatic; 180based on petroleum- and coal-derivedmonomers with a ring and ball softeningpoint of 10° C. and a number averagemolecular weight below 5000.Extending oil - petroleum derived; 20solubility parameter about 7.8;less than 0.1% volatility at 150° C.Titanium dioxide 15______________________________________
The ink is screen printed onto glass and set by oven heating for 2 minutes at 135° C. The resulting film is dry and scratch resistant.
EXAMPLE 9
The ink of Example 1 is screen printed onto cotton fabric. The ink is set by IR radiation as in Example 1. The cotton fabric is laundered in an automatic washing machine with a detergent with no loss of image.
EXAMPLE 10
A paste is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 120Hydrocarbon resin - largely aromatic; 160based on petroleum- and coal-derivedmonomers with a ring and ball softeningpoint of 10° C. and a number averagemolecular weight below 5000.Ink varnish - phenolic-modified 100pentaerythritol ester of rosin dissolvedin alkali-refined linseed oil with asolubility parameter of about 7.8 in aratio of 40:60 and less than 0.1%volatility at 150° C.______________________________________
The paste is printed as an overprint varnish on a lithographic offset press. The printed sheets are heated to 200° C. for 2 minutes in a forced air oven. After setting, the coating is dry and smudge resistant.
EXAMPLE 11
A paste is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - largely aromatic; 100based on petroleum- and coal-derivedmonomers with a ring and ball softeningpoint of 10° C. and a number averagemolecular weight below 5000.Ink varnish - phenolic-modified 80pentaerythritol ester of rosin dissolvedin alkali-refined linseed oil with asolubility parameter of about 7.8 in aratio of 40:60 and less than 0.1%volatility at 150° C.Extending oil - petroleum derived; 20solubility parameter of about 7.8;less than 0.1% volatility at 150° C.Titanium dioxide 14______________________________________
The paste is roll-coated onto paper and heated by passing under an IR lamp, which results in rapid setting of the paste film. After setting, the coating is dry and resistant to smearing.
EXAMPLE 12
A paste is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrocarbon resin - largely aliphatic; 160based on petroleum-derived monomerswith a ring and ball softening point of10° C. and a number average molecularbelow 5000.______________________________________
The paste is blade-coated onto a Bonderite 100 treated cold rolled steel panel. The coated panel is heated for five minutes in a forced-air oven at 175° C. On cooling, the resulting coating is dry and rub-resistant.
EXAMPLE 13
The paste of Example 12 is doctored onto two pieces of bleached poplin. The coated fabrics are pressed together with an iron at 120° C. for under one minute. On cooling, a strong fabric-to-fabric bond results.
EXAMPLE 14
The paste of Example 12 is pressed into a metal mold which had previously been coated with a mold release. The filled mold is placed in an oven at 200° C. for 10 minutes. On cooling, the resulting molded object is removed from the mold and has accurately replicated the design of the mold cavity.
EXAMPLE 15
An ink is prepared as in Example 1 with the following formulation:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Resin-transesterification products of 160of 2-ethylhexanol with dimethylterephthalate process residue largelycomprising methyl and benzyl esters ofbiphenyldicarboxylic and tricarboxylicacids with a viscosity above 2000 centi-poise and a number average molecularweight below 5000.Carbon black 26______________________________________
The ink is printed on a lithographic press and on a Van der Cook proofing press and prints are set by passing under an IR lamp as described in Example 1. After setting, the ink is dry and smudge-resistant.
EXAMPLE 16
A fusible paste ink is prepared with the following composition:
______________________________________Ingredients Parts by Weight______________________________________Poly(vinyl acetate) 100Hydrogenated methyl ester of rosin 240with a viscosity of about 5500centipoisePhenolic-modified pentaerythritol 20ester of rosinCarbon black 40______________________________________
The ink is prepared by (1) dissolving the phenolicmodified pentaerythritol ester of rosin in the hydrogenated methyl ester of rosin; (2) dispersing the polystyrene in about two-thirds of the above solution on a three-roll mill; (3) dispersing the carbon black in the remaining one-third of the resin solution on a three-roll mill; and (4) blending the two dispersions together with a light mixing pass on a three-roll mill.
The ink is printed on a Little Joe press. Prints are set by placing in an oven at 150° C. for 90 seconds, in an oven at 200° C. for 30 seconds and on a curved hot plate at 288° C. for 3 seconds.
EXAMPLE 17
A paste is prepared as in Example 16 with the omission of the carbon black. The paste is used as an overprint varnish by printing on a sheet-fed lithographic press. The resulting clear coating is set by placing in an oven at 150° C. for 90 seconds.
EXAMPLE 18
Finely divided vinyl acetate-ethyl acetate copolymer is prepared exactly as described in Example 1 except that in place of the vinyl acetate there is used an 85:15 mixture of vinyl acetate and ethyl acrylate. The resulting dispersion contains 51.4% solids, and has a particle size of 0.45 micron. The polymer has a reduced specific viscosity of 1.32 determined in chloroform solution at 25° C., which indicates a molecular weight above 100,000, and has a second order transition temperature of 19° C.
To 100 parts of the above dispersion are added 51.4 parts of the hydrogenated methyl ester of rosin. After evaporation of volatile diluents, the resulting dispersion is mixed with a dispersion of carbon black in the hydrogenated methyl ester of rosin and ink varnish to give a composition identical to that of Example 1 except for substitution of the polymer component.
The ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging or smearing.
EXAMPLE 19
Finely divided vinyl acetate-ethyl acetate copolymer is prepared exactly as described in Example 1 except that in place of the 59.3 parts vinyl acetate there is used a 70:30 mixture of vinyl acetate and ethyl acrylate and the post-heating time at 85° C. is three hours. The resulting dispersion contains 50.8% solids and has a particle size of 0.44 micron. The polymer has a reduced specific viscosity of 1.24 which corresponds to a molecular weight above 100,000 and has a second order transition temperature of 6° C.
To 100 parts of the above dispersion is added 300 parts of the hydrogenated methyl ester of rosin in which is dispersed 50 parts of carbon black. After evaporation of volatile diluents, the resulting ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 20
Finely divided vinyl acetate-methyl methacrylate copolymer is prepared exactly as described in Example 1 except that in place of the vinyl acetate there is used a 75:25 mixture of vinyl acetate and methyl methacrylate and the heating temperature is maintained in the range of 75° to 85° C. After the postheating period, 60 parts of unreacted vinyl acetate is removed by evaporation with about 180 parts of the hydrocarbon solvent so that the ratio of the monomers in the polymer is about 68:32. The resulting dispersion has a solids content of 52.4% and the particle size of 0.41 micron. The reduced specific viscosity of the polymer is 1.54 which corresponds to a molecular weight of approximately 217,000. The polymer has a glass transition temperature of 38° C.
To 100 parts of the above dispersion is added 200 parts of the hydrogenated methyl ester of rosin in which is dispersed 25 parts of carbon black. After evaporation of the volatile diluents, the resulting ink is printed and set as in Example 1. After setting, the ink is dry and resistant to smudging and smearing.
EXAMPLE 21
Finely divided vinyl acetate-ethyl acrylate copolymer is prepared exactly as described in Example 1 except that in place of vinyl acetate there is used a 60:40 mixture of vinyl acetate and ethyl acrylate. The postheating time is extended to 2-1/2 hours at 80° C. followed by distillation to remove 66.5 parts of a mixture of unreacted monomer and solvent. The resulting dispersion contains 53.6% solids and has a particle size of 0.43 micron. The polymer has a reduced specific viscosity of 1.24 which indicates a molecular weight above 100,000 and has a glass transition temperature of 0° C.
100 parts of this dispersion is mixed with 52.4 parts of the hydrogenated methyl ester of rosin and the volatile hydrocarbons removed by distillation under reduced pressure. The resulting dispersion is mixed with a dispersion of carbon black in the hydrogenated methyl ester of rosin plus ink varnish.
The final composition is:
______________________________________Ingredients Parts by Weight______________________________________Vinyl acetate--ethyl acrylate 100copolymerHydrogenated methyl ester of rosin 180with a viscosity of 5800 cps.Ink varnish - pentaerythritol ester 60of dimerized rosin liquid iso-phthalic alkyl resin in a weightratio of 1:2 and less than 0.1%volatility at 150° C.Carbon black 60______________________________________
The ink is printed on paper on a lithographic offset press as described in Example 1. After setting, the ink is dry and resistant to smudging or smearing. | It has been discovered that pastes of particulate, thermoplastic, poly(vinyl acetate) type polymers dispersed in a soft resinous phase can be prepared which heat-set by fusion of the thermoplastic binder. When pigmented or otherwise colored, these formulations have utility as printing inks. When uncolored, they can be used as clear overprint coatings. In addition, these fusible pastes have utility as specialty coatings in adhesives and can be fabricated into self-supporting shapes. | 2 |
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